Dry and steam reforming of biomass pyrolysis gas for rich hydrogen gas

Biomass pyrolysis gas (including H₂, CO, CH₄, CO₂, C₂H₄, C₂H₆ and etc.) reforming for hydrogen production over Ni/Fe/Ce/Al₂O₃ catalysts was presented in this study. This study investigated how the operating conditions, such as the calcinations temperature of catalysts, the reaction temperature, the gas hourly space velocity (GHSV) and the ratio of H₂O/C, affect the conversion of CH₄ and CO₂ and the selectivity of hydrogen from dry and steam reforming of pyrolysis gas. The experimental results indicated that, under the conditions: the reaction temperature of 600 °C, the GHSV of 900 h⁻¹ and H₂O/C of 0.92, the reaction efficiency is the optimal. Especially, the concentration of H₂, CO, CH₄, CO₂, and C₂H_n (C₂H₄ and C₂H₆) were 36.80%, 10.48%, 9.61%, 42.62%, 0.49% respectively. The conversion of CH₄ and CO₂ reached 45.9% and 51.09%, respectively. There were all kinds of reactions during the processing of reforming of pyrolysis gas. And the main reactions changed with the operation condition. It was due to the promoting or inhibiting interaction among different constituents in the pyrolysis gas and the different activity of catalysts in the different operation condition.     

Influence on hydrogen production of the minor components of natural gas during its decomposition using carbonaceous catalysts

In this work, the catalytic decomposition of the minor hydrocarbons present in natural gas, such as ethane and propane, over a commercial carbon black (BP2000) is studied. The influence of the reaction temperature on the product gas distribution was investigated. Increasing reaction temperatures were found to increase both hydrocarbon conversion and hydrogen selectivity. Carbon produced by ethane and propane was predominantly deposited as long filaments formed by spherical aggregates with diameters on the order of nanometres. Furthermore, the influence of ethane and propane on methane decomposition over BP2000 was also investigated, showing enrichment in hydrogen concentration with the addition of small amounts of these hydrocarbons in the feed. Additionally, the positive catalytic effect of H₂S on methane decomposition over BP2000 is addressed.     

Natural gas based hydrogen production with zero carbon dioxide emissions

A novel process flowsheet is presented that co-produces hydrogen and formic acid from natural gas, without emitting any carbon dioxide. The principal technologies employed in the process network include combustion, steam methane reforming (SMR), pressure swing adsorption, and formic acid production from CO₂ and H₂. Thermodynamic analysis provides operating limits for the proposed process, and the use of reaction clusters leads to the synthesis of a feasible process flowsheet. Heat and power integration studies show this flowsheet to be energetically self-sufficient through the use of heat engine and heat pump subnetworks. Operating cost/revenue studies, using current market prices for natural gas, hydrogen and formic acid, identify the proposed design’s operating revenue to cost ratio to be 9.29.     

A perspective on the production of hydrogen from solar-driven thermal decomposition of methane

In addition to “green” hydrogen from electrolysis of the water molecule with solar-photovoltaic or wind electricity, and “white” hydrogen, based on solar-thermal driven thermochemical splitting of the water molecule, there is another emerging opportunity to produce CO2 free hydrogen at a reduced cost. The perspective advocates in favor of “aquamarine” hydrogen, based on the solar-thermal driven thermal decomposition of methane. This pathway has an energy requirement that is much less than white and green hydrogen, and even if based on hydrocarbon fuel, has no direct production of CO₂ as a by-product, but rather carbon particles of commercial interest. Catalytic methane decomposition can be based on self-standing/supported metal-based catalysts such as Fe, Ni, Co, and Cu, metal oxide supports such as SiO₂, Al₂O₃, and TiO₂, and carbon-based catalysts such as carbon blacks, carbon nanotubes, and activated carbons, the pathway of higher technology readiness level (TRL). Thus, catalytic methane decomposition appears to be a highly promising approach, with undoubtedly many challenges, but also huge opportunities following pathways to be further refined through research and development (R&D).     

Optimization of hydrogen production by filtration combustion of natural gas by water addition

The effect of adding steam during filtration combustion of natural gas–air mixtures was studied with the aim to evaluate the optimization of hydrogen production. Temperature, velocity, chemical products of combustion waves, and conversion from fuel to H₂ and CO were evaluated in the range of equivalence ratio (φ) from stoichiometric (φ = 1.0) to φ = 3.0 and steam content in the mixture from 0% to 39%, at filtration velocities from 12 to 25 cm/s. Numerical simulation was carried out using GRI-MECH 3.0. Results suggest that H₂ and CO concentrations, dominant for rich and ultrarich combustion, are products from partial oxidation and steam natural gas reforming processes. Experimental and numerical results show that hydrogen yield increase with an increase of steam content in the natural gas–air mixtures.     

Catalysts evaluation for production of hydrogen gas and carbon nanotubes from the pyrolysis-catalysis of waste tyres

Six different types of catalysts (nickel, iron, and cobalt each supported by γ-Al₂O₃ and activated carbon) that were prepared via impregnation were used to produce hydrogen (H₂) and carbon nanotubes (CNTs) from the pyrolytic product of waste tyres. A two-stage pyrolytic-catalytic reactor was constructed, in which the waste tyre was pyrolyzed in the first pyrolysis reactor, and the resultant pyrolysis vapors underwent the reforming and upgrading step in the downstream catalytic reactor. The results showed that the interaction between the active metal and its support had a remarkable effect on the production of H₂ and CNTs. Compared with the series of γ-Al₂O₃ supported catalysts, all the activated carbon-supported catalysts showed higher H₂ yields and better CNTs quality. For the same catalyst support (γ-Al₂O₃ or activated carbon), the higher yield of H₂ and better quality of CNTs were obtained by the Ni catalysts, followed by the Fe catalysts and the Co catalysts. Among all the catalysts, Ni supported by activated carbon exhibited the best catalytic performance, producing the highest hydrogen yield (59.55 vol.%) and the best CNT quality. Further investigation about the influence of CH₄ and naphthalene as the carbon source on generated CNTs revealed that CH₄ led to longer CNT length and higher graphitization than naphthalene.     

Influence of feedstock properties and pyrolysis conditions on biochar carbon stability as determined by hydrogen pyrolysis

We produced 18 thermosequences of biochar from common feedstocks at ten temperatures from 300 to 900 °C to investigate their influence on carbon stabilization in biochar. Using hydrogen pyrolysis we were able to isolate the stable polycyclic aromatic carbon (SPAC) fraction that is likely to be resistant to mineralization on centennial timescales. SPAC formation was generally <20% of total organic carbon (TOC) at temperatures <450 °C and rises to >80% of TOC at temperatures above 600–700 °C depending on feedstock type. SPAC formation was retarded in feedstocks with high ash contents, and further retarded in those feedstocks when the final hold time at maximum pyrolysis temperature was reduced from one hour to 10 min. Given that aromatization of organic material in many feedstocks is usually completed by ca. 450 °C, the data suggests that a significant pool of aromatic biochar carbon exists in a ‘semi-labile’ form that may not be persistent on centennial timescales. For most feedstocks biochar yield and SPAC content are optimized at pyrolysis temperatures of 500–700 °C.     

Two-step steam pyrolysis of biomass for hydrogen production

In this study, different char based catalysts were evaluated in order to increase hydrogen production from the steam pyrolysis of olive pomace in two stage fixed bed reactor system. Biomass char, nickel loaded biomass char, coal char and nickel or iron loaded coal chars were used as catalyst. Acid washed biomass char was also tested to investigate the effect of inorganics in char on catalytic activity for hydrogen production. Catalysts were characterized by using Brunauer–Emmet–Teller (BET) method, X-ray diffraction (XRD) analyzer, X-ray fluorescence (XRF) and thermogravimetric analyzer (TGA). The results showed that the steam in absence of catalyst had no influence on hydrogen production. Increase in catalytic bed temperature (from 500 °C to 700 °C) enhanced hydrogen production in presence of Ni-impregnated and non-impregnated biomass char. Inherent inorganic content of char had great effect on hydrogen production. Ni based biomass char exhibited the highest catalytic activity in terms of hydrogen production. Besides, Ni and Fe based coal char had catalytic activity on H₂ production. On the other hand, the results showed that biomass char was not thermally stable under steam pyrolysis conditions. Weight loss of catalyst during steam pyrolysis could be attributed to steam gasification of biomass char itself. In contrast, properties of coal char based catalysts after steam pyrolysis process remained nearly unchanged, leading to better thermal stability than biomass char.     

Detecting hydrogen concentrations during admixing hydrogen in natural gas grids

The first applications of hydrogen in a natural gas grid will be the admixing of low concentrations in an existing distribution grid. For easy quality and process control, it is essential to monitor the hydrogen concentration in real time, preferably using cost effective monitoring solutions. In this paper, we introduce the use of a platinum based hydrogen sensor that can accurately (at 0.1 vol%) and reversibly monitor the concentration of hydrogen in a carrier gas. This carrier gas, that can be nitrogen, methane or natural gas, has no influence on the accuracy of the hydrogen detection. The hydrogen sensor consists of an interdigitated electrode on a chip coated with a platinum nanocomposite layer that interacts with the gas. This chip can be easily added to a gas sensor for natural gas and biogas that was already developed in previous research. Just by the addition of an extra chip, we extended the applicability of the natural gas sensor to hydrogen admixing. The feasibility of the sensor was demonstrated in our own (TNO) laboratory, and at a field test location of the HyDeploy program at Keele University in the U.K.     

Synergistic effect of curcumin and activated carbon catalyst enhancing hydrogen production from biomass pyrolysis

This study observes the synergistic effect of low cost and environmentally friendly catalysts, Activated Carbon and curcumin on the production of hydrogen gas in the biomass pyrolysis process. The Study used turmeric containing curcumin as an anti-oxidant agent added to the activated carbon (AC) catalyst. Biomass from coconut wood was pyrolyzed up to 550 °C using a fixed bed reactor. Both AC and curcumin were combined with a ratio of 1:0, 1:1, 1: 3, 0:1, and 3:1. The addition of AC and curcumin was able to increase the production of hydrogen and methane gas. The combination of AC and curcumin with 1:1 ratio was able to increase hydrogen gas by 25.6%. In addition, this combination was also increase methane gas by 71.8%.Curcumin as an anti-oxidant is able to prevents recombination reactions between radical molecules. Activated carbon surface is more protected from free radicals attacking and sticking to the surface. The phi-phi interaction between the two aromatic rings and the surface of activated carbon produces electrostatic forces on the surface of activated carbon to become stronger therefore it is more reactive in cracking hydrocarbon molecules and producing hydrogen gas. Software simulation, SEM, XRD, and FTIR tests were performed to support the analysis of experimental results.     

Modeling study on the production of hydrogen/syngas via partial oxidation using a homogeneous charge compression ignition engine fueled with natural gas

The production of hydrogen and syngas from natural gas using a homogeneous charge compression ignition reforming engine is investigated numerically. The simulation tool used was CHEMKIN 3.7, using the GRI-3 natural gas combustion mechanism. This simulation was conducted on the changes in hydrogen and syngas concentration according to the variations of equivalence ratio, intake temperature, oxygen enrichment, engine speed, initial pressure, and fuel additives with partial oxidation combustion. The simulation results indicate that the hydrogen/syngas yields are strongly dependent on the equivalence ratio with maxima occurring at an optimal equivalence ratio varying with engine speed. The hydrogen/syngas yields increase with increasing intake temperature and oxygen contents in air. The hydrogen/syngas yields also increase with increasing initial pressure, especially at lower temperatures, yet high temperature can suppress the pressure effect. Furthermore, it was found that the hydrogen/syngas yields increase when using fuel additives, especially hydrogen peroxide. Through the parametric screening studies, optimum operating conditions for natural gas partial oxidation reforming are recommended at 3.0 equivalence ratio, 530 K intake temperature, 0.3 oxygen enrichment, 500 rpm engine speed, 1 atm initial pressure, and 7.5% hydrogen peroxide.     

Hydrogen separation from blended natural gas and hydrogen by Pd-based membranes

Hydrogen separation membranes based on a heated metal foil of a palladium alloy, offer excellent permeability for hydrogen as a result of the solution-diffusion mechanism. Here, the possibility to separate hydrogen from the mixture of Natural Gas (NG) and hydrogen (NG+H₂) with various NG concentrations using Pd, PdCu₅₃ and PdAg₂₄ hydrogen purification membranes is demonstrated. Hydrogen concentrations above ∼25% (for Pd and PdCu₅₃) and ∼15% (for PdAg₂₄) were required for the hydrogen separation to proceed at 400 °C and 5 bar pressure differential. Hydrogen permeability of the studied alloys could be almost fully recovered after switching the feed gas to pure hydrogen, indicating no significant interaction between the natural gas components and the membranes surface at the current experimental condition. Hydrogen flux of the membranes at various pressure differential was measured and no changes in the hydrogen permeation mechanism could be noticed under (NG 50%+H₂) mixture. The hydrogen separation capability of the membranes is suggested to be mainly controlled by the operating temperature and the hydrogen partial pressure.     

Study on the stratification of the blended gas in the pipeline with hydrogen into natural gas

When blending hydrogen into existing natural gas pipelines, the non-uniform concentration distribution caused by the density difference between hydrogen and natural gas will result in the fluctuations of local hydrogen partial pressure, which may exceed the set one, leading to pipeline failure, leakage, measurement error, and terminal appliance. To solve the problem, the H₂–CH₄ stratification in the horizontal and undulated pipe was investigated experimentally and with numerical simulations. The results show that in the gas stagnant situation, hydrogen-methane blending process will cause an obvious stratification phenomenon. The relations between the elevation, pressure, hydrogen fraction, etc., and the gas stratification are figured out. Moreover, even when the blended gas flows at a low rate, the hydrogen-caused stratification should also be considered. Thereafter, the blended gas should be controlled into a situation with low pressure and high speed, which could help to set the pressure, speed, the fraction of H₂.     

An energy-efficient plasma methane pyrolysis process for high yields of carbon black and hydrogen

A novel thermal plasma process was developed, which enables economically viable commercial-scale hydrogen and carbon black production. Key aspects of this process are detailed in this work. Selectivity and yield of both solid, high-value carbon and gaseous hydrogen are given particular attention. For the first time, technical viability is demonstrated through lab scale reactor data which indicate methane feedstock conversions of >99%, hydrogen selectivity of >95%, solid recovery of >90%, and the ability to produce carbon particles of varying crystallinity having the potential to replace traditional furnace carbon black. The energy intensity of this process was established based on real-time operation data from the first commercial plant utilizing this process. In its current stage, this technology uses around 25 kWh per kg of H2 produced, much less than water electrolysis which requires approximately 60 kWh per kg of H2 produced. This energy intensity is expected to be reduced to 18–20 kWh per kg of hydrogen with improved heat recovery and energy optimization.     

Effective use of hydrogen sulfide and natural gas resources available in the Black Sea for hydrogen economy

In this article, we propose a novel system to effectively deploy an integrated fuel processing system for hydrogen sulfide and natural gas resources available in the Black Sea to be used for a quick transition to the hydrogen economy. In this regard, the proposed system utilizes offshore wind and offshore photovoltaic power plants to meet the electricity demand of the electrolyzer. A PEM electrolyzer unit generates hydrogen from hydrogen sulfide that is available in the Black Sea deep water. The generated hydrogen and sulfur gas from hydrogen sulfide are stored in high-pressure tanks for later use. Hydrogen is blended with natural gas, and the blend is utilized for industrial and residential applications. The investigated system is modeled with the Aspen Plus software, and hydrogen production, blending, and combustion processes are analyzed accordingly. With the hydrogen addition up to 20% in the blend, the carbon dioxide emissions of combustion decrease from 14.7 kmol/h to 11.7 kmol/h, when the annual cost of natural gas is reduced from 9 billion $ to 8.3 billion $. The energy and exergy efficiencies for the combustion process are increased from 84% to 97% and from 62% to 72%, respectively by a 20% by volume hydrogen addition into natural gas.     

The effects of hydrogen enriched natural gas under different engine loads in a diesel engine

Natural gas, which is among the alternative fuels, has become widespread in the transportation as it is both economical and environmentally friendly. While the use of natural gas is at a significant level in spark ignition engines, it has not yet been implemented in compression ignition engines (CI) as it worsens combustion due to ignition delay. In CI engines, however, the combustion properties of natural gas (NG) can be improved by adding hydrogen (H₂) to NG. This is one of the methods applied to use natural gas in CI engines. In this experimental study, two different volumetric rates of NG and NG/H₂ mixtures were added to the combustion air in a CI engine, and engine performance and emissions were examined under different engine loads. The experiments were performed at two different engine speeds, four different engine loads and no-load condition. An engine cylinder pressure of 59.16 bar, which is the closest value to the 59.39 bar obtained in the use of diesel fuel, was obtained at 1500 rpm for “Diesel + NG(500 g/h)” and 59.9 bar (highest values) was obtained for “Diesel + (500 g/h) [80%NG+20%H₂]" at 1750 rpm. For “Diesel + NG(250 g/h)” (Mix1) and “Diesel + NG(500 g/h)” (Mix2), as the engine speed increases, at the point where the maximum in-cylinder pressure is obtained occurs further to the right from top dead center (TDC). With the addition of 500 g/h NG, an increase of 4.5% was achieved in the cylinder pressure at full load, while an increase of 6.5% was achieved in the case of using “Diesel + (500 g/h) [80%NG+20%H₂]". Although the effect of the NG and NG/H₂ mixtures on in-cylinder pressure was small, the fuel consumption and thermal efficiency improved. Substantial improvements in hydrocarbon (HC) emissions were observed with the use of “Diesel + (250 g/h)[80%NG+20%H₂]”. Carbon dioxide (CO₂) emissions decreased with speed increase, but no significant differences in terms of CO₂ emissions were observed between the mixtures. There was a maximum difference of 15% between the diesel and the mixtures in CO₂ emissions. Although there was a decrease in nitrogen oxide (NO_x) levels with the increase in engine speed, the lowest NO_x emissions of 447.6 ppmvol was observed in “Diesel + NG(250 g/h)” (Mix1) at 1750 rpm at maximum load.     

Experimental investigation on performance of hydrogen additions in natural gas combustion combined with CO2

Natural gas with H₂ is widely used for lean-burn combustion, which leads to NO_x emission as the main problem for it. For decreasing NO_x emission and increasing thermal efficiency, the investigation on seeking the influence of H₂ fractions on the mixture of CH₄ and CO₂ was conducted. Firstly, the ignition timing was decided through thermal efficiency and brake mean effective pressure (BMEP) for CH₄ only. Then, combustion characteristics of CH₄, CH₄+CO₂ and CH₄+CO₂+H₂ were compared with volume percentage of H₂ changing from 5% to 30%. Finally, the H₂ injection strategy was checked between closed and open valve injections. Among these discussions, thermal efficiency, power output, BMEP and fuel consumption were evaluated. Results show that CO₂ addition decreases power output and BMEP, leading to much more fuel consumption and lower thermal efficiency. When H₂ is added, at the rich mixture conditions (λ＜1.0), power output and thermal efficiency decrease sharply as the mixture is enriched. However, at the lean-burn conditions (λ＞1.0), the decrease in flow rate of lower heating value (LHV) and increase in power output finally result in the higher efficiency with H₂ addition. Moreover, when λ＞1.0, both low fuel consumption and high efficiency can be obtained with H₂ addition to achieve the high BMEP. Furthermore, the open valve injection could obtain higher thermal efficiency, power output and BMEP with lower fuel consumption, suggesting that the H₂ injection strategy should be well controlled with the ignition timing.     

Performance evaluation of membrane on catalyst module for hydrogen production from natural gas

We have been developing a hydrogen production module with a Pd-based membrane on catalyst (MOC) from natural gas. The MOC module is expected to be more compact and cheaper than the conventional hydrogen production module. To evaluate the hydrogen production performance of the MOC module and to clear the factor that dominates the effective hydrogen production, we compared the reforming performance of the catalytic support without hydrogen permeable membrane and the MOC module at various reaction conditions. As a result, it was cleared that hydrogen permeation through the membrane improves the methane conversion drastically in the MOC module by comparing with the support only module and changing the experimental conditions.     

Technical,economic, and environmental analyses of the modernization of a chamber furnace operating on natural gas or hydrogen

The paper presents a technical, economic and environmental analyses of a chamber furnace used to heat the charge before forging. The energy efficiency of the furnace before the modernization was 18%, after the modernization it was 31% (partial modernization due to large financial outlays). Other variants were also analysed: complete modernization, the variant of furnace modernization with 30% hydrogen content in the gas and the variant with 100% hydrogen as fuel. The analyses showed that with the current gas price (0.025 EUR/kWh) and the price of emission allowances (nearly 60 EUR/MgCO₂) and 100 cycles/year, the difference in Net Present Value (NPV) before base variant and partial modernization is around 900,000 EUR and before base variant and full modernization is 1,200,000 EUR. The introduction of the gas and 30% of hydrogen co-combustion option versus the base scenario option for 150 cycles per year results in a NPV difference of at least 2 million EUR. The option of 100% hydrogen as a fuel is the most advantageous from the point of view of reducing CO₂ emissions - it is largely influenced by the rising prices of CO₂ emission allowances.     

Analysis and techno-economic assessment of renewable hydrogen production and blending into natural gas for better sustainability

In this study, comprehensive thermodynamic analysis and techno-economic assessment studies of the renewable hydrogen production and its blending with natural gas in the existing pipelines are performed. Solar and wind energy-based on-grid and off-grid power systems are designed and compared in energy, exergy, and cost. Solar PV panels and wind turbines are particularly considered for electricity and hydrogen production for residential applications in an environmentally benign way. Fuel cell units are included to supply continuous electricity in the off-grid system. Here, the heat required for a community consisting of 100 houses is provided by hydrogen and natural gas mixture as a more environmentally benign fuel. The costs of capital, fuel, operation, and maintenance are calculated and evaluated in detail. The total net present costs are calculated as $6.95 million and $2.47 million for the off-grid and on-grid power systems, respectively. For the off-grid system, energy and exergy efficiencies are calculated as 32.64% and 40.73%, respectively. Finally, the energy and exergy efficiencies of the on-grid system are determined as 26.58% and 35.25%, respectively.