Storage of hydrogen,natural gas,and carbon dioxide – Geological and legal conditions

The analysis of geological and reservoir conditions of the underground storage of hydrogen, methane, and carbon dioxide, that are important when choosing rock formations for the storage of gas, was presented. Physico-chemical properties of the discussed gases, affecting underground storage, were taken into account. Aquifers, hydrocarbon reservoirs, and caverns leached in salt rocks were analyzed. Legal aspects of underground gas storage were indicated.The physico-chemical conditions of the gases considered (especially molecular mass, and dynamic viscosity) are important for the selection of geological structures for their storage. The reservoir tightness is one of the most important geological and reservoir conditions when taking the appropriate porosity and permeability of rocks building underground storage sites into account. Salt caverns should be mainly used for hydrogen storage due to the tightness of rock salt. Geochemical and microbiological interactions affecting the operation of the underground storage site and its tightness are especially important and should be taken into account. The size of the underground storage site, while not as crucial in the case of H₂ storage, is important for CO₂ storage. When it comes to reservoir conditions, the amount of cushion gas and storage efficiency are important. The legal status of gas storage sites is highly variable. While there are existing regulations regarding natural gas storage, CO₂ storage requires further legislation. In the case of H₂ storage legal regulations need to be developed based on the experience of storage of other gases. The potential competition from other entities focused on the use of underground space for gas storage should be taken into account.     

Biogas to high purity hydrogen by methane dry reforming in TZFBR+MB and exhaustion by Steam-Iron Process. Techno–economic assessment

A techno-economic study has been carried out with the aim of analyzing the performance (product distribution and energy yields) and estimating the production costs of high purity hydrogen obtained from biogas. For such purpose and taking advantage of empirical data developed in our laboratory, it has been proposed a system consisting of a two-zone fluidized bed reactor aided by a system of permselective (Pd/Ag) metallic membranes inserted in the fluidized bed (TZFBR+MB), and a battery of several fixed bed reactors operating cycles of reduction and oxidation (Steam-Iron Process -SIP-). The feed has always been an equimolar mixture of CH₄ and CO₂ simulating a sweetened biogas. The first reactor (TZFBR+MB) can produce a stream of pure hydrogen (i.e. PEMFC quality) as permeated flow through the MB, and a retentate stream rich in all species resulting from the methane dry reforming reaction (MDR) and the water gas shift equilibrium (WGS). The singularity of this kind of complex reactors is that regeneration of the catalyst is performed in the same reactor and simultaneously to the MDR reaction because of the two-zone. Due to the reductive behavior of the retentate stream, it can be fed to a bed of solid where up to two different oxygen carriers (iron oxide with additives and cobalt ferrite) can be reduced to their metallic state. Once the solid has been completely reduced, it can be reoxidized with steam releasing a high purity hydrogen stream. Both reactors (i.e. TZFBR+MB and SIP) have been coupled in different degrees. A performance (hydrogen and energy yields) as well as costs analysis (fixed assets and operating costs) have been performed with the aid of Aspen HYSYS v9.0, used for dimensioning the equipment needed to process up to 1350 kg/h of biogas. On this way, the integrated process enhances the efficiencies of every single process allowing pure hydrogen yields up to 68% at 575 °C in the TZFBR+MB and an overall energy efficiency greater than 45%. Production costs have been found to be in the range from 4 to 15 €/kg, still high but not so far away from the target of DOE fixed in 2 $/kg by 2020.     

Can hydrogen or natural gas be alternatives for aviation? – A life cycle assessment

Between 1989 and 2011 the aviation traffic has been growing 4.6% per year. The increase on aviation traffic had consequences in terms of greenhouse gases (GHGs) and local pollutant emissions (e.g. carbon monoxide – CO, hydrocarbons – HC, nitrogen oxides – NO_x). In order to minimize this problem, the evaluation of sustainable alternatives to current fuel (jet fuel A) has been discussed but their impact on emissions is still unclear. The main research goals of this paper are: (i) to evaluate if the well-to-wake energy consumption in aviation can be reduced with alternative fuels as liquid natural gas (LNG) and/or liquid hydrogen (LH₂) and (ii) to assess if alternative fuels can be used in aviation to minimize carbon dioxide emissions and local pollutants.     

Effects of initial pressure and hydrogen concentration on laminar combustion characteristics of diluted natural gas–hydrogen–air mixture

In this study, the experiment study about the laminar burning velocity and the flame stability of CO₂ diluted natural gas–hydrogen–air mixture was conducted in a constant volume combustion vessel by using the high-speed schlieren photography system. The unstretched laminar burning velocity and the Markstein length at different hydrogen fractions, dilution ratios and equivalence ratios and with different initial pressures were obtained. The flame stability was studied by analyzing the Markstein length, the flame thickness, the density ratio and the flame propagation schlieren photos. The results showed that the unstretched laminar burning velocity would be reduced with the increase of the initial pressure and dilution ratio and would be increased with the increase of the hydrogen fraction of the mixture. Meanwhile, the Markstein length would be increased with the increase of the equivalence ratio and the dilution ratio. Slight flaws occurred at the early stage. At a specific equivalence ratio, a higher initial pressure and hydrogen fraction would cause incomplete combustion.     

Investigation of effects of sulfur on dry reforming of biogas over nickel–iron based catalysts

The aim of this study is to maintain and increase the activity of the catalyst in the presence of H₂S with the addition of iron to the Ni catalyst. Alumina-supported monometallic iron and bimetallic nickel-iron catalysts with different weight percentages (8% Fe, 3% Ni – 3% Fe and 8% Ni – 8% Fe) were synthesized using the wet impregnation method in this study. Alumina was prepared by the sol-gel method. The activities of these synthesized catalysts in the methane dry reforming reaction were investigated at different H₂S concentrations (0 ppm, 2 ppm, and 50 ppm) with a total flow rate of 60 mL/min containing an equimolar ratio of CH₄, CO₂, and Ar at 750 °C and atmospheric pressure. To investigate the effect of sulfur compounds on the catalytic activity, the catalysts were also exposed to different gas compositions such as the mixture of H₂S + He, H₂S + CO₂ + He, and H₂S + CO₂ + CH₄ + He. In this case, FT-IR with a gas cell was used to determine the components in the gas stream at the reactor outlet. To explain catalytic performance, characterization studies were carried out using XRD, N₂ adsorption/desorption, DRIFT, SEM, TGA, and XPS analysis. All-synthesized materials showed Type-IV isotherm with a hysteresis loop corresponding to an ordered mesoporous structure. The DRIFT analysis showed a decrease in the Lewis acid sites after the addition of iron into the Ni-catalysts. In the activity test carried out in the presence of 50 ppm H₂S, it was observed that the iron-containing 8Ni–8Fe@SGA catalyst increased the sulfur resistance slightly, compared to the monometallic 8Ni@SGA catalyst. TGA analysis showed that Fe addition reduced coke deposition, as the Ni–Fe catalyst had a lower nickel crystal size than the Ni-based catalyst. FTIR analysis with a gas cell showed that sulfur in H₂S transformed to other sulfur compounds such as COS and/or SO₂ during dry reforming of biogas over alumina-supported Ni–Fe catalysts.     

The progress in water gas shift and steam reforming hydrogen production technologies – A review

Hydrogen has been widely considered a clean fuel of the future, with the highest mass based energy density of known fuels. Water gas shift (WGS) and steam reforming (SR) are the major reactions used for hydrogen production, and improved catalysts are essential to the future of the WGS and SR processes. Much progress in the different aspects of these fields has been made recently, which includes approaches to preparation and characterization, doping and promotion, as well as evaluation of catalysts, especially nanocatalysts. Significant improvements have been realized in increasing the stability of the catalysts, the overall conversion of raw materials, and the hydrogen production selectivity. This review aims to introduce these hydrogen production processes, to present developments in these areas, and discusses recent improvements that have made noteworthy impacts.     

LNG import quotas in Lithuania – Economic effects of breaking Gazprom's natural gas monopoly

Until 2014, Russia's Gazprom had a natural gas monopoly in Lithuania. In order to break the Russian monopoly, the Lithuanian state financed an import terminal for liquefied natural gas (LNG) in Klaipėda. In addition to building the terminal, Lithuania signed a long-term contract (LTC) which can be interpreted as a minimum import volume quota for LNG having higher marginal supply costs than Russian gas. This study assesses the potential of such a minimum import volume quota to mitigate the market power of a monopolistic supplier. A market consisting of a dominant supplier with low marginal supply costs and a competitive fringe with high marginal supply costs is analyzed. It is shown that there is a minimum import volume quota for fringe supplies that optimizes the consumer surplus, which is adjusted by a compensation paid for the fringe's market entry. Therefore, the Lithuanian decision to incentivize the market entry of high-cost LNG can be rationalized.     

Wind hydrogen energy system and the gradual replacement of natural gas in the State of Ceará – Brazil

The original model for the solar hydrogen energy system created by Veziroglu and Basar in the 70’s was adapted to the State of Ceará – Brazil. The State of Ceará has one of the greatest wind potentials in Brazil and it is estimated to be around 35 GW. At the present year, there are 494 MW wind farms in operation. The aforementioned State also has a natural gas grid of pipelines serving a great number of consumers. There are studies in literature considering the injection of hydrogen into the natural gas pipeline up to 20% in volume without substantial modifications in the natural gas infrastructure. The main objective of this article is to use that model in order to evaluate long term scenarios in which the off peak wind generated hydrogen gradually replaces natural gas in such important State of Brazil. The system is supposed to start in the year 2015 and the economical revenue when it is fully implemented can reach respectively US$ 730 million or US$ 1 billion in the slow or fast scenario of hydrogen introduction into the energy matrix of that important State of Brazil.     

Catalysts based on Co-Birnessite and Co-Todorokite for the efficient production of hydrogen by ethanol steam reforming

Two structured manganese oxides (Birnessite and Todorokite) containing Co have been studied in the steam reforming of ethanol. It has been found that both materials are active in the hydrogen production, exhibiting high values of conversion of ethanol and selectivities to hydrogen (100% and 70%, respectively). The best results have been obtained with the catalyst based on Todorokite material. Characterization by DRX, BET area, TPR and TEM has allowed to find that the excellent performance exhibited by this material could be attributed to the lower size of the Co metallic particles present in this sample (6 nm vs 12 nm in Birnessite). This lower size could be related to the especial microporous structure of Todorokite precursor, which could provide high-quality positions for the stabilization of the Co metal particles during calcination and reduction steps. Catalytic deactivation has also been considered. Deactivation was found higher for Todorokite-based catalyst, which presented the largest amount of deposited carbon (26.2 wt% for Co-TOD vs 10.6 wt% for Co-BIR). On the other hand, the degree of metal sintering was found similar in both catalysts. Therefore, the deactivation of the catalysts has been attributed primarily to the deposition of coke. The results presented here show that it is possible to prepare new catalysts based on manganese oxides with Birnessite and Todorokite structure and promoted with Co with high catalytic performance in the steam reforming of ethanol.     

Energy and exergy analyses of a solar driven Mg–Cl hybrid thermochemical cycle for co-production of power and hydrogen

Analysis and performance assessment of a solar driven hydrogen production plant running on an Mg–Cl cycle, are conducted through energy and exergy methods. The proposed system consists of (a) a concentrating solar power cycle with thermal energy storage, (b) a steam power plant with reheating and regeneration, and (c) a hybrid thermochemical Mg–Cl hydrogen production cycle. The results show that higher steam to magnesium molar ratios are required for full yield of reactants at the hydrolysis step. This ratio even increases at low temperatures, although lowering the highest temperatures appears to be more favorable for linking such a cycle to lower temperature energy sources. Reducing the maximum cycle temperature decreases the plant energy and exergy efficiencies and may cause some undesirable reactions and effects. The overall system energy and exergy efficiencies are found to be 18.8% and 19.9%, respectively, by considering a solar heat input. These efficiencies are improved to 26.9% and 40.7% when the heat absorbed by the molten salt is considered and used as a main energy input to the system. The highest exergy destruction rate occurs in the solar field which accounts for 79% of total exergy destruction of the integrated system.     

Combustion behaviors of a direct-injection engine operating on various fractions of natural gas–hydrogen blends

Combustion behaviors of a direct injection engine operating on various fractions of natural gas–hydrogen blends were investigated. The results showed that the brake effective thermal efficiency increased with the increase of hydrogen fraction at low and medium engine loads and high thermal efficiency was maintained at the high engine load. The phase of the heat release curve advanced with the increase of hydrogen fraction in the blends. The rapid combustion duration decreased and the heat release rate increased with the increase of hydrogen fraction in the blends. This phenomenon was more obviously at the low engine speed, suggesting that the effect of hydrogen addition on the enhancement of burning velocity plays more important role at relatively low cylinder air motion. The maximum mean gas temperature and the maximum rate of pressure rise increased remarkably when the hydrogen volumetric fraction exceeds 20% as the burning velocity increases exponentially with the increase of hydrogen fraction in fuel blends. Exhaust HC and _CO2${\mathrm{CO}}_2$ concentrations decreased with the increase of the hydrogen fraction in fuel blends. Exhaust _NOx${\mathrm{NO}}_x$ concentration increased with the increase of hydrogen fraction at high engine load. The study suggested that the optimum hydrogen volumetric fraction in natural gas–hydrogen blends is around 20% to get the compromise in both engine performance and emissions.     

Effect of hydrogen addition on early flame growth of lean burn natural gas–air mixtures

Effect of hydrogen addition on early flame growth of lean burn natural gas–air mixtures was investigated experimentally and numerically. The flame propagating photos of premixed combustion and direct-injection combustion was obtained by using a constant volume vessel and schlieren photographic technique. The pressure derived initial combustion durations were also obtained at different hydrogen fractions (from 0% to 40% in volumetric fraction) at overall equivalence ratio of 0.6 and 0.8, respectively. The laminar premixed methane–hydrogen–air flames were calculated with PREMIX code of CHEMKIN II program with GRI 3.0 mechanism. The results showed that the initial combustion process of lean burn natural gas–air mixtures was enhanced as hydrogen is added to natural gas in the case of both premixed combustion and direct-injection combustion. This phenomenon is more obvious at leaner mixture condition near the lean limit of natural gas. The mole fractions of OH and O are increased with the increase of hydrogen fraction and the position of maximum OH and O mole fractions move closing to the unburned mixture side. A monotonic correlation between initial combustion duration with the reciprocal maximum OH mole fraction in the flames is observed. The enhancement of the spark ignition of natural gas with hydrogen addition can be ascribed to the increase of OH and O mole fractions in the flames.     

Water-gas shift assisted autothermal reforming of methane gas – transient and cold start studies

A study has been carried out to investigate the dynamic behaviour of water-gas shift assisted autothermal reforming (ATR-WGS) utilising a 2-D heterogeneous kinetic model. The purpose of this study is to gain insights to the dynamic changes of ATR-WGS during cold start and when subjected to a sudden change in square-pulse flow rate. In addition to analysis of ATR-WGS, the model can also aid in guiding the design of a feedback controller aimed at improving the dynamic response of the system. Cold start time for ATR-WGS reactor was found to be longer than autothermal reforming (ATR) reactor due to the addition of a slower water-gas shift (WGS) process. It was also observed that WGS plays an important role in the final products of the reaction. In addition to these findings, the investigations in the transient performance of ATR-WGS showed that there are serious overshoot/undershoot of performance related parameters in the transients, whose values are quite different from those under steady state conditions.     

Catalytic exhaust gas fuel reforming for diesel engines—effects of water addition on hydrogen production and fuel conversion efficiency

Previous work in our laboratory has shown that the exhaust gas assisted fuel reforming process has the potential to provide a solution to the diesel engine exhaust emission problems. When simulated reformer product gas rich in hydrogen is fed to the engine, a reduction of both NO_x and smoke emissions can be achieved. In this paper, the optimisation of the reforming process by water addition in the reactor is presented. Using a prototype catalyst at 290°C reactor inlet temperature, up to 15% more hydrogen in the reformer product was obtained compared to operation without water. The process has been found to be mainly a combination of the fuel oxidation, steam reforming and water gas shift reactions. The reforming process efficiency has been shown to improve considerably with water addition up to a certain level after which the adverse effects of the exothermic water gas shift reaction become significant.     

Experimental and modeling study of performance and emissions of SI engine fueled by natural gas–hydrogen mixtures

Based on CFD software and reaction kinetics software, multi-dimensional CFD Model coupled with detail reaction kinetics is built to study the combustion process in H₂/CNG Engine. Detail reaction mechanism is used to simulate the chemistry of combustion and a combustion model considering the turbulent mixing effects was also applied. To reduce the computation time, the coupled software is reprogrammed to have the function of parallel computing and the revised software is computed in a Massively Parallel Processor. The model is validated using the experiment data from a modified diesel engine. The results show: cylinder pressure from simulation has a good agreement with experiment data and CO and NO_x emission is well predicted by the model in a wide range.     

Steam reforming of liquefied natural gas (LNG) for hydrogen production over nickel–boron–alumina xerogel catalyst

A series of mesoporous nickel–boron–alumina xerogel (x-NBA) catalysts with different boron/nickel molar ratio (x = 0–1) were prepared by an epoxide-driven sol–gel method. The effect of boron/nickel molar ratio on the catalytic activities and physicochemical properties of nickel–boron–alumina xerogel catalysts was investigated in the steam reforming of liquefied natural gas (LNG). All the mesoporous x-NBA catalysts showed similar surface area. Introduction of boron increased interaction between nickel and support. In addition, introduction of boron into x-NBA catalysts reduced methane activation energy and increased nickel surface area. Promotion of boron had a positive effect on the catalytic activity due to the increase of adsorbed methane and nickel surface area. The amount of adsorbed methane and nickel surface area exhibited volcano-shaped trends with respect to boron/nickel molar ratio. LNG conversion and hydrogen yield increased with increasing the amount of adsorbed methane and with increasing nickel surface area. Among the catalysts, 0.3-NBA, which retained the largest amount of adsorbed methane and the highest nickel surface area, showed the best catalytic performance. It was also revealed that x-NBA catalysts showed strong coke resistance during the steam reforming reaction.     

Economic evaluation of natural gas transportation from Iran’s South-Pars gas field to market

The worldwide consumption of natural gas is rapidly increasing. To satisfy such a demand, there are some plans to transport natural gas from South-Pars gas field, the largest natural gas field of Iran, to some energy consuming countries. There are several possible technologies for transporting gas from production fields to consuming markets as gas, including PNG (pipeline natural gas), LNG (liquefied natural gas), CNG (compressed natural gas) and NGH (natural gas hydrate). Gas transmission projects are sensitive to technology selection and depending on the capacity and distance; chosen technology may affect the economy of the entire project noticeably. In this work, transporting 100 × 10⁶ standard m³/d natural gas from port of Assaluyeh in south of Iran to potential markets using alternative technologies such as PNG, LNG, CNG and NGH has been investigated. To do such a study, required processes for converting natural gas to desired product and then transporting it to market have been designed and using an economical model, cost of transporting natural gas as a function of distance, has been estimated. Results show for the investigated case, PNG has the lowest production cost for distances up to 7600 km and for larger distances, LNG has the lowest production cost.     

A novel system for the production of pure hydrogen from natural gas based on solid oxide fuel cell–solid oxide electrolyzer

In this paper, a novel process for the production of pure hydrogen from natural gas based on the integration of solid oxide fuel cells (SOFCs) and solid oxide electrolyzer cells (SOECs) is presented. In this configuration, the SOFC is fed by natural gas and provides electricity and heat to the SOEC, which carries out the separation of steam into hydrogen and oxygen. Depending on the system layout considered, the oxygen available at the SOEC anode outlet can be either mixed with the SOFC cathode stream in order to improve the SOFC performance or regarded as a co-product. Two configurations of the cell stack are studied. The first consists of a stack with the same number of SOFCs and SOECs working at the same current density. In this case, since in typical operating conditions the voltage delivered by the SOFC is lower than the one required by the SOEC, the required additional power is supplied by means of an electric grid connection. In the second case, the electricity balance is compensated by providing additional SOFCs to the stack, which are fed by a supplementary natural gas feed. Simulations carried out with Aspen Plus show that pure hydrogen can be produced with a natural gas to hydrogen LHV-efficiency that is about twice the value of a typical water electrolyzer and comparable to that of medium-scale reformers.     

Analysis on the feasibility of biomass power plants adding to the electric power system – Economic,regulatory and market aspects – State of Pará, Brazil

This paper presents an analysis of the feasibility of implementing biomass power plants, through thermoelectric power generation, and adding such plants to the electric system of the local electric utility by means of independent power production. Economic, regulatory, and market issues are also addressed.The biomass being considered is produced by the lumber sector, since that is one of the industrial sectors generating the largest amount of residues in a concentrated manner in the region under study, and also considering the fact that the disposal of such residues is currently difficult for the lumber companies.The locations with the largest production of residues, as well as the size of potential plants, are identified, the generation costs of the plants calculated, and the feasibility for implementing the plants is evaluated considering the market and the regulation of the Brazilian electric power sector.     

Experimental investigation on performance and emissions of a spark-ignition engine fuelled with natural gas–hydrogen blends combined with EGR

An experimental investigation on the influence of different hydrogen fractions and EGR rates on the performance and emissions of a spark-ignition engine was conducted. The results show that large EGR introduction decreases the engine power output. However, hydrogen addition can increase the power output at large EGR operation. Effective thermal efficiency shows an increasing trend at small EGR rate and a decreasing trend with further increase of EGR rate. In the case of small EGR rate, effective thermal efficiency is decreased with the increase of hydrogen fraction; while in the case of large EGR rate, thermal efficiency is increased with increasing of hydrogen fraction. For a specified hydrogen fraction, NO_x concentration is decreased with the increase of EGR rate and this effectiveness becomes more obviously at high hydrogen fraction. HC emission is increased with the increase of EGR rate and it decreases with the increase of hydrogen fraction. CO and CO₂ emissions show little variations with EGR rate, but they decrease with the increase of hydrogen fraction. The study shows that natural gas–hydrogen blend combining with EGR can realize high-efficiency and low-emission spark-ignition engine.