Source of methane and methods to control its formation in single chamber microbial electrolysis cells

Methane production occurs during hydrogen gas generation in microbial electrolysis cells (MECs), particularly when single chamber systems are used which do not keep gases, generated at the cathode, separate from the anode. Few studies have examined the factors contributing to methane gas generation or the main pathway in MECs. It is shown here that methane generation is primarily associated with current generation and hydrogenotrophic methanogenesis and not substrate (acetate). Little methane gas was generated in the initial reaction time (<12 h) in a fed batch MEC when acetate concentrations were high. Most methane was produced at the end of a batch cycle when hydrogen and carbon dioxide gases were present at the greatest concentrations. Increasing the cycle time from 24 to 72 h resulted in complete consumption of hydrogen gas in the headspace (applied voltage of 0.7 V) with methane production. High applied voltages reduced methane production. Little methane (<4%) accumulated in the gas phase at an applied voltage of 0.6–0.9 V over a typical 24 h cycle. However, when the applied voltage was decreased to 0.4 V, there was a greater production of methane than hydrogen gas due to low current densities and long cycle times. The lack of significant hydrogen production from acetate was also supported by Coulombic efficiencies that were all around 90%, indicating electron flow was not altered by changes in methane production. These results demonstrate that methane production in single chamber MECs is primarily associated with current generation and hydrogen gas production, and not acetoclastic methanogenesis. Methane generation will therefore be difficult to control in mixed culture MECs that produce high concentrations of hydrogen gas. By keeping cycle times short, and using higher applied voltages (≥0.6 V), it is possible to reduce methane gas concentrations (<4%) but not eliminate methanogenesis in MECs.     

Reduction time effect on structure and performance of Ni–Co/MgO catalyst for carbon dioxide reforming of methane

Reducing catalysts with hydrogen is an important process for carbon dioxide reforming methane since metallic active sites are exposed and dispersed during the reduction process. In this work, Ni–Co/MgO catalysts were prepared for syngas production by using a multiple-impregnation method with a carbon dioxide reforming methane reaction. Activity evaluation showed that catalysts that reduced for 1 h exhibited superior catalytic activity with methane and carbon dioxide conversion at 92% and 97%, respectively, and the syngas ratio close to unity (0.98). The high activity is ascribed to the better metal dispersion (10.5%) and smaller active metal particle size (10 nm). Raman spectra analysis indicated that catalysts that reduced for a longer time possessed larger active metal particle size, and were more susceptible to the formation of graphite-like carbon deposits, which were difficult to be removed by the active oxygen species derived from carbon dioxide dissociation.     

Calcium looping gasification for high-concentration hydrogen production with CO2 capture in a novel compact fluidized bed: Simulation and operation requirements

The coal/CaO/steam gasification system is one of the clean coal technologies being developed for hydrogen production with inherent carbon dioxide separation. A novel reactor configuration for the system is proposed in this paper. It consists of three major counterparts: a gasifier, a riser and a regenerator. A regenerable calcium-based sorbent CaO is used to remove carbon dioxide. In the gasifier, the coal-steam gasification reaction occurs with in situ carbon dioxide removal by carbonation reaction. The removal of carbon dioxide favors the gasification and water-shift reaction equilibrium and enables the production of a hydrogen-rich gas stream. CaO is regenerated in the regenerator by burning the unreacted char with oxygen, and a pure stream of carbon dioxide is separated after a cyclone. The regenerated CaO then flows into the riser above the gasifier, and removes the carbon dioxide in the outlet gases from the gasifier and drives the water-gas shift reaction forward, further improving the hydrogen purity. In this work, the feasibility and optimum process conditions of the proposed system were described. The hydrogen purity can reach 96 vol% at a steam flow 80 mol/s and CaO recycle rate 30 mol/s when the carbon conversion rate is 0.50. Increasing the steam flow and CaO recycle rate can enhance the hydrogen yield and purity. With the rise of operation pressure from 1 bar to 10 bar, the hydrogen yield and purity decrease and methane yield increases. High pressure leads to higher calcination temperature. At 10 bar, the temperature for CaCO₃ decomposition is approximately 1100 °C, at such temperature, the sorbent is easy to deactivate. The appropriate temperatures in the gasifier and the riser are 700 and 600 °C, respectively. An analysis of heat integration is conducted. The maximum carbon conversion rate is ∼0.65. A hydrogen production efficiency of 58.5% is obtained at a carbon conversion rate 0.50, steam flow 60 mol/s and CaO recycle rate 30 mol/s, with a hydrogen purity of 93.7 vol%.     

Modeling & optimization of renewable hydrogen production from biomass via anaerobic digestion & dry reformation

There is a growing interest in the usage of hydrogen as an environmentally cleaner form of energy for end users. However, hydrogen does not occur naturally and needs to be produced through energy intensive processes, such as steam reformation. In order to be truly renewable, hydrogen must be produced through processes that do not lead to direct or indirect carbon dioxide emissions. Dry reformation of methane is a route that consumes carbon dioxide to produce hydrogen. This work describes the production of hydrogen from biomass via anaerobic digestion of waste biomass and dry reformation of biogas. This process consumes carbon dioxide instead of releasing it and uses only renewable feed materials for hydrogen production. An end-to-end simulation of this process is developed primarily using Aspen HYSYS® and consists of steady state models for anaerobic digestion of biomass, dry reformation of biogas in a fixed-bed catalytic reactor containing Ni–Co/Al₂O₃ catalyst, and a custom-model for hydrogen separation using a hollow fibre membrane separator. A mixture-process variable design is used to simultaneously optimize feed composition and process conditions for the process. It is identified that if biogas containing 52 mol% methane, 38 mol% carbon dioxide, and 10 mol% water (or steam) is used for hydrogen production by dry reformation at a temperature of 837.5 °C and a pressure of 101.3 kPa; optimal values of 89.9% methane conversion, 99.99% carbon dioxide conversion and hydrogen selectivity 1.21 can be obtained.     

A modified steam-methane-reformation reaction for hydrogen production

Hydrogen is mostly produced by the Steam Methane Reforming (SMR) reaction which adds many tonnes of carbon emissions to the environment for each tonne of hydrogen. A modified scheme for carbon-emission free production of hydrogen, which involves sodium hydroxide, methane and steam, has been explored here. The modification of the SMR reaction isCH₄ + 2NaOH + H₂O = Na₂CO₃ + 4H₂The modified reaction has several advantages: it does not require catalysis, the temperature of reaction is considerably reduced and the products are industrially important. By this process, we can produce hydrogen without any carbon dioxide emission as shown in this theoretical and experimental study. The reaction has been studied in the temperature range of 873-1073 K in an open configuration for 30 min and at various methane and constant water vapor flow. It is determined that at a methane flow rate of 25 ml/min the reaction is 98% complete at 873 K.     

One step methane production based on catalytic pressurized calcium looping gasification with in-situ CO2 capture and self-sustained heat supply

Catalytic steam hydrogasification of coal is a direct method for methane production. Calcium looping concept is usually used in coal gasification process for in-situ carbon dioxide removal and heat supply. In this paper, a new process combining catalytic steam hydrogasification and calcium looping was proposed and investigated using a self designed instantaneously feeding reactor under high-temperature and pressurized conditions. The effects of operation conditions (including hydrogen concentration with a range of 0–50 vol%, gasification pressure with a range of 0.1–3.5 MPa, gasification temperature with a range of 700–800 °C, and gasification-calcination cycle number up to six) on the performance of the new process have been studied. The results show that: (i) increasing H₂ concentration is beneficial to methane products; (ii) high temperature and low pressure are not conducive to methane production and carbon dioxide capture as well as the self-sustained heat supply in gasifier; (iii) the methane content and carbon conversion can be maintained at 30–40 vol% and 75–80% for the durability tests. According to the performance of gas products, 750 °C 3.5 MPa and Ca/C = 0.5 are suggested for the new process. In addition, the gasification reactivity can be affected by the Ca–K-Char interaction as indicated by the XRD, FT-IR and SEM-EDX analysis.     

A strategy of mid-temperature natural gas based chemical looping reforming for hydrogen production

Steam methane reforming (SMR) needs the reaction heat at a temperature above 800 °C provided by the combustion of natural gas and suffers from adverse environmental impact and the hydrogen separated from other chemicals needs extra energy penalty. In order to avoid the expensive cost and high power consumption caused by capturing CO₂ after combustion in SMR, natural gas Chemical Looping Reforming (CLR) is proposed, where the chemical looping combustion of metal oxides replaced the direct combustion of NG to convert natural gas to hydrogen and carbon dioxide. Although CO₂ can be separated with less energy penalty when combustion, CLR still require higher temperature heat for the hydrogen production and cause the poor sintering of oxygen carriers (OC). Here, we report a high-rate hydrogen production and low-energy penalty of strategy by natural gas chemical-looping process with both metallic oxide reduction and metal oxidation coupled with steam. Fe₃O₄ is employed as an oxygen carrier. Different from the common chemical looping reforming, the double side reactions of both the reduction and oxidization enable to provide the hydrogen in the range of 500–600 °C under the atmospheric pressure. Furthermore, the CO₂ is absorbed and captured with reduction reaction simultaneously.Through the thermodynamic analysis and irreversibility analysis of hydrogen production by natural gas via chemical looping reforming at atmospheric pressure, we provide a possibility of hydrogen production from methane at moderate temperature. The reported results in this paper should be viewed as optimistic due to several idealized assumptions: Considering that the chemical looping reaction is carried out at the equilibrium temperature of 500 °C, and complete CO₂ capture can be achieved. It is assumed that the unreacted methane and hydrogen are completely separated by physical adsorption. This paper may have the potential of saving the natural gas consumption required to produce 1 m³ H₂ and reducing the cost of hydrogen production.     

Coke-resistance over Rh–Ni bimetallic catalyst for low temperature dry reforming of methane

Methane and carbon dioxide can be converted into syngas using the prospective dry reforming of methane technology. Carbon deposition is a major cause of catalyst deactivation in this reaction, especially at low temperature. The superior stability of bimetallic catalysts has made their development more and more appealing. Herein, a series of bimetallic RhNi supported on MgAl₂O₄ catalysts were synthesized and used for low temperature biogas dry reforming. The results demonstrate that the bimetallic RhNi catalyst can convert CH₄ and CO₂ by up to 43% and 52% over at low reaction temperature (600 °C). Moreover, the reaction rate of CH₄ and CO₂ of RhNi–MgAl₂O₄ remains stable during the 20 h long time stability test, most importantly, there was no obviously carbon deposition observed over the spent catalyst. The enhanced coking resistance should be attributed to the addition of a little amount of noble metal Rh can efficiently suppress dissociation of CH_X1 species into carbon, and the high surface areas of MgAl₂O₄ support can also promote the adsorption and activation of carbon dioxide to generate more O1 species. Balancing the rate of methane dissociation and carbon dioxide activation to inhibit the development of carbon deposition is a good strategy, which provides a guidance for design other high performance dry reforming of methane catalysts.     

Effects of hydrogen and carbon dioxide on the laminar burning velocities of methane–air mixtures

The effects of different mole fractions of hydrogen and carbon dioxide on the combustion characteristics of a premixed methane–air mixture are experimentally and numerically investigated. The laminar burning velocity of hydrogen-methane-carbon dioxide-air mixture was measured using the spherically expanding flame method at the initial temperature and pressure of 283 K and 0.1 MPa, respectively. Additionally, numerical analysis is conducted under steady 1D laminar flow conditions to investigate the adiabatic flame temperature, dominant elementary reactions, and NO formation. The measured velocities correspond with those estimated numerically. The results show that increasing the carbon dioxide mole fraction decreases the laminar burning velocity, attributed to the carbon dioxide dilution, which decreases the thermal diffusivity and flame temperature. Conversely, the velocity increases with the thermal diffusivity as the hydrogen mole fraction increases. Moreover, the hydrogen addition leads to chain-branching reactions that produce active H, O, and OH radicals via the oxidation of hydrocarbons, which is the rate-determining reaction. Furthermore, an increase in the mole fractions of hydrogen and carbon dioxide decreases the NO production amount.     

A thermodynamic study of propanol reforming in presence of hydrazine for hydrogen production

Thermodynamic analysis of hydrogen production from propanol reforming reactions, by decomposition and steam reforming, in presence of hydrazine was evaluated as a function of temperature (300–900 K) at a constant pressure of 1 atm. The molar ratio of reactants were varied to identify the conditions leading to hydrogen rich product stream with low carbon formation. Steam reforming of propanol displayed higher hydrogen production and a gradual decrease in carbon content with an increase in the steam/propanol ratio. Addition of hydrazine leads to a further enhancement in hydrogen amount along with a suppression in coking. A similar trend was observed in case of propanol decomposition reaction. Addition of hydrazine leads to a favorable condition for hydrogen production along with a decrease in carbon formation. In both, steam reforming and decomposition, methane and water seem to be the stable products at low temperature, which react together at elevated temperatures following steam reforming of methane to generate CO and hydrogen. Hydrazine, on the other hand diminishes carbon at low temperature and produces ammonia, which decomposes at higher temperature to generate hydrogen and nitrogen. It is clear that steam assists in eliminating carbon at higher temperature whereas hydrazine is helpful in removing carbon formation at lower temperature. Also, a considerably high ratio of H₂/CO can be maintained in both the reactions, propanol steam reforming and propanol decomposition, by introducing a hydrazine stream in the feed.     

Insights into the hydrogen generation from water-iron rock reactions at low temperature and the key limiting factors in the process

Hydrogen generation from water-rock reactions is mostly studied at high temperature. This study investigated the process at low temperature (5–20 °C) using both synthetic and natural iron minerals (magnetite, goethite and hematite) for a better understanding about the reaction pathway and the key factors involved. Maximum hydrogen generation detected was 6.8 μmol/g with natural goethite. Characterization of the minerals by X-ray diffraction (XRD), X-ray fluorescence (XRF), Scanning electron microscopy (SEM), Energy dispersive spectroscopy (EDS) and aqueous phase by Inductively coupled plasma atomic emission spectrometer (ICP-AES) and ferrozine spectrophotometry revealed hydrogen generation to be related to the composition and specific surface area of the minerals. Low concentration of methane (200 nmol/g from natural magnetite) was also detected from natural minerals, which indicated catalytic effects. The study is significant for hydrogen generation at low temperature and yield insights on fate of carbon dioxide in the underground reservoirs and a sustainable environment.     

Hydrogen and syngas production from propane and polyethylene

Hybrid filtration combustion of propane in a porous medium composed of aleatory polyethylene pellets and alumina spheres is studied to examine the suitability of the concept for hydrogen and syngas production. Temperature, velocity, and chemical products of the combustion waves were recorded experimentally in the range of equivalence ratios from stoichiometry (φ = 1.0) to φ = 1.65. The model predictions for combustion in inert porous media using GRI 3.0 reaction mechanism are in good qualitative agreement with experimental data. Hydrogen, carbon monoxide, methane and carbon dioxide are dominant combustion products for upstream sub-adiabatic temperatures recorder in all the range of equivalence ratios studied. The maximum hydrogen and carbon monoxide yields are close to 48% and 89%, respectively.     

Progress of hydrogen gas generation by reaction between iron and steel powder and carbonate water in the temperature range near room temperature

Hydrogen gas generation from water in the temperature range of 10–60 °C using iron and carbon dioxide was studied. During the reaction, carbon dioxide consumption and hydrogen generation were observed, and the stoichiometry of the redox reaction with iron carbonation was checked. The rate of the reaction steadily increased with the temperature, and the time required to consume half of the carbon dioxide at 60 °C was less than one-fifth of that at 10 °C. The activation energy was determined by examining the temperature dependence of the reaction rate. Carbon dioxide used in the reaction precipitated as carbonate in the aqueous phase, covering the raw material iron and hindering the progress of hydrogen generation reaction. Experiments following the same procedure were performed using steel and sludge from steel processing, which contained elements other than iron, to show that hydrogen generation and carbon dioxide fixation were also possible.     

Hydrogen production from carbon dioxide reforming of methane over Ni-Co/MgO-ZrO2 catalyst: Process optimization

Greenhouse gases, carbon dioxide and methane are utilized in the production of hydrogen through carbon dioxide reforming of methane catalyzed by Ni-Co/MgO-ZrO₂ catalyst. Design of Experiments (DOE) was used to study the effects of process variables such as, carbon dioxide to methane ratios (1-5), gas hourly space velocity (8400-200,000 mL/g/h), oxygen concentration in the feed (3-8 mol%) and reaction temperature (700-800 °C) over methane conversion and yield of hydrogen. The ANOVA analysis indicated that the effect of each process variable was significant to its respective responses in the proposed quadratic model. The response surface methodology (RSM) was used to find the optimum value of the process variables by maximizing the hydrogen yield in the process model. The optimum space velocity as 145,190 mL/g/h at reaction temperature 749 °C with carbon dioxide to methane ratio of 3 and 7 mol% of oxygen in the feed gave 88 mol% of CH₄ conversion and 86 mol% of hydrogen yield, respectively. The experiments were run at the optimum condition gave 87.7 mol% methane conversion and 85.5 mol% of hydrogen yield, which were in good agreement with the simulated values obtained from the model. The catalyst stability and its regeneration characteristics were studied at the optimum condition by monitoring methane conversion and hydrogen yield with time on stream.     

Influence of process parameters on direct solar-thermal hydrogen and graphite production via methane pyrolysis

Current hydrogen and carbon production technologies emit massive amounts of CO₂ that threaten Earth's climate stability. Here, a new solar-thermal methane pyrolysis process involving flow through a fibrous carbon medium to produce hydrogen gas and high-value graphitic carbon product is presented and experimentally quantified. A 10 kW_e solar simulator is used to instigate the methane decomposition reaction with direct irradiation in a custom solar reactor. From localized solar heating of fibrous medium, the process reaches steady-state thermal and chemical operation from room temperature within the first minute of irradiation. Additionally, no measurable carbon deposition occurs outside the fibrous medium, leaving the graphitic product in a form readily extractable from the solar reactor. Parametric variations of methane inlet flow rate (10–2000 sccm), solar power (0.92–2.49 kW) and peak flux (1.3–3.5 MW/m²), operating pressure (1.33–40 kPa), and medium thickness (0.36–9.6 mm) are presented, with methane conversion varying from 22% to 96%.     

Cu–Zn–Al based catalysts for low temperature bioethanol steam reforming by solar energy

Bioethanol steam reforming is one of the most promising route to produce hydrogen from a renewable liquid biofuel. Activity of two Cu–Zn–Al based catalysts was investigated at low temperatures, ranging from 420 to 500 °C, in view of temperature limitations associated with solar energy supply by parabolic trough technology. At 450 °C the space velocity effect was also investigated, by varying the weight hourly space velocity (WHSV) from 1.67 to 3.32 h⁻¹. In each experimental conditions, together with the expected hydrogen and carbon dioxide, also methane, ethylene, acetaldehyde and diethylether were detect as products, so indicating the presence of several parallel reaction pathways. A good selectivity to ethanol reforming was obtained only at 500 °C (with values of the H₂/CO₂ mol ratio of 3.4 and 4.5) with both catalysts, while at lower temperatures alcohol dehydration into acetaldehyde seemed to be the main reaction.     

Natural Fe-based catalysts for the production of hydrogen and carbon nanomaterials via methane decomposition

Tierga and Ilmenite Fe-based ores are studied for the first time in the catalytic decomposition of methane (CDM) for the production of carbon dioxide-free hydrogen and carbon nanomaterials. Tierga exhibits superior catalytic performance at 800 °C. The effect of the reaction temperature, space velocity and reducing atmosphere in the catalytic decomposition of methane is evaluated using Tierga. The highest stability and activity (70 vol% hydrogen concentration) is obtained at 850 °C using methane as a reducing agent. Reduction with methane causes the fragmentation of the iron active phase and inhibits the formation of iron carbide, improving its activity and stability in the CDM. Hybrid nanomaterials composed of graphite sheets and carbon nanotubes with a high degree of graphitization are obtained. Considering its catalytic activity, the carbon quality, and the low cost of the material, Tierga has a competitive performance against synthetic iron-catalysts for carbon dioxide-free hydrogen and solid carbon generation.     

Kinetic model of homogeneous thermal decomposition of methane and ethane

In this paper, the homogeneous decomposition of methane and ethane is modeled in a well stirred flow reactor. The kinetics of this process is represented by a reaction mechanism of 242 reactions and 75 species, based on a mechanism developed for hydrocarbon combustion and soot formation. It is shown that this model correctly predicts the hydrogen yield from pyrolysis in a temperature range of 600–1600 °C, and pressure range of 0.1–10 atm. Furthermore, the effect of temperature, pressure and residence time on the amount of hydrogen produced from the decomposition of methane, ethane, natural gas, and a mixture of methane and argon is studied. The model predicts that the use of ethane or its addition to methane increases the speed of hydrogen production at low temperatures and pressures. The addition of a noble gas like argon also increases the yield of hydrogen at high pressures.     

NO emission from non-premixed MILD combustion of biogas-syngas mixtures in opposed jet configuration

In this paper NO emission from MILD combustion of the mixture biogas-syngas is deeply elucidated, five NO routes were considered, specifically: thermal, prompt, NNH, N₂O and reburning. Several operating conditions are studied namely: fuel mixture composition, oxygen concentration in the oxidizer and injection velocity or strain rate. Biogas is modeled by a mixture of methane and carbon dioxide; while, syngas is considered to be composed by hydrogen and carbon monoxide, this gives a fuel mixture of CH₄/CO₂/H₂/CO. Volume of methane and hydrogen are varied alternatively from 0 to 50% in fuel mixture. Oxidizer is composed by O₂/N₂ mixture where oxygen volume is increased from 4 to 21%. Finally, injection strain rate is varied from apparition to vanishment of combustion. Atmospheric pressure is considered with constant fuel and oxidizer injection temperatures of 300 K and 1200 K respectively. Chemical kinetics of such complicated system is handled by a composed mechanism from the USC C₁–C₄ and the Gri 2.11 N-sub mechanism. It is found that under MILD regime, temperature intervals and levels are enhanced by hydrogen compared to methane. Furthermore, temperature levels keep relatively low which guarantees MILD regime. Contrariwise, when oxygen increases in oxidizer, temperature grows up rapidly and the MILD regime disappears. However, if strain rate augments, temperature shows a steep increase then reduces monotonically. It is observed that for low methane volume in the fuel mixture, NNH route dominates NO production. Whereas, when CH₄ increases, the prompt route is enhanced and exceeds NNH one at a methane volume of 12%. When hydrogen increases, prompt and NNH routes are enhanced with a domination of the prompt route until 44% of hydrogen volume. Oxygen increasing in the oxidizer improves thermal mechanism which surpasses prompt one at 17% of oxygen volume and governs NO production. Globally, the third most important route in NO production is the reburning one which is enhanced by all parameters except strain rate.     

Ni/Ce-MCM-41 mesostructured catalysts for simultaneous production of hydrogen and nanocarbon via methane decomposition

For the first time, simultaneous production of hydrogen and nanocarbon via catalytic decomposition of methane over Ni-loaded mesoporous Ce-MCM-41 catalysts was investigated. The catalytic performance of the Ni/Ce-MCM-41 catalysts is very stable and the reaction activity remained almost unchanged during 1400 min steam on time at temperatures 540, 560 and 580 °C, respectively. The methane conversion level over these catalysts reached 60–75% with a 100% selectivity towards hydrogen. TEM observations revealed that most of the Ni particles located on the tip of the carbon nanofibers/nanotubes in the used catalysts, keeping their exposed surface clean during the test and thus remaining active for continuous reaction without obvious deactivation. Two kinds of carbon materials, graphitic carbon (C_g) as major and amorphous carbon (C_A) as minor were produced in the reaction, as confirmed by XRD analysis and TEM observations. Carbon nanofibers/nanotubes had an average diameter of approximately 30–50 nm and tens micrometers in length, depending on the reaction temperature, reaction time and Ni particle diameter. Four types of carbon nanofibers/nanotubes were detected and their formations greatly depend on the reaction temperature, time on steam and degree of the interaction between the metallic Ni and support. The respective mechanisms of the formation of nanocarbons were postulated and discussed.