Analysis and Removal of Product Gas Contaminants Present in Gasification Processes

Energy demand and economic development are intrinsically linked. Earlier economic development came at the price of serious environmental pollution, posing a risk to life on earth. Thus, a transition from fossil to renewable energy is needed. Among the renewable energy technologies, gasification of biomass promises high process efficiency and flexibility concerning the feedstock and products. In such a process, gas contaminants have to be removed to protect downstream equipment and the environment. Finding an optimal configuration of process steps in gas cleanup chains, offering reliability, availability and high efficiency at low operating and capital costs is still a challenge and one of the major hurdles for commercial deployment of biomass gasification processes. This thesis aimed to investigate the gas cleanup chain as part of gasification processes. Two aspects, the analysis of gas contaminants and their elimination, were examined. At first, three analytical methods, aimed at the detection of sulphur containing hydrocarbons, tars and trace elements, were developed. In the next step, these analytical tools were employed to investigate the performance of gas cleanup units, intended for the removal of the sulphur containing hydrocarbon thiophene, tars and the trace element Se. The removal of thiophene by activated carbons (AC) was explored experimentally and theoretically. Experiments were performed in a packed bed column between 100-200°C. The adsorption process was described by a 1D approach, including mass transfer phenomena and axial dispersion. Experimental validation showed good agreement between measured and predicted breakthrough times and capacities. A global sensitivity analysis (GSA) was performed to rank the importance of model input factors and gain further process insight. The work showed that ACs are a promising option for thiophene removal and provided a generic approach for the application of GSA to adsorption models. In this context, the analysis demonstrated that the selection of common model assumptions deserves as much attention as the model parameters. Further work chapter aimed at understanding the effect of H2O, H2 and H2S on the decomposition of thiophene over CaO. Experiments were performed in a fixed bed reactor at 810°C. The factors were varied as part of a full factorial design at two levels. Results were fitted to a linear model with interactions. Analysis showed that H2O and H2S had a major effect on thiophene conversion, while that of H2 was less pronounced. Interactions between varied factors were found to be negligible. A UV-Vis method was developed to obtain online information on tar compound concentrations in real process gases in the low ppmv region. Spectra were analysed for their tar composition by two chemometric approaches. Applied to two case studies, the developed tool proved to be a rapid, sensitive tool, applicable to qualitative process monitoring with the added benefit of quantification in gases with a limited number of tar compounds. An ICP-MS was employed as a tool for the online detection of trace elements. The low detection limits (< 2 ppbv for H2Se, PH3; < 0.1 ppbv for AsH3; < 0.01 ppbv for Hg) and the high temporal resolution render this method a quick and robust tool for the performance evaluation of sorbent materials. A case study investigated the capture of H2Se by a Zn/Al2O3 sorbent between 150-350°C.

Novel structured adsorber and oxidation catalysts for the removal of VOCs in low concentration

Kim Martin Nikolajsen

One possibility for the removal of volatile organic compounds (VOCs) is catalytic oxidation. For the removal of VOCs in low concentration (≲ 3000 ppmv for propane) it is not possible to sustain the required oxidation temperature over the catalyst without external heating. An approach to overcome this problem is to concentrate the VOC by adsorption, in a "two-step adsorption-incineration" process. This is an unsteady state process in which the VOC laden effluent gas is cleaned by passing it through an adsorber. Once the adsorber is saturated the VOC is desorbed by heating and purging. The concentrated VOC from the desorber can then be oxidized over the catalyst, producing enough heat to sustain the oxidation temperature. Conventional adsorbents have some drawbacks such as tailing during desorption due to the large particle size, high pressure drop and hot-spot formation. The objective of this work was to develop, characterize and test the adsorbent and catalyst, with low resistance to mass transfer resulting from thin films of active material, for the two-step adsorption-incineration process. Both the adsorbent and the oxidation catalysts were supported on sintered metal fibers (SMF). This is a novel, structured support offering several advantages over conventional randomly packed beds: Low pressure drop, due to the high porosity of the SMF, which is important where large flow rates and/or high quantities of gas must be treated. High thermal conductivity, due to the metallic nature, leading to smaller temperature gradients in the fixed-bed. A very high geometric surface area, due to the small fiber size. On the order of 200,000 m2/m3 with a fiber diameter of 20 µm. Furthermore, a mathematical model was developed to show the feasibility of the coupling of the two steps in the process. The adsorber was made from a thin, homogeneous film of MFI-type zeolite covering the fibers of the SMF. The film was grown by the seed-film method by hydrothermal treatment. A 3 µm film was obtained with 10 wt.% zeolite on the fiber after 24 h synthesis at 125 °C. This material had a specific surface area of 30 m2/g. The adsorption equilibrium of propane was described well by the Langmuir isotherm and the heat of adsorption was found to be ΔH0ads = - 43.1 kJ/mol. Isothermal breakthrough curves were measured as a function of temperature and film thickness. A mathematical model, comprised of a tanks-in-series model with a linear driving force (LDF) mass transfer description, successfully described the breakthrough behavior. The overall mass transfer was found to be solely due to diffusion in the zeolite film. However, the thin films show very low resistance to mass transfer leading to low internal concentration gradients and efficient utilization of the adsorbent. The pressure drop was measured and compared to that of a randomly packed fixed-bed of spheres. The equivalent diameter for a constant volumetric flow rate and superficial cross sectional area was dp = 180 µm, for a fiber diameter of df = 26 µm at 10 wt.% zeolite loading. The oxidation catalysts were all supported on SMF and cobalt oxide was used as the active phase. Three different groups of catalysts were developed. The support was modified by coating the fibers either with a thin film of fine powder (alumina or catalyst powder) or with a MFI-type zeolite film identical to the adsorbent. The third group was made from cobalt oxide impregnated directly on the oxidized fibers. The latter type of catalyst was found to be the most active during the screening experiments. The base support composition was varied (stainless steel (SS), FeCrAlloy and inconel) to investigate the support effect on the kinetics. The stainless steel and FeCrAlloy supports had similar activities, surpassing that of the inconel supported catalyst, which might be attributed to a Co3O4 surface enriched with iron from the support. Between the 1.1 wt.%Co3O4/SMFSS and 1.5 wt.%Co3O4/SMFFeCrAlloy catalyst the FeCrAlloy based had the highest normalized activity at low temperature (< 310 °C), low propane mole fraction (0.13 %) and high oxygen mole fraction (16.7 %). The chemical kinetics were determined from a novel and efficient experimental design. The apparent activation energy for this catalyst was found to be 87.5 ± 2.6 kJ/mol, with reaction orders in propane of 0.38 ± 0.04 and in oxygen of 0.30 ± 0.08. The catalysts were tested up to 350 °C. Mass transfer limitations were absent and the kinetics was described well with the power rate law as compared to the Mars-van Krevelen model. Catalysts based on Co3O4, supported directly on oxidized SMF, are very active catalysts, simple to prepare, withstand deactivation due to hot-spot formation and show great potential in comparison to the industrial reference catalyst (copper and manganese oxide supported on alumina). The adiabatic desorption process was investigated by mathematical modeling. Simply purging the adsorption bed with the hot exhaust gas from the reactor cannot result in the concentration of the VOC due to the high heat capacity of the fixed-bed. Hence, it will be necessary to use either a high heat carrier like steam, with the adverse effects of drying and separation of water and VOC, or an approach in which the desorber is heated prior to purging the bed, changing the adsorption equilibrium in favor of high gas concentrations. For the latter method, the minimum theoretical propane mole fraction for an autothermal process was found to be 350 ppmv to sustain a catalytic incinerator at 250 °C. Finally, it can be concluded that for the first time zeolite films on SMF were used as structured adsorbents, leading to very low internal mass transfer and increased process efficiency. Furthermore, the advantages of the SMF can be exploited in a catalytic oxidizer, which can be combined with the adsorber to annihilate VOCs in low concentrations. A novel method for the deposition of fine powder catalyst on SMF was also developed for the first time.

EPFL2007

Identification of parameters affecting the outcome of biochemical methane potential (BMP) tests

Jonas Stöckli

Anaerobic digestion of organic waste to methane gas (CH4) is an attractive method to produce renewable energy. Due to the trend towards the reuse of waste and away from fossil energy sources, this technology saw a worldwide development in the recent years. A fundamental parameter in this domain is the Biochemical Methane Potential (BMP), which defines the amount of CH4 which can be produced out of a certain organic substrate. Such information is essential in order to plan and optimise anaerobic digestion plants, and to evaluate the reactor feed with a new substrate or a new substrate combination (co-digestion). BMPs are assessed in batch test, which can be regarded as the simulation of a full-scale biogas plant. Two experiments are required, the test in which the test substrate is digested on the inoculum, and the blank, in which the inoculum is digested alone. The part of the inoculum which can be digested is called endogenous substrate. Since the test experiment produced not only on the test substrate but only on the endogenous substrate, the CH4 production on the test substrate alone is obtained by the subtraction of the test production minus the blank production. The units of a BMP are generally indicated in litre of CH4 per gram of volatile solids (VS) test substrate [L/gVS]. Despite the importance and the wide application of this parameter, its exact determination remains a challenging issue and results are often not consistent in between (inter-) and within (intra-) laboratories. Experimental protocols exist but do not lead to a satisfactory BMP tests consistency neither. The aim of this study was to identify parameters affecting the outcome of BMP tests, based on the investigation of two different data sets. An inter-laboratory study of BMP tests providing the final BMP values of 327 experiments and information about 40 related experimental parameters, and a second data set containing the complete CH4 production curves of 136 BMP experiments provided by one single laboratory. The method consisted in graphical and statistical analysis (Mixed Effect Modelling), using [R] programming language and software environment. This study found out, that a significant part of the inter-laboratory BMP inconsistency can be explained by an imprecise assessment of the VS, which was not expected. As the VS of the substrate are directly implied in the computation of the BMP, the impact was significant and therefore the BMP were corrected regarding the VS imprecision. With these data, up to 70% of the inconsistency of BMPs could be explained by inter-laboratory effects. The statistical analysis led to the conclusion that the concentration of the endogenous substrate and the moisture content in the digestate would be the principal factors affecting the outcome of BMP tests. An effort was made to identify and correct errors contained in CH4 production curves, which turned out to be delicate for certain cases. Also indications regarding the precision and the reliability of BMPs were formulated. Further, the investigation of the CH4 production curves led to the development of a new method in order to compute the BMP result. This method was based on the fact, that a certain inoculum reaches always the same slope toward the end of the experiment, no matter what was digested before. The advantage of this method would be that the experiment end-point could be set clearly and that the concentration of the endogenous substrate would not have an impact on the outcome of a BMP test. According to the findings of this report, it was proposed to add the following requirements into experimental protocols for BMP tests: Tests, blanks and the analysis of VS should be carried out in triplicates and their standard deviation should be indicated for each of them, together with the BMP result If triplicates contain set-up errors, these experiments must be repeated, including the corresponding blank/test In the annex: An experimental protocol for the TS and VS analyses An indication of a required moisture content of the digestate (mechanism to investigate in detail first) An indication of the range of required VS concentrations or a maximal production rate for blank tests according to certain experimental conditions (mechanism to investigate in detail first). This report identified several parameters, which contribute to the inter-laboratory inconsistency of BMPs. These findings should be investigated further in order to prove and quantify their impact. An effort should be made to demonstrate the newly developed BMP-computation-method, which could eventually lead to more consistent results. The limitation of this study was, that a relatively low amount of data was available compared to their characteristics. Consequently, the findings could only be proven on a few examples and should therefore only be seen as evidences. Further, this led also to the risk of overfitting, since a relative high amount of parameters needed to be included into the statistical model.

2012

Realization and study of InAs/GaAs quantum dot superluminescent diodes emitting at 1.3µm

Marco Rossetti

A quantum dot is a semiconductor nanostructure that confines the motion of conduction band electrons and valence band holes in all three spatial directions, thus creating fully discrete energy levels. The confinement in the InAs/GaAs material system is generated by the bandgap difference for the two materials (∼ 0.4 eV for InAs, and ∼ 1.4 eV for GaAs) which provides a minimum of potential energy for both electrons and holes inside the InAs nanoparticle. The appearance of new nanoscale effects modifies the electro-optical properties of such a system which makes possible the improvement of existing device performance or even fascinating novel device applications. For the creation of coherent structures with very high purity and high density, as it is required for application in light emitting devices, self-assembling is a very important pathway. The quantum dot creation mostly relies on the relaxation of the strain accumulated during the growth of lattice mismatched materials, which happens in a non-equlibrium condition. This results in a statistical distribution of all the parameters characterizing the InAs nanocrystals as size, composition and strain, whose direct manifestation is the inhomogeneously broadened light emission deriving from quantum dot ensembles. At the dawning of the quantum dot development the broadening was considered as a limiting factor for application in semiconductor lasers. Today, it is considered favorably for all the applications where a broad gain spectrum is required as optical amplifiers, monolithic and external-cavity tunable lasers, and superluminescent diodes. The objective of this thesis is the application of InAs/GaAs self-assembled quantum dots to the active region of high power and broad-band superluminescent diodes emitting in the 1.3 μm wavelength region. Superluminescent diodes are edge-emitting semiconductor light sources based on the amplification of spontaneous emission along a waveguide where optical gain is achieved through current injection. They combine the high power and brightness of laser diodes with the low coherence of LEDs. The latter is a fundamental feature for the application in optical coherence tomography medical imaging, where the image resolution is related to the spectral bandwidth of the light source used. The achievement of bandwidths larger than 100 nm are demonstrated in this work through the optimization of molecular beam epitaxy growth conditions. This may be done optimizing the statistical size-dispersion of the dot ensemble, or through the use of different dot layers emitting at slightly different wavelengths. The large bandwidth emission is obtained also due to the peculiar energy structure of this material, for which a multi-state emission appears under particular injection conditions. As a term of comparison, best commercial single-chip superluminescent diodes for the imaging application at 1.3 μm show bandwidths around 60 nm. Moreover, the discrete nature of the energy levels in InAs quantum dots together with the implementation of a GaAs-based technology can be beneficial for the device temperature stability (the competing technology, based on InP, suffers from strong thermal degradation). The analysis and understanding of the device temperature characteristics will be detailed in the last chapter of the manuscript. Even though standard devices show an important temperature dependence, a better stability may be achieved through the use of p-doped active regions. In the last few years quantum dot devices have shown outstanding properties if compared to the competing quantum well technology. Low threshold currents, high temperature stability and low chirp in lasers, large bandwidths and low gain saturation in amplifiers have been demonstrated. However, in spite of the large interest among the scientific community, many of the microscopic processes at the origin of the electro-optical characteristics of this material are not completely understood yet. The physics of the quantum dot active material, will be modeled in this work through the use of systems of rate equations with different complexity depending on the system they are applied to. We will provide a mean-field rate equation model allowing to get insights about carrier dynamics in QD lasers. Also, we will develop two different traveling-wave rate equation models, one for the modeling of the L-I characteristics and the other for the modeling of the spectral characteristics of quantum dot superluminescent diodes. Considering the carrier and photon density distributions across the device cavity is essential in superluminescent diodes, where the high single pass gain results in large non-homogeneities of photon and carrier distributions. The work is motivated by an industrial cooperation with EXALOS AG, a leading company in the development, manufacturing, and sales of broadband superluminescent diodes.

EPFL2007

Novel structured adsorber and oxidation catalysts for the removal of VOCs in low concentration

Kim Martin Nikolajsen

EPFL2007

Identification of parameters affecting the outcome of biochemical methane potential (BMP) tests

Jonas Stöckli

2012

Realization and study of InAs/GaAs quantum dot superluminescent diodes emitting at 1.3µm

Marco Rossetti

EPFL2007