Fluidized Bed Steam Reforming Research Articles

Influence of indirectly heated steam-blown gasification process conditions on biochar physico-chemical properties

Our work provides a thorough characterization of different biochars produced by a novel 50 kWth Indirectly Heated Bubbling Fluidized Bed Steam Reformer. This study investigates the effect of temperature and gasification agent on the physico-chemical properties of biochars. We combined macro, micro and nano characterization techniques to provide a clear picture of the biochar characteristics, surface functionality and its “inert” nature toward potential applications. Our results demonstrate that indirect gasification is capable of producing carbon-rich biochars (> 92%) with increased porosity (89–198 cm3.g−1), high heating value (28–31 MJ.kg−1 a.r.) and aromaticity compared to the parent biomass. All biochars have lower O/C (0.02–0.04) and H/C atomic ratios (0.09–0.19), similar to anthracite. For the range of tested gasification conditions, air/steam gasification at an equivalence ratio of 0.20 and steam-to-biomass ratio of 1.2 provides the highest biochar yield (7.3%), while maintaining syngas composition optimal. On the other hand, air gasification produces biochars with relatively high content of inorganic elements. Indirectly heated biochars are compliant with the European Biochar Certificate regarding the carbon content, O/C ratio, H/C ratio. Our biochars may provide an improvement in agricultural yield and CO2 adsorption, especially those produced under air/steam gasification conditions. Our novel indirect design not only constitutes a promising development in the field of biomass allothermal gasification but also can help improving gasification circularity through the production of high quality biochar.

Two phase modelling of Geldart B particles in a novel indirectly heated bubbling fluidized bed biomass steam reformer

This work focuses on the numerical modelling and experimental validation of the hydrodynamic behaviour of a novel 50 kWth indirectly heated bubbling fluidized bed steam reformer. The hydrodynamic behaviour of fluidized beds with immersed vertical tubes and complex fluidized bed geometries in general have not been thoroughly investigated in terms of numerical modelling coupled with experimental validation for pilot scale reactors. Therefore, the present study contributes to the fluidized bed hydrodynamics numerical modelling field, while investigating a novel reactor concept. Simulations were performed employing the Two-Fluid Model approach, using the Kinetic Theory of Granular Flows (KTGF) and the adjusted Syamlal O’Brien drag model. The reactor’s hydrodynamic behaviour was simulated successfully, as showcased by a comparison of global hydrodynamic metrics (bed height, pressure drop) between computational and experimental results. Simulations were performed with and without considering an additional nitrogen gas feed on the side of the reactor (feeding system pressurization). Overall, for both cases, for realistic values of the particle restitution coefficient channelling of the gas flow near the reactor walls was observed. Larger bubbles appeared to be forming near the outer wall of the reactor for the no side-flow simulations. The opposite behaviour was encountered for the side-flow simulations due to stream-like behaviour of the side-flow moving up against the reactor’s outer wall. The choice to limit the simulations to a 72° symmetry domain was validated, indicating the possibility of further reduction. Finally, it was argued that increasing the reactor’s diameter could potentially lead to a reduction of the observed channelling of the fluidization media and improve the mixing achieved in the reactor and thus the conversion efficiency of the IHBFBSR during gasification applications.

Gasification of woody biomass in a novel indirectly heated bubbling fluidized bed steam reformer

Within this work, a novel 50 kWth indirectly heated bubbling fluidized bed steam reformer (IHBFBSR) is presented, along with its commissioning experiments. In the IHBFBSR, heat is provided through two radiant tube natural gas burners in the bed and the freeboard area. The aim of this innovative design is sufficient heat provision for biomass steam reforming and cracking reactions and heat loss reduction, thus allowing the possibility of scaling-up to an industrial level. Experiments were performed with two woody biomass feedstocks and two bed material particle sizes under different operating conditions (steam to biomass ratio, lambda, temperature), in order to identify the setup's main characteristics. Product gas composition and quality, as well as the cold gas efficiency of the IHBFBSR were in reasonable agreement to similar systems, however carbon conversion prediction needs further improvement. H2 production and tar removal are favoured by small bed material particle sizes as well as by char accumulation in the bed area. Furthermore, air injection above the bed led to improved H2/CO ratios and lower tar yields compared to when air is used as a fluidization agent. Overall, it was shown that the IHBFBSR technology constitutes a promising development in the field of biomass allothermal gasification.

Enhancement of Hydrogen Production by Fluidization in Industrial-Scale Steam Reformers

In this paper, the effect of the fluidization concept on the performance of methane steam reforming has been investigated by comparing a fluidized-bed steam reformer (FBSR) with an industrial-scale conventional steam reformer (CSR). Also, a fluidized-bed thermally coupled steam reformer (TCFBSR) and a fixed-bed thermally coupled steam reformer (TCSR) have been compared. In thermally coupled reactors, the hydrogenation of nitrobenzene to aniline exothermic reaction is employed. A steady state one dimensional heterogeneous model is applied to analyze methane conversion and hydrogen production for steam reforming of methane in different reactors (CSR, FBSR, TCSR, and TCFBSR). The modeling results show that, in FBSR, hydrogen production and methane conversion are increased by 2.13 and 0.52%, respectively, in comparison with CSR. Also, by using fluidized catalysts instead of fixed ones in TCSR, methane conversion and hydrogen yield are increased from 0.2776 to 0.2934 and from 0.9649 to 0.9836, respectively. These improvements represent the appropriate effect of the fluidization concept on the enhancement of hydrogen production in different steam reformers.

Mineral assemblage transformation of a metakaolin-based waste form after geopolymer encapsulation

Mitigation of hazardous and radioactive waste can be improved through conversion of existing waste to a more chemically stable and physically robust waste form. One option for waste conversion is the fluidized bed steam reforming (FBSR) process. The resulting FBSR granular material was encapsulated in a geopolymer matrix referred to here as Geo-7. This provides mechanical strength for ease in transport and disposal. However, it is necessary to understand the phase assemblage evolution as a result of geopolymer encapsulation. In this study, we examine the mineral assemblages formed during the synthesis of the multiphase ceramic waste form. The FBSR granular samples were created from waste simulant that was chemically adjusted to resemble Hanford tank waste. Another set of samples was created using Savannah River Site Tank 50 waste simulant in order to mimic a blend of waste collected from 68 Hanford tank. Waste form performance tests were conducted using the product consistency test (PCT), the Toxicity Characteristic Leaching Procedure (TCLP), and the single-pass flow-through (SPFT) test. X-ray diffraction analyses revealed the structure of a previously unreported NAS phase and indicate that monolith creation may lead to a reduction in crystallinity as compared to the primary FBSR granular product.

Catalytic steam reforming of butanol in a fluidized bed and comparison with other oxygenated compounds

Fluidized bed steam reforming of butanol was studied at 650°C, atmospheric pressure and a steam to carbon (S/C) molar ratio of 14.7. The influence of the space velocity (GC1HSV) was tested with different catalysts. The use of a Ni/Al catalyst with 28.5wt.% Ni content gave almost equilibrium conditions at a GC1HSV of around 11000h−1. At higher GC1HSV values, carbon conversion to gas and gas yields diverged from equilibrium values. The catalyst composition was also analysed using several Ni/Al research catalysts modified with Ca or Mg, studying their effect on the nickel reducibility and activity. A comparative study of steam reforming of oxygenated compounds (butanol, ethanol, acetol and acetic acid) was also carried out. The steam reforming of alcohols showed high stability over time in comparison to the other compounds. The characterization of used catalysts by FESEM and TPO showed a greater proportion of refractory carbon when using acetic acid and acetol in comparison to the alcohol steam reforming which, in addition, presented less carbon content on the catalyst surface.

Hydrodynamics of a Novel Design Circulating Fluidized Bed Steam Reformer Operating in the Dense Suspension Upflow Regime

Circulating fluidized bed steam reformers (CFBSR) represent an important alternative for hydrogen production, a promising energy carrier. Although the reactor hydrodynamics play crucial role, modeling efforts to date are limited to one-dimensional models, thus ignoring many of the flow characteristics of fluidized beds that have strong effects on the reactor efficiency. The flow inside the riser is inherently complex and requires at least two-dimensional modeling to capture its details. In the present work, the computational fluid dynamics (CFD) simulations of the hydrodynamics of the riser part of a novel CFBSR were carried out using two-phase Eulerian-Eulerian approach coupled with kinetic theory of granular flow and K-ε model. Cold flow simulations were carried under different fluidization regimes. It was found that catalyst of Geldart's type “A” particle is more efficient for flow inside the catalytic reactor and dense suspension upflow (DSU) fluidization regime yields the best homogeneous catalyst distribution in the riser and thus best reactor performance. The optimum range for catalyst flux was found to be higher than 1150 kg/m2·s for a gas flux of 6.78 kg/m2·s. It was also noted that the value of 500 Kg/m2·s for catalyst flux represents the critical value below which the riser will operate under pneumatic transport regime.

Pilot Scale Production of Mixed Alcohols from Wood

An integrated thermochemical biomass to ethanol process was demonstrated at the pilot scale at the National Renewable Energy Laboratory (NREL). A total of 233 h of pilot scale mixed alcohol production was achieved, comprising 81 h of continuous operation in methanol-derived syngas followed by 152 h of continuous operation in biomass-derived syngas. During this period the system generated 20 L of mixed alcohol product. The fully integrated biomass to mixed alcohol process was comprised of a solids feeder, fluidized bed indirect steam gasifier, thermal cracker, char collector, fluidized bed steam reformer, packed bed polishing steam reformer, scrubber, pressure-swing CO2 adsorber, and gas-phase continuously stirred tank gas-to-liquid reactor (CSTR). Additional pumps, compressors, and blowers were used to convey gases, solids, and liquids. Tars and methane were reformed using sequential steps: first in a fluidized bed using an NREL-developed Ni-based catalyst followed by a fixed bed reactor loaded with pelle...

Performance of the Fluidized Bed Steam Reforming product under hydraulically unsaturated conditions

Several candidates for supplemental low-activity waste (LAW) immobilization at the Hanford site in Washington State, USA are being considered. One waste sequestering technology considered is Fluidized Bed Steam Reforming (FBSR). The granular product resulting from the FBSR process is composed primarily of an insoluble sodium aluminosilicate matrix with the dominant phases being feldspathoid minerals with a 1:1:1 molar ratio of Na, Al and Si. To demonstrate the durability of the product, which can be disposed of at the unsaturated Integrated Disposal Facility (IDF) at Hanford, a series of tests has been performed using the Pressurized Unsaturated Flow (PUF) system, which allows for the accelerated weathering of the solid materials. The system maintains hydraulically unsaturated conditions, thus mimicking the open-flow and transport properties that will be present at the IDF. Two materials were tested using the system: 1) the FBSR granular product and 2) the FBSR granular product encapsulated in a geopolymer to form a monolith. Results of the experiments show a trend of relatively constant effluent concentration of Na, Si, Al, and Cs as a function of time from both materials. The elements I and Re show a steady release throughout the yearlong test from the granular material but their concentrations seem to be increasing at one year from the monolith material. This result suggests that these two elements may be present in the sodalite cage structure rather than in the predominant nepheline phase because their release occurs at a different rate compared to nepheline phase. Also, these elements to not seem to reprecipitate when released from the starting material. Calculated one-year release rates for Si are on the order of 10−6 g/(m2 d) for the granular material and 10−5 g/(m2 d) for the monolith material while Re release is seen to be two orders of magnitude higher than Si release rates. SEM imaging and XRD analysis show how the alteration of the two materials is dependent on their depth in the column. This phenomenom is a result of depth-dependent solution concentrations giving rise chemical environments that may be supersaturated with respect to a number of mineral phases.

Opportunities for Advanced Ceramics and Composites in the Nuclear Sector

Ceramics have played a crucial role in the development of fission based nuclear power, in glass & glass composite high level wasteforms, in composite cements to encapsulate intermediate level wastes (ILW) and also for oxide nuclear fuels based on UO2 and PuO2/UO2 mixed oxides. They are also used as porous filters with the ability to absorb radionuclides (RN) from air and liquids and are playing a key role in the cleanup at Fukushima. Non‐oxides also find current fission applications including in graphite moderators and B4C control rods. Ceramics will continue to be significant in the near‐term expansion of nuclear power via next‐step developments of fuels with inert matrices or based on thoria and in wasteforms using alternative composite cements or single or multiphase ceramics that can host Pu & other difficult RN. Longer term advances for Generation IV reactors, which will operate at higher temperatures & with higher fuel burn‐up require innovative fuel developments potentially via carbides & nitrides or composite fuel systems. Novel non‐thermal (cement‐like) and thermal techniques are currently being developed to treat some of the difficult legacy wastes. Non‐thermally derived wasteforms developed from geopolymers, composite cements, hydroceramics, and phosphate‐bonded ceramics and thermally derived wasteforms made by Hot Isostatic Pressing and fluidized bed steam reforming (FBSR) as well as vitrification techniques based on cold crucible melting (CCM), Joule‐heater in‐container melting and plasma melting (PM) are described. Future developments in waste treatment will be based on separation technologies for partitioning individual RN along with design & construction of RN‐containing ceramic targets for inducing transmutation reactions. Near demonstration actinide‐hosting ceramic wasteforms including multiphase Synroc systems are described. Opportunities also exist for ceramics in structural applications in Generation IV reactors such as composite SiC/SiC and C/C for fuel cladding and control rods and MAX phases and ultrahigh‐temperature ceramics (UHTCs) may find near core fuel coating and cladding applications. Uses of ceramics in fusion reactor systems will be both functional (ceramic superconductors in magnet systems for plasma control and in Li silicate breeder blankets in tokamaks) and structural including as sapphire diagnostic windows, graphite diverters, and plasma facing C and UHTCs. In all these cases, performance is limited by poorly understood radiation damage and interface controlled processes, which demands a combined modeling/experimental approach.

Hydrodynamic Characteristics of a Novel Circulating Fluidized Bed Steam Reformer Operating in the Fast Fluidization Regime

Circulating Fluidized Bed Steam Reformers (CFBSRs) represent an important alternative for the production of syngas for the Fisher-Tropsch (FT) process and for hydrogen production. Most research regarding this novel CFBSRs did not consider its hydrodynamic characteristics. In this work, the riser Computational Fluid Dynamics (CFD) simulations were investigated using two phase Eulerian-Eulerian approach coupled with kinetic theory of granular flow with k-epsilon model to describe the turbulence of each phase. The model equations were solved via the commercial CFD package FLUENT, which uses the finite volume numerical approach. Cold flow simulations were carried out under the fast fluidization regime and results were validated qualitatively against available experimental data. The radial segregation of the catalyst, the velocity distribution of both phases and other characteristics of the flow were captured by the simulation. This work showed that for operation under high density and high flux conditions, solids flux should be higher than 300 kg/m2s and inlet void fraction lower than 85%.

Technoeconomic Analysis of a Lignocellulosic Biomass Indirect Gasification Process To Make Ethanol via Mixed Alcohols Synthesis

A technoeconomic analysis of a 2000 tonne/day lignocellulosic biomass conversion process to make mixed alcohols via gasification and catalytic synthesis was completed. The process, modeled using ASPEN Plus process modeling software for mass and energy calculations, included all major process steps to convert biomass into liquid fuels, including gasification, gas cleanup and conditioning, synthesis conversion to mixed alcohols, and product separation. The gas cleanup area features a catalytic fluidized-bed steam reformer to convert tars and hydrocarbons into syngas. Conversions for both the reformer and the synthesis catalysts were based on research targets expected to be achieved by 2012 through ongoing research. The mass and energy calculations were used to estimate capital and operating costs that were used in a discounted cash flow rate of return analysis for the process to calculate a minimum ethanol selling price of $0.267/L ($1.01/gal) ethanol (U.S.$2005).

Hydrogen production from fluidized bed steam reforming of hydrocarbons

Steam reforming of methane, kerosene and heavy oil over a nickel/alumina commercial catalyst and other materials such as limestone, dolomite and iron ore, was studied using a 5 cm i.d. fluidized bed reactor. The effects of operating parameters on conversion, hydrogen yield, product gas composition and elutriation of fine catalysts were investigated. It was found that a fluidized bed is flexible enough to handle various feedstocks, including hydrocarbons heavier than naphtha, because it permits the addition of catalyst to, or withdrawals of, coked catalyst from the bed. The yield of hydrogen obtained from fluidized bed steam reforming of heavy oil at 800‡C over limestone was similar to that obtained over commercial nickel-based catalyst. This indicates that limestone could be a promising catalyst for the production of hydrogen from heavy oil. However, hydrogen yield decreased with reaction time in the experiments using the limestone catalyst. The main cause of the decrease in hydrogen yield was elutriation of fine catalysts from the bed during the reaction.

Environmental Issues and Waste Management Technologies in the Ceramic and Nuclear Industries -II

Abstract