Effects of ammonia borane on the combustion of an ethanol droplet at atmospheric pressure

Adding compounds rich in hydrogen to liquid fuels has the potential to change combustion behavior and enhance performance. One potential additive is ammonia borane (AB), which contains 19.6 wt.% hydrogen and can be dissolved in anhydrous ethanol (up to 6.5 wt.%). The particular system studied here would have limited use due to energy density and stability but is studied as a model system. Single droplet combustion experiments were performed with AB concentrations in ethanol varying from 0 to 6 wt.%. Measurements performed using high speed (5 kHz) planar laser-induced fluorescence (PLIF) indicate that hydrogen gas addition from the decomposition of AB continues throughout the droplet burning process. The hydrogen addition leads to an increase in the D² law rate constant, k₀, of up to 16%. While AB (and residual material) participates throughout the combustion process, it dramatically impacts the combustion behavior at the end of the droplet lifetime as the concentration of AB residual grows within the droplet. This results in droplet shattering, causing fine atomization and rapid combustion of the remaining fuel. Boron is also oxidized in this short period of time, increasing the energy released. In combustors, droplet shattering could enhance mixing and increase combustion efficiency. Thus, the approach of adding compounds rich in hydrogen is a promising method to introduce H₂ gas to practical combustion systems, while enhancing performance.     

Effect of heat exchanger material and fouling on thermoelectric exhaust heat recovery

Thermoelectric devices are being investigated as a means of improving fuel economy for diesel and gasoline vehicles through the conversion of wasted fuel energy, in the form of heat, to useable electricity. By capturing a small portion of the energy that is available with thermoelectric devices can reduce engine loads thus decreasing pollutant emissions, fuel consumption, and CO₂ to further reduce green house gas emissions. This study is conducted in an effort to better understand and improve the performance of thermoelectric heat recovery systems for automotive use. For this purpose an experimental investigation of thermoelectrics in contact with clean and fouled heat exchangers of different materials is performed. The thermoelectric devices are tested on a bench-scale thermoelectric heat recovery apparatus that simulates automotive exhaust. It is observed that for higher exhaust gas flowrates, thermoelectric power output increases from 2 to 3.8 W while overall system efficiency decreases from 0.95% to 0.6%. Degradation of the effectiveness of the EGR-type heat exchangers over a period of driving is also simulated by exposing the heat exchangers to diesel engine exhaust under thermophoretic conditions to form a deposit layer. For the fouled EGR-type heat exchangers, power output and system efficiency is observed to be 5-10% lower for all conditions tested.     

Partial oxidation of ethanol in a membrane reactor for high purity hydrogen production

Partial oxidation of ethanol was performed in a dense Pd–Ag membrane reactor over Rh/Al₂O₃ catalyst in order to produce a pure or, at least, CO_x-free hydrogen stream for supplying a PEM fuel cell. The membrane reactor performances have been evaluated in terms of ethanol conversion, hydrogen yield, CO_x-free hydrogen recovery and gas selectivity working at 450 °C, GHSV ∼ 1300 h⁻¹, O₂:C₂H₅OH feed molar ratio varying between 0.33:1 and 0.62:1 and in a reaction pressure range from 1.0 to 3.0 bar. As a result, complete ethanol conversion was achieved in all the experimental tests. A small amount of C₂H₄ and C₂H₄O formation was observed during reaction. At low pressure and feed molar ratio, H₂ and CO are mainly produced, while at stronger operating conditions CH₄, CO₂ and H₂O are prevalent compounds. However, in all the experimental tests no carbon formation was detected. As best results of this work, complete ethanol conversion and more than 40.0% CO_x-free hydrogen recovery were achieved.     

Experimental study and chemical analysis of n-heptane homogeneous charge compression ignition combustion with port injection of reaction inhibitors

The control of ignition timing in the homogeneous charge compression ignition (HCCI) of n-heptane by port injection of reaction inhibitors was studied in a single-cylinder engine. Four suppression additives, methanol, ethanol, isopropanol, and methyl tert-butyl ether (MTBE), were used in the experiments. The effectiveness of inhibition of HCCI combustion with various additives was compared under the same equivalence ratio of total fuel and partial equivalence ratio of n-heptane. The experimental results show that the suppression effectiveness increases in the order MTBE < isopropanol ? ethanol < methanol. But ethanol is the best additive when the operating ranges, indicated thermal efficiency, and emissions are considered. For ethanol/n-heptane HCCI combustion, partial combustion may be observed when the mole ratio of ethanol to that of total fuel is larger than 0.20; misfires occur when the mole ratio of ethanol to that of total fuel larger than 0.25. Moreover, CO emissions strongly depend on the maximum combustion temperature, while HC emissions are mainly dominated by the mole ratio of ethanol to that of total fuel. To obtain chemical mechanistic informations relevant to the ignition behavior, detailed chemical kinetic analysis was conducted. The simulated results also confirmed the retarding of the ignition timing by ethanol addition. In addition, it can be found from the simulation that HCHO, CO, and C₂H₅OH could not be oxidized completely and are maintained at high levels if the partial combustion or misfire occurs (for example, for leaner fuel/air mixture).     

Ethanol electrooxidation on a carbon-supported Pt catalyst at elevated temperature and pressure: A high-temperature/high-pressure DEMS study

The electrooxidation of ethanol on a Pt/Vulcan catalyst was investigated in model studies by on-line differential electrochemical mass spectrometry (DEMS) over a wide range of reaction temperatures (23–100 °C). Potentiodynamic and potentiostatic measurements of the Faradaic current and the CO₂ formation rate, performed at 3 bar overpressure under well-defined transport and diffusion conditions reveal significant effects of temperature, potential and ethanol concentration on the total reaction activity and on the selectivity for the pathway toward complete oxidation to CO₂. The latter pathway increasingly prevails at higher temperature, lower concentration and lower potentials (∼90% current efficiency for CO₂ formation at 100 °C, 0.01 M, 0.48 V), while at higher ethanol concentrations (0.1 M), higher potentials or lower temperatures the current efficiency for CO₂ formation drops, reaching values of a few percent at room temperature. These trends result in a significantly higher apparent activation barrier for complete oxidation to CO₂ (68 ± 2 kJ mol⁻¹ at 0.48 V, 0.1 M) compared to that of the overall ethanol oxidation reaction determined from the Faradaic current (42 ± 2 kJ mol⁻¹ at 0.48 V, 0.1 M). The mechanistic implications of these results and the importance of relevant reaction and mass transport conditions in model studies for reaction predictions in fuel cell applications are discussed.     

Hydrogen production with CO2 capture by coupling steam reforming of methane and chemical-looping combustion: Use of an iron-based waste product as oxygen carrier burning a PSA tail gas

In this work it is analyzed the performance of an iron waste material as oxygen carrier for a chemical-looping combustion (CLC) system. CLC is a novel combustion technology with the benefit of inherent CO₂ separation that can be used as a source of energy for the methane steam reforming process (SR). The tail gas from the PSA unit is used as fuel in the CLC system.The oxygen carrier behaviour with respect to gas combustion was evaluated in a continuous 500 W_th CLC prototype using a simulated PSA off-gas stream as fuel. Methane or syngas as fuel were also studied for comparison purposes. The oxygen carrier showed enough high oxygen transport capacity and reactivity to fully convert syngas at 880 °C. However, lower conversion of the fuel was observed with methane containing fuels. An estimated solids inventory of 1600 kg MW_th⁻¹ would be necessary to fully convert the PSA off-gas to CO₂ and H₂O. An important positive effect of the oxygen carrier-to-fuel ratio up to 1.5 and the reactor temperature on the combustion efficiency was found.A characterization of the calcined and after-used particles was carried out showing that this iron-based material can be used as oxygen carrier in a CLC plant since particles maintain their properties (reactivity, no agglomeration, high durability, etc.) after more than 111 h of continuous operation.     

A two-step chemical scheme for kerosene-air premixed flames

A reduced two-step scheme (called 2S_KERO_BFER) for kerosene-air premixed flames is presented in the context of Large Eddy Simulation of reacting turbulent flows in industrial applications. The chemical mechanism is composed of two reactions corresponding to the fuel oxidation into CO and H₂O, and the CO − CO₂ equilibrium. To ensure the validity of the scheme for rich combustion, the pre-exponential constants of the two reactions are tabulated versus the local equivalence ratio. The fuel and oxidizer exponents are chosen to guarantee the correct dependence of laminar flame speed with pressure. Due to a lack of experimental results, the detailed mechanism of Dagaut composed of 209 species and 1673 reactions, and the skeletal mechanism of Luche composed of 91 species and 991 reactions have been used to validate the reduced scheme. Computations of one-dimensional laminar flames have been performed with the 2S_KERO_BFER scheme using the CANTERA and COSILAB softwares for a wide range of pressure ([1; 12] atm), fresh gas temperature ([300; 700] K), and equivalence ratio ([0.6; 2.0]). Results show that the flame speed is correctly predicted for the whole range of parameters, showing a maximum for stoichiometric flames, a decrease for rich combustion and a satisfactory pressure dependence. The burnt gas temperature and the dilution by Exhaust Gas Recirculation are also well reproduced. Moreover, the results for ignition delay time are in good agreement with the experiments.     

Autothermal reforming of JP8 on a Pt/Rh catalyst: Catalyst durability studies and effects of sulfur

Autothermal reforming (ATR) of commercial grade JP8 was performed on a Pt/Rh catalyst deposited on a monolith. This study investigated catalyst performance under three test conditions: (i) 120 startup and shutdown cycles, (ii) 80 h of continuous operation with sulfur-free fuel, and (iii) 370 h of testing with JP8 containing 125 ppm of sulfur. Axial reactor temperature profiles and gas composition data showed that startup and shutdown cycling had no impact on catalyst performance. When durability testing was done with fuel containing 125 ppm of sulfur, the catalyst deactivated initially, which was reflected by a decrease in H₂ concentration and decrease in fuel conversion. However, after 250 h of operation the activity stabilized at 66% fuel conversion and product concentrations were constant for the remaining 120 h of testing. The presence of sulfur resulted in higher CO selectivity, lower H₂ concentrations, and lower fuel conversions compared to data with sulfur-free fuel. The data suggests that the presence of sulfur primarily affects steam reforming reactions, and CO oxidation. Regeneration was attempted with air and with fuel-lean combustion but initial H₂ yields and carbon selectivity were not achieved.     

Experimental and numerical study of oxy‐methane flames in a porous‐plate reactor mimicking membrane reactor operation

The work investigates the reacting flow field, oxy‐methane flame characteristics and location, and the species distributions in a porous‐plate reactor mimicking the operation of oxygen transport membrane reactors (OTMRs). The study was performed experimentally and numerically considering ranges of operating equivalence ratio, from 0.5 to 1.0, and CO₂ concentrations in the total oxidizer flow (O₂ and CO₂), from 0% to 55% (by Vol). Oxygen was supplied through a slightly pressurized top and bottom chambers to cross the two porous plates to the central chamber, where a premixed mixture of CH₄ and CO₂ is introduced. ANSYS Fluent 17.1 software was used to solve for conservation and radiative transfer equations in the full three‐dimensional (3‐D) domain. The modified Westbrook‐Dryer (Oxy‐WD) two‐step reduced mechanism for oxy‐methane combustion was adapted for the calculations of chemical kinetics. The captured flame shapes using a high‐speed camera were compared with the calculated ones, and the results showed good agreements. At fixed equivalence ratio, elongated flames were obtained at higher CO₂ concentrations due to the increase in the mainstream Reynolds number and reduction in reaction rates, which delays the completeness of combustion. At fixed CO₂ concentration, the increase in equivalence ratio resulted in more compact and intense flames. The effective mixing and flame stability resulted in complete fuel conversion under stoichiometric condition. Stable flames were located between the two porous plates at reasonable distance. This perfect flame location prevents the thermal fracture of the membranes and improves their oxygen permeation flux, resulting in better combustion characteristics when the results are projected on the case of OTMRs. This implies efficient and safe applicability of the OTMRs by the condition that membranes can provide sufficient oxygen flux for complete combustion. A warm outer recirculation zone (ORZ) was created beside each porous plate, which helps anchoring the flame at the leading edge of the porous plate. The range of temperature within the ORZ was 800 to 1600 K, which lies in the operability limits of membranes for the case of OTMRs. The effective complete mixing and flame stability resulted in complete fuel conversion under stoichiometric condition. The temperature and species distributions within the reactor are presented in detail over wide ranges of operating conditions. The results recommended the reactor operation under stoichiometric combustion condition based on performance and economic points of views. The results are promising when projected on the application of the OTMRs under oxy‐combustion conditions for clean and efficient energy production.     

Energy balance and GHG-abatement cost of cassava utilization for fuel ethanol in Thailand

Since 2001, in order to enhance ethanol's cost competitiveness with gasoline, the Thai government has approved the exemption of excise tax imposed on ethanol, controlling the retail price of gasohol (a mixture of ethanol and gasoline at a ratio of 1:9) to be less than that of octane 95 gasoline, within a range not exceeding 1.5 baht a litre. The policy to promote ethanol for transport is being supported by its positive effects on energy security and climate change mitigation. An analysis of energy, greenhouse gas (GHG) balances and GHG abatement cost was done to evaluate fuel ethanol produced from cassava in Thailand. Positive energy balance of 22.4 MJ/L and net avoided GHG emission of 1.6 kg CO₂ eq./L found for cassava-based ethanol (CE) proved that it would be a good substitute for gasoline, effective in fossil energy saving and GHG reduction. With a GHG abatement cost of US$99 per tonne of CO₂, CE is rather less cost effective than the many other climate strategies relevant to Thailand in the short term. Opportunities for improvements are discussed to make CE a reasonable option for national climate policy.     

A high-performance no-chamber fuel cell operated on ethanol flame

A no-chamber solid-oxide fuel cell operated on a fuel-rich ethanol flame was reported. Heat produced from the combustion of ethanol thermally sustained the fuel cell at a temperature of 500–830 °C. Considerable amounts of hydrogen and carbon monoxide were also produced during the fuel-rich combustion which provided the direct fuels for the fuel cell. The location of the fuel cell with respect to the flame was found to have a significant effect on the fuel cell temperature and performance. The highest power density was achieved when the anode was exposed to the inner flame. By modifying the Ni + Sm_0.2Ce_0.8O_1.9 (SDC) anode with a thin Ru/SDC catalytic layer, the fuel cell envisaged not only an increase of the peak power density to ∼200 mW cm⁻² but also a significant improvement of the anodic coking resistance.     

Reduction of energy cost and CO2 emission for the furnace using energy recovered from waste tail-gas

In this research, the waste tail gas emitted from petrochemical processes, e.g. catalytic reforming unit, catalytic cracking unit and residue desulfurization unit, was recovered and reused as a replacement of natural gas (NG). On-site experimental results show that both the flame length and orange-yellowish brightness decrease with more proportion of waste gas fuel added to the natural gas, and that the adiabatic temperature of the mixed fuel is greater than 1800 °C. A complete replacement of natural gas by the recovered waste gas fuel will save 5.8 × 10⁶ m³ of natural gas consumption, and 3.5 × 10⁴ tons of CO₂ emission annually. In addition, the reduction of residual O₂ concentration in flue gases from 4% to 3% will save 1.1 × 10⁶ m³ of natural gas consumption, reduce 43.0% of NO_x emission, and 1.3 × 10³ tons of CO₂ emission annually. Thus, from the viewpoint of the overall economics and sustainable energy policy, recovering the waste tail gas energy as an independent fuel source to replace natural gas is of great importance for saving energy, reducing CO₂ emission reduction, and lowering environmental impact.     

Oxidative steam reforming of ethanol over Ru–Al2O3 catalyst in a dense Pd–Ag membrane reactor to produce hydrogen for PEM fuel cells

This study focuses on the influence of oxygen addition on ethanol steam reforming (ESR) reaction performed in a dense Pd–Ag membrane reactor (MR) for producing hydrogen directly available for feeding a polymer electrolyte membrane fuel cell (PEMFC). In particular, oxygen addition can prevent ethylene and ethane formation caused by dehydration of ethanol as well as carbon deposition. The MR is operated at 400 °C, H₂O:C₂H₅OH = 11:1 as feed molar ratio and space velocity (GHSV) ∼2000 h⁻¹. A commercial Ru-based catalyst was packed into the MR and a nitrogen stream of 8.4 × 10⁻² mol/h as sweep gas was flowed into the permeate side of the reactor. Both oxidative ethanol steam reforming (OESR) and ESR performances of the Pd–Ag MR were analyzed in terms of ethanol conversion to gas, hydrogen yield, gas selectivity and CO-free hydrogen recovery by varying O₂:C₂H₅OH feed molar ratio and reaction pressure. Moreover, the experimental results of the OESR and ESR reactions carried out in the same Pd–Ag MR are compared in order to point out the benefits due to the oxygen addition. Experimentally, this work points out that, overcoming O₂:C₂H₅OH = 1.3:1, ethanol conversion is lowered with a consequent drops of both hydrogen yield and hydrogen recovery. Vice versa, a complete ethanol conversion is achieved at 2.5 bar and O₂:C₂H₅OH = 1.3:1, whereas the maximum CO-free hydrogen recovery (∼30%) is obtained at O₂:C₂H₅OH = 0.6:1.     

Efficient electrochemical oxidation of ethanol to carbon dioxide in a fuel cell at ambient temperature

A carbon dioxide monitor has been used to follow the Faradaic yield of CO₂ from the oxidation of ethanol vapour in a direct ethanol PEM fuel cell at ambient temperature. The time resolution of the CO₂ measurements (ca.15 s at half height for a burst of CO₂) was sufficient to observe stripping of adsorbed CO from the anode, and to monitor CO₂ yields as a function of time during linear sweep and pulse experiments. It has been demonstrated that CO₂ yields can be increased dramatically by pulsing the potential or current such that adsorbed CO is stripped from the electrode and then ethanol is allowed to readsorb. Yields of CO₂ as high as 80% have been sustained for as long as 50 s under current pulsing conditions. An average CO₂ yield of 45% was obtained during 600 s of pulsing the current between 0 and 4 mA cm⁻² at 1 Hz.     

Numerical analysis of the influence of two-phase flow mass and heat transfer on n-heptane autoignition

This paper investigates the influence of liquid fuel presence on the autoignition of n-heptane/air mixtures over a wide range of conditions encountered in internal combustion engines. To this end, evaporating droplet physics and skeletal chemistry mechanisms are simultaneously solved considering a homogeneous constant-pressure reactor. A skeletal mechanism is introduced to account for specific kinetics behavior in the Negative Temperature Coefficient (NTC) region. The impact of mass and heat source terms during evaporation is emphasized by comparing a two-phase flow scenario with a purely gaseous case. The competition between fuel vapor availability and the evaporation-induced gas temperature decrease is specific to two-phase flow autoignition. On the one hand, droplet evaporation delay restricts the gaseous local fuel/air equivalence ratio and consequently the kinetics runaway. On the other hand, temperature reduction due to evaporation may either reduce or enhance chemical reactivity, depending on the local thermodynamic conditions lying either inside or outside the NTC region. By simultaneously accounting for evaporation source terms and skeletal chemistry, we can reproduce the already experimentally observed transformation of the NTC region into a Zero Temperature Coefficient (ZTC) region depending on thermodynamic conditions and droplet size. The ZTC phenomenon appears when combustion heat-release starts before complete droplet evaporation. Since the ZTC behavior can be captured using the point source approach, in which droplets are considered only as zero-dimensional source terms of mass and energy, the present results pave the way for future exploration of NTC chemistry in sprays with a direct numerical simulation of discrete particles considering detailed chemistry and turbulent flows.     

Pressurization effect on dry reforming of biogas in kilohertz spark-discharge plasma

To produce high-concentration syngas (CO + H₂) from biogas, the effect of pressurization on dry reforming of biogas (CH₄/CO₂ = 60%/40%) in kilohertz spark-discharge plasma was reported for the first time by elevating the pressure from 1 bar to 2 bar. It was found that elevating the pressure could not only increase the reactant conversions, but also reduce energy cost and increase fuel-production efficiency at the same specific energy input (SEI). In particular, pressurization exhibited a significantly positive effect on increasing CO₂ conversion and decreasing energy cost for converting CO₂. Syngas concentration as high as 83% (H₂/CO = 1.4) was achieved with a ratio of the flow rates of product gas (dry basis) to feeding gas, 1.7, at 2 bar and SEI = 753 kJ/mol. The by-product, H₂O, was produced with only about 5% of hydrogen-based selectivity in this work. At 2 bar, the effect of SEI was investigated by varying the power and flow rate, respectively. Compared with those at 1 bar, with the increase in SEI, reactants conversion increased fast, energy cost rose slowly and fuel-production efficiency decreased slowly at 2 bar.     

Catalytic combustion of 1-butanol coupled with heat harvesting for compact power

A combustor paired with a heat-harvesting device, such as a thermoelectric or thermal photovoltaic device, can utilize high energy-dense liquid fuels while avoiding direct chemical-to-electrical conversion issues such as electrode and electrolyte poisoning. Therefore, the system is an attractive alternative to batteries and fuel cells for portable power applications. In the current study, a 1-butanol fed catalytic combustor using a Rh/Al₂O₃ catalyst was tested with a heat extractor, in this case being a stainless steel rod with a copper heat sink that was designed to thermally mimic a small thermoelectric module. The effects of residence time, fuel flow rate, and rod size on reactor/extractor temperatures and the energy balance were observed. Fuel-lean equivalence ratios were also studied and shown to have little effect on performance. Residence time does not have a direct effect; however, it does provide a catalytic stability limit for the fuel flow rate. The difference in the hot and cold side temperatures of the rod is dependent on the fuel flow rate and length of the rod. The greatest difference observed in these temperatures was 513 °C using the long-sized (15 cm) rod. The percentage of fuel energy conducted through the rod is only dependent on the rod size, with a maximum around 40% using the short rod. These results provide important design guidelines for the catalytic combustion of energy-dense liquid fuels as an excellent alternative heat source for either direct use or electrical power conversion.     

A climate protection strategy for Germany—40% reduction of CO2 emissions by 2020 compared to 1990

This paper presents measures and instruments for Germany to achieve the goal of 40% CO₂-emission reduction until 2020 by reducing energy-related emissions by 224 million tonne (Mt). The most important measures in this regard are cuts in electricity generation (savings of 40 Mt), fuel switching and increased energy conversion efficiency (30 Mt) and an augmented 26% share of renewable energies in the provision of electrical energy (44 Mt). Average cost of the measures are at 50 euro per tonne avoided CO₂, which corresponds to an additional monthly expenditure per household of less than 25 euro.     

Multi-objective optimization of cassava-based fuel ethanol used as an alternative automotive fuel in Guangxi,China

Multi-objective optimization of net energy, external costs of environment pollutant-emissions, and cost of using cassava-based fuel ethanol as an alternative automotive fuel in Guangxi has been conducted based on its holistic life cycle, from feedstock production to fuel combustion. A new indicator, cost of net energy (CNE), linking net energy-yield, external cost of environment pollutant-emissions, and production cost (the lower the CNE reading, the better the total performance) of ethanol–gasoline blends, is proposed for carrying out multi-objective optimization. On the life-cycle basis, CNE of ethanol–gasoline blends is found to obtain its lowest value, i.e. 0.119  RMB/MJ, when processing fuel during the ethanol conversion stage was natural gas and the ratio of ethanol blended with gasoline was 5%. From the standpoint of the CNE indicator, the most viable implement form of cassava-based fuel ethanol should be used as one of oxygenate additives. The recommended processing fuel during ethanol conversion stage should be natural gas.     

Cost-effective CO2 emission reduction through heat,power and biofuel production from woody biomass: A spatially explicit comparison of conversion technologies

Bioenergy is regarded as cost-effective option to reduce CO₂ emissions from fossil fuel combustion. Among newly developed biomass conversion technologies are biomass integrated gas combined cycle plants (BIGCC) as well as ethanol and methanol production based on woody biomass feedstock. Furthermore, bioenergy systems with carbon capture and storage (BECS) may allow negative CO₂ emissions in the future. It is still not clear which woody biomass conversion technology reduces fossil CO₂ emissions at least costs. This article presents a spatial explicit optimization model that assesses new biomass conversion technologies for fuel, heat and power production and compares them with woody pellets for heat production in Austria. The spatial distributions of biomass supply and energy demand have significant impact on the total supply costs of alternative bioenergy systems and are therefore included in the modeling process. Many model parameters that describe new bioenergy technologies are uncertain, because some of the technologies are not commercially developed yet. Monte-Carlo simulations are used to analyze model parameter uncertainty. Model results show that heat production with pellets is to be preferred over BIGCC at low carbon prices while BECS is cost-effective to reduce CO₂ emissions at higher carbon prices. Fuel production – methanol as well as ethanol – reduces less CO₂ emissions and is therefore less cost-effective in reducing CO₂ emissions.