Hydrogen energy from coupled waste gasification and cement production—a thermochemical concept study

A plant concept for hydrogen production from waste gasification coupled with cement manufacturing is presented. Hot precalcined cement meal, from the operating cement process, is used as heat carrier to provide energy required by the parallel arranged gasifier. The amount of CaO present in the cement meal operates simultaneously as an effective in situ _CO2${\mathrm{CO}}_2$-sorbent. First, a practical case study was devised to be able to perform simulations for estimation of expected hydrogen yield. The influence of different operation parameters of the gasifier and the hydrogen separation unit (steam-to-fuel ratio, pyrolysis temperature, PSA efficiency) was studied based on chemical equilibrium calculations. The simulation results indicate, that the coupling provides advantages for both processes. The production of a hydrogen-rich gas via thermal gasification benefits from the continuously available fresh CaO, which improves fuel conversion reactions and captures _CO2${\mathrm{CO}}_2$ in situ. High-calorific streams from gasification process remaining after hydrogen separation may substitute fossil fuels needed for cement process. For a steam/fuel ratio of 0.3 and a PSA efficiency of 0.7, the calculated hydrogen energy yield is 46% of fuel energy input.     

Development and environmental impact of hydrogen supply chain in Japan: Assessment by the CGE-LCA method in Japan with a discussion of the importance of biohydrogen

Hydrogen is an attractive and clean source of energy with a high energy content and environmentally friendly production using green power. Hydrogen is therefore considered to be one of the future alternatives to fossil fuels that can limit the damage done by climate change. A dynamic GTAP model with LCA method is utilized herein in this investigation to forecast the development of the hydrogen supply chain and CO₂ emissions in Japan. The supply chain incorporates six hydrogen-related industries – biohydrogen, steam reforming, electrolysis, hydrogen fuel cell vehicles (HFCV), hydrogen fuel cells (HFC), and hydrogen fueling stations.     

A review on reforming bio-ethanol for hydrogen production

Bio-ethanol is a prosperous renewable energy carrier mainly produced from biomass fermentation. Reforming of bio-ethanol provides a promising method for hydrogen production from renewable resources. Besides operating conditions, the use of catalysts plays a crucial role in hydrogen production through ethanol reforming. Rh and Ni are so far the best and the most commonly used catalysts for ethanol steam reforming towards hydrogen production. The selection of proper support for catalyst and the methods of catalyst preparation significantly affect the activity of catalysts. In terms of hydrogen production and long-term stability, MgO, ZnO, _CeO2${\mathrm{CeO}}_2$, and _La2O3${\mathrm{La}}_2{\mathrm{O}}_3$ are suitable supports for Rh and Ni due to their basic characteristics, which favor ethanol dehydrogenation but inhibit dehydration. As Rh and Ni are inactive for water gas shift reaction (WGSR), the development of bimetallic catalysts, alloy catalysts, and double-bed reactors is promising to enhance hydrogen production and long-term catalyst stability. Autothermal reforming of bio-ethanol has the advantages of lesser external heat input and long-term stability. Its overall efficiency needs to be further enhanced, as part of the ethanol feedstock is used to provide low-grade thermal energy. Development of millisecond-contact time reactor provides a low-cost and effective way to reform bio-ethanol and hydrocarbons for fuel upgrading. Despite its early R&D stage, bio-ethanol reforming for hydrogen production shows promises for its future fuel cell applications.     

Hydrogen injection as additional fuel in gas turbine combustor. Evaluation of effects

Industrial gas turbines fuelled by fossil fuels have been used widely in power generation and combined heat and power for many years. However they have to meet severe _NOx${\mathrm{NO}}_x$, CO and _CO2${\mathrm{CO}}_2$ (greenhouse effect) emissions legislation in many countries. This paper reports a study on injection of small quantities of hydrogen in a hydrocarbon fuelled burner like additionally fuel to reduce the pollutants emissions. Hydrogen is injected in the primary zone, premixed with the air. Using this injection together lean primary zone, it is possible to reduce the _NOx${\mathrm{NO}}_x$ level while CO an HC levels remains approximately constant.     

Selective CO oxidation with real methanol reformate over monolithic Pt group catalysts: PEMFC applications

Alumina supported Pt group metal monolithic catalysts were investigated for selective oxidation of CO in hydrogen-rich methanol reforming gas for proton exchange membrane fuel cell (PEMFC) applications. The results are described and discussed in the present paper and show that Pt/γ_Al2O3$\mathrm{Pt}/\gamma {\mathrm{Al}}_2{\mathrm{O}}_3$ was the most promising candidate to selectively oxidize CO from an amount of about 1 vol% to less than 100 ppm. We have investigated the effect of the O₂ to CO feed ratio, the feed concentration of CO, the presence of H₂O and/or CO₂, and the space velocity on the activity, selectivity and stability of Pt/Al₂O₃ monolithic catalysts. Afterwards, the Pt/Al₂O₃ catalyst was scaled up and applied in 5 kW hydrogen producing systems based on methanol steam reforming and autothermal reforming. The hydrogen produced was then used as fuel for an integrated PEMFC.     

Hydrogen production from biogas using hot slag

Possibility of hydrogen production from biogas using hot slag has been studied, in which decomposition rate of _CO2${\mathrm{CO}}_2$–_CH4${\mathrm{CH}}_4$ in a packed bed of granulated slag was measured at constant flow-rate and pressure. The molten slag, discharged at high temperature over 1700 K from smelting industries such as steelmaking or municipal waste incineration. It has enough potential for replacing energy required for hydrogen production due to the catalytic steam reforming or carbon decomposition of hydrocarbon. However, heat recovery of hot slag has never been established. Therefore, the objective of this work is to generate hydrogen from methane using heated slag particles as catalyst, in which the effect of temperature on the hydrogen generation was mainly investigated at range from 973 to 1273 K. In the experiments a mixed gas of _CH4${\mathrm{CH}}_4$ and _CO2${\mathrm{CO}}_2$ was continuously introduced into the packed bed of hot slag at constant flow-rate and atmospheric pressure and then the outlet gas was monitored by gas chromatography. The results indicate that slag acted as not only thermal media but also good catalyst, for promoting decomposition. The product gases were mainly hydrogen and carbon monoxide with/without solid carbon deposition on the surface of slag, depending on the reaction temperature. Increasing temperature led to large hydrogen generation with decreasing un-reacted methane in the outlet gas, at when the largest methane conversion was about 96%. The results suggested a new energy-saving process of hydrogen production, in which the waste heat from molten slag can replace the energy required for hydrogen production, reducing carbon dioxide emission.     

Hydrogen production by using manganese ferrite: Evidences and benefits of a multi-step reaction mechanism

Hydrogen production by water splitting with _MnFe2O4/_Na2CO3${\mathrm{MnFe}}_2{\mathrm{O}}_4/{\mathrm{Na}}_2{\mathrm{CO}}_3$ system was studied at 973 K. An intermediate phase, resulting from decarbonatation of _MnFe2O4/_Na2CO3${\mathrm{MnFe}}_2{\mathrm{O}}_4/{\mathrm{Na}}_2{\mathrm{CO}}_3$ mixture in inert atmosphere, proved to be effective in hydrogen reduction from water with stoichiometric yield. The presence of a highly reactive intermediate phase suggests the feasibility of a high efficiency, three-step, thermochemical cycle for hydrogen production. In fact, the possibility of obtaining _CO2${\mathrm{CO}}_2$ separately from the gases mixture dramatically enhances process efficiency.     

Lifecycle impacts of natural gas to hydrogen pathways on urban air quality

In this paper we examine the potential air quality impacts of hydrogen transportation fuel from a lifecycle analysis perspective, including impacts from fuel production, delivery, and vehicle use. We assume that hydrogen fuel cell vehicles are introduced in a specific region, Sacramento County, California. We consider two levels of market penetration where 9% or 20% of the light duty fleet are hydrogen fuel cell vehicles. The following three natural gas to hydrogen supply pathways are assessed in detail and compared in terms of emissions and the resulting changes in ambient air quality: (1) onsite hydrogen production; (2) centralized hydrogen production with gaseous hydrogen pipeline delivery systems; and (3) centralized hydrogen production with liquid hydrogen truck delivery systems. All the pathways examined use steam methane reforming (SMR) of natural gas to produce hydrogen. The source contributions to incremental air pollution are estimated and compared among hydrogen pathways. All of the hydrogen pathways result in extremely low contributions to ambient air concentrations of _NOx${\mathrm{NO}}_x$, CO, particulates, and _SOx${\mathrm{SO}}_x$, typically less than 0.1% of the current ambient pollution for both levels of market penetration. Among the hydrogen supply options, it is found that the central SMR with pipeline delivery systems is the lowest pollution option available provided the plant is located to avoid transport of pollutants into the city via prevailing winds. The onsite hydrogen pathway is comparable to the central hydrogen pathway with pipeline systems in terms of the resulting air pollution. The pathway with liquid hydrogen trucks has a greater impact on air quality relative to the other pathways due to emissions associated with diesel trucks and electricity consumption to liquefy hydrogen. However, all three hydrogen pathways result in negligible air pollution in the region.     

Analysis of the benefits of carbon credits to hydrogen addition to midsize gas turbine feedstocks

The addition of hydrogen to the natural gas feedstocks of midsize (30–150 MW) gas turbines was analyzed as a method of reducing nitrogen oxides (_NOx)$({\mathrm{NO}}_x)$ and _CO2${\mathrm{CO}}_2$ emissions. In particular, the costs of hydrogen addition were evaluated against the combined costs for other current _NOx${\mathrm{NO}}_x$ and _CO2${\mathrm{CO}}_2$ emissions control technologies for both existing and new systems to determine its benefits and market feasibility. Markets for _NOx${\mathrm{NO}}_x$ emissions credits currently exist in California and the Northeast States and are expected to grow. Although regulations are not currently in place in the United States, several other countries have implemented carbon tax and carbon credit programs. The analysis thus assumes that the United States adopts future legislation similar to these programs. Therefore, potential sale of emissions credits for volunteer retrofits was also included in the study. It was found that hydrogen addition is a competitive alternative to traditional emissions abatement techniques under certain conditions. The existence of carbon credits shifts the system economics in favor of hydrogen addition.     

Reactor concept for improved heat integration in autothermal methanol reforming

With regard to mobile applications, the autothermal methanol reforming process as hydrogen source for PEM-fuel cells has advantages compared to the externally heated steam reforming reaction in terms of control and transient behaviour. However, thermal (hot-spot) control of the autothermal process turns out to be the key issue for scale-up in order to ensure selectivity, catalyst stability and process safety. Therefore, a novel reactor concept based on flow redirection around catalytically coated plates has been developed. It shows a low pressure drop, improves heat integration and solves the scale-up problem of autothermal processes like autothermal methanol reforming. These improvements have been shown in experiments using Cu/Zn/_Al2O3$\mathrm{Cu}/\mathrm{Zn}/{\mathrm{Al}}_2{\mathrm{O}}_3$ as catalyst.     

Impact of hydrogen on the environment

The present work considers the impact of hydrogen fuel on the environment within the cycles of its generation and combustion. Hydrogen has been portrayed by the media as a fuel that is environmentally clean because its combustion results in the formation of harmless water. However, hydrogen first must be generated. The effect of hydrogen generation on the environment depends on the production process and the related by-products. Hydrogen available on the market at present is mainly generated by using steam reforming of natural gas, which is a fossil fuel. Its by-product is CO₂, which is a greenhouse gas and its emission results in global warming and climate change. Therefore, hydrogen generated from fossil fuels is contributing to global warming to the similar extent as direct combustion of the fossil fuels. On the other hand hydrogen obtained from renewable energy, such solar energy, is environmentally clean during the cycles of its generation and combustion. Consequently, the introduction of hydrogen economy must be accompanied by the development of hydrogen that is environmentally friendly. The present work considers several aspects related to the generation and utilisation of hydrogen obtained by steam reforming and solar energy conversion (solar-hydrogen).     

Thermal efficiency evaluation of open-loop SI thermochemical cycle for the production of hydrogen,sulfuric acid and electric power

Total thermal efficiency of a new open-loop SI thermochemical cycle for the production of hydrogen, sulfuric acid and electric power was investigated. The new system without _CO2${\mathrm{CO}}_2$ emission is composed of sulfuric acid industry process which provides the chemical reactant _SO2${\mathrm{SO}}_2$ and heat, electric energy demands of the system and SI open-loop cycle separated into the Bunsen reaction system, the _HIx${\mathrm{HI}}_x$ system and the _H2SO4${\mathrm{H}}_2{\mathrm{SO}}_4$ concentration system. The selection of SI cycle to run in an open-loop fashion for China is tied-up with two important facts: (1) sulfur iron ore as _SO2${\mathrm{SO}}_2$ source is inexpensive and abundantly available; (2) the product sulfuric acid, in addition to hydrogen, is valuable and marketable. The mass and heat balance of the process were calculated with the optimized conditions. Thermal efficiency for hydrogen production was 66.3% with ideal operating conditions of the EED cell and heat exchangers in the case of generating electric power without waste heat and was 70.9% in the case of high performance waste heat recovery.     

Hydrogen generation from liquid phase catalytic reforming of sugar solutions using metal-supported catalysts

Most of the hydrogen production processes are designed for large-scale industrial uses and are not suitable for a compact hydrogen device to be used in systems like solid polymer fuel cells. Integrating the reaction step, the gas purification and the heat supply can lead to small-scale hydrogen production systems. The aim of this research is to study the influence of several reaction parameters on hydrogen production using liquid phase reforming of sugar solution over Pt, Pd, and Ni supported on nanostructured supports. It was found that the desired catalytic pathway for _H2${\mathrm{H}}_2$ production involves cleavage of C–C, C–H and O–H bonds that adsorb on the catalyst surface. Thus a good catalyst for production of _H2${\mathrm{H}}_2$ by liquid-phase reforming must facilitate C–C bond cleavage and promote removal of adsorbed CO species by the water–gas shift reaction, but the catalyst must not facilitate C–O bond cleavage and hydrogenation of CO or _CO2${\mathrm{CO}}_2$. Apart from studying various catalysts, a commercial Pt/γ$\gamma$-alumina catalyst was used to study the effect of temperature at three different temperatures of 458, 473 and 493 K. Some of the spent catalysts were characterised using TGA, SEM and XRD to study coke deposition. The amorphous and organised form of coke was found on the surface of the catalyst.     

Hydrogen perspectives in Italy: Analysis of possible deployment scenarios

The paper analyses Italian hydrogen scenarios to meet climate change, environmental and energy security issues. An Italy-Markal model was used to analyse the national energy–environment up to 2050. About 40 specific hydrogen technologies were considered, reproducing the main chains of production, transport and consumption, with a focus on transport applications. The analysis is based on the Baseline and Alternative scenario results, where hydrogen reaches a significant share. The two scenarios constitute the starting points to analyse the hydrogen potential among the possible energy policy options. The energy demand in the Baseline scenario reaches values around 240 Mtoe at 2030, with an average annual growth of 0.9%. The Alternative scenario reduces consumption down to 220 Mtoe and stabilizes the _CO2${\mathrm{CO}}_2$ emissions. The Alternative scenario expects a rapid increase of hydrogen vehicles in 2030, up to 2.5 million, corresponding to 1 Mtoe of hydrogen consumption. A sensitivity analysis shows that the results are rather robust.     

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.     

Hydrogen economy in Taiwan and biohydrogen

This study analyzed how production technology advances and how economic structure reformation affects transition to a hydrogen economy in Taiwan before 2030. A model, called “Taiwan general equilibrium model-energy, for hydrogen (TAIGEM-EH)”, was the forecast tool used to consider steam reforming of natural gas, the biodegradation of biomass and water electrolysis using nuclear power or renewable energies of hydrogen production industries. Owing to increase in the prices of oil and concern for global warming effects, hydrogen will have a 10.3% share in 2030 when demands for hydrogen production could be met if strong technological progress in hydrogen production were made. With reformed economic structure and strong support to progress in production technologies, hydrogen's share can reach 22.1% in 2030 and become the dominating energy source from then onwards. In the four scenarios studied, including developing country with three levels of effort and developed country with strong effort, the biohydrogen production industry can become a main supplier of hydrogen in the market if its technological progress can be competitive to other _CO2${\mathrm{CO}}_2$-free alternatives.     

Experimental investigation on the effect of natural gas composition on performance of autothermal reforming

This paper presents experimental study on catalytic autothermal reforming (ATR) of natural gas (NG) for hydrogen (_H2${\mathrm{H}}_2$) production over sulfide nickel catalyst supported on gamma alumina. The experiments are conducted on a cylindrical reactor of 30 mm in diameter and 200 mm in length with “simulated” NG of different composition under thermal-neutral conditions and fed with different molar air to fuel ratio (A/F$A/F$) and molar water to fuel ratio (W/F)$(W/F)$. The results showed that reforming performance is significantly dependent on A/F$A/F$, W/F$W/F$ and concentration of _C2+${\mathrm{C}}_{2+}$ hydrocarbons in inlet fuel. Fuels containing higher _C2+${\mathrm{C}}_{2+}$ hydrocarbons concentration have optimum performance in terms of more _H2${\mathrm{H}}_2$ at higher A/F$A/F$ and W/F$W/F$ but lower conversion efficiency. Good performance for ATR of fuel containing 15%–20% _C2H6${\mathrm{C}}_2{\mathrm{H}}_6$ can be achieved at A/F=5–7$A/F=5–7$ and W/F=4–6$W/F=4–6$, much higher than that for optimum performance of ATR of methane (A/F=3,W/F=2–2.5$A/F=3,W/F=2–2.5$). _CO2${\mathrm{CO}}_2$ in the inlet fuel does not have significant effect on the reversed water–gas shift reaction. Its effect on reforming performance is mainly due to the dilution of inlet fuel and products.