Rozprawy doktorskie na temat „Methane production”

This research investigates a novel approach to methanol production from methane. The high use of fossil fuels in New Zealand and around the world causes global warming. Using clearer, renewable fuels the problem could potentially be reduced. Biomass energy is energy stored in organic matter such as plants and animals and is one of the options for a cleaner, renewable energy source. A common biofuel is methane that is produced by anaerobic digestion. Although methane is a good fuel, the energy is more accessible if it is converted to methanol. While technology exists to produce methanol from methane, these processes are thermo-chemical and require large scale production to be economic. Nitrosomonas europaea, a nitrifying bacterium, has been shown to oxidize methane to methanol (Hyman and Wood 1983). This research investigates the possibility of converting methane into methanol using immobilized N. europaea for use in smaller applications. A trickle bed bioreactor was developed, containing a pure culture of N. europaea immobilized in a biofilm on ceramic raschig rings. The reactor had a biomass concentration of 7.82 ± 0.43 g VSS/l. This was between 4 – 15 times higher than other systems aimed at biologically producing methanol. However, the immobilization dramatically affected the methanol production ability of the cells. Methanol was shown to be produced by the immobilized cells with a maximum production activity of 0.12 ± 0.08 mmol/gVSS.hr. This activity was much lower than the typical reported value of 1.0 mmol/g dry weight.hr (Hyman and Wood 1983). The maximum methanol concentration achieved in this system was 0.129 ± 0.102 mM, significantly lower than previous reported values, ranging between 0.6 mM and 2 mM (Chapman, Gostomski, and Thiele 2004). The results also showed that the addition of methane had an effect on the energy gaining metabolism (ammonia oxidation) of the bacteria, reducing the ammonia oxidation capacity by up to 70%. It was concluded, because of the low methanol production activity and the low methanol concentrations produced, that this system was not suitable for a methanol biosynthesis process.

Most of the coal properties depend on carbon content and vitrinite reflectance, which are rank dependent parameters. In this study, a new approach was followed by constructing a simulation input database with rank-dependent coal properties published in the literature which are namely cleat spacing, coal porosity, density, and parameters related to strength of coal, shrinkage, swelling, and sorption. Simulations related to enhanced coalbed methane (ECBM) recovery, which is the displacement of adsorbed CH4 in coal matrix with CO2 or CO2/N2 gas injection, were run with respect to different coal properties, operational parameters, shrinkage and swelling effects by using a compositional reservoir simulator of CMG (Computer Modeling Group) /GEM module. Sorption-controlled behavior of coalbeds and interaction of coal media with injected gas mixture, which is called shrinkage and swelling, alter the coal properties controlling gas flow with respect to injection time. Multicomponent shrinkage and swelling effects were modeled with extended Palmer and Mansoori equation. In conclusion, medium-volatile bituminous coal rank, dry coal reservoir type, inverted 5-spot pattern, 100 acre drainage area, cleat permeability from 10 to 25 md, CO2/N2 molar composition between 50/50 % and 75/25 %, and drilling horizontal wells rather than vertical ones are better selections for ECBM recovery. In addition, low-rank coals and dry coal reservoirs are affected more negatively by shrinkage and swelling. Mixing CO2 with N2 prior to its injection leads to a reduction in swelling effect. It has been understood that elastic modulus is the most important parameter controlling shrinkage and swelling with a sensitivity analysis.

Sewage sludge is treated with the biological process of anaerobic digestion in which organic material of a substrate is degraded by microorganisms in the absence of oxygen. The result of this degradation is biogas, a mixture mainly of methane and carbon dioxide. Biochemical Methane Potential tests are used to provide a measure of the anaerobic degradability of a given substrate. This study aims to determine the methane potential in Sjöstadsverket’s sludge this will moreover determine the viability of recycling the digested sludge back into the anaerobic system for further digestion. Batch digestion tests were performed in both Sjöstadsverket’s (S1) and Henriksdal’s (H2) sludge, for a reliable comparison. An inoculum to substrate ratio of 2:1 based on VS content was used and BMP tests presented results that S1 and H2 in the 20 days of incubation produced 0.29 NLCH4/gVS and 0.33 NLCH4/gVS respectively. A second experiment considering the same amount of substrate (200ml) and inoculum (200ml) for each sample, showed that Control S1 had a higher methane potential than Control H2, 0.31 NL/gVS and 0.29 NL/gVS respectively. All the samples containing Sjöstadsverket’s inoculum presented a higher volume of total accumulated gas (measured in Normal Liters), however methane potentials are low. Results demonstrated that methane production in samples S1 and Control S1 was originating from the grams of VS in the inoculum itself after depletion of all the soluble organic material in the substrate. This suggested that Sjöstadsverket’s sludge can endure a higher organic load rate and that the digested sludge still has potential to produce biogas, hence the recycling of this can enhance the biogas production in the digestion system.

Organic matter has accumulated as peat in bogs since the last glacial retreat and its anaerobic decay by microbial communities produces methane (CH₄). CH₄ released from northern Boreal peat currently represents a significant proportion of the global budget but their contribution under future climates is uncertain. It is the surface peat 0-500 mm below the water table that is most important for emissions. This study aims to describe the vertical distribution of the gases CH₄, CO₂, O₂ and Ar and their fine scale (0.6 mm) variability in surface peat cores from a rain-fed bog using Quadrupole Mass Spectrometry (QMS). Direct links between the physical structure of peat and distribution of microbial communities have been investigated to identify the determinants of gas distribution.

Thesis (Ph. D.)--Massachusetts Institute of Technology, Dept. of Earth, Atmospheric, and Planetary Sciences, 2001.
Includes bibliographical references (p. 118-134).
The oceans are a small source of non-methane hydrocarbons (NMHC), a suite of volatile organics whose chemical destruction mechanism by reaction with hydroxyl radical can significantly affect the oxidation capacity of the atmosphere. Little is known about the water column cycling processes that constrain this source; previous work has established a photochemical source for many alkenes, and a phytoplanktonic source for isoprene. The focus of this thesis was to gain further insight on marine microbiological cycling of NMHC. This included investigations on two main themes. The first was the effect of different physiological conditions on phytoplanktonic isoprene production. A variety of phytoplankton were examined for the ability to produce isoprene. All were found to have constant isoprene production rates per cell during exponential growth, with decreasing rates as the populations senesced. A positive allometric relationship between isoprene production rate and cell volume was found; highest production rates were found for the largest cell tested, Emiliania huxleyi, and lowest rates for Prochlorococcus, the smallest. Isoprene production in Prochlorococcus was found to be a function of light intensity and temperature, with patterns similar to the relationships between growth rate of this species and these environmental parameters. The second theme investigated was the effect that heterotrophic marine plankton might have on NMHC cycling. We detected no clear production or consumption of any NMHC, except isoprene, from any of the phytoplankton or other organisms tested.
(cont.) The heterotrophic bacteria examined had no detectable effect on isoprene production per Prochlorococcus cell in a dual-species culture, but a temporary production of isoprene was detected from bacterial cultures grown in organically-enriched media. Nanoflagellate grazing by Cafeteria roenbergensis on Prochlorococcus had no detectable effect on NMHC cycling except to control the total phytoplankton counts, and thus total isoprene production. Besides controlling phytoplankton counts, phage lysis of Prochlorococcus had no detectable effect on NMHC cycling except to decrease isoprene production per Prochlorococcus cell during the latent period of infection. Any other effect these particular organisms may have on NMHC cycling likely involves other processes, such as photochemistry.
by Stephanie Lyn Shaw.
Ph.D.

To develop anaerobic digestion (AD), innovative solutions to increase methane yields in existing AD processes are needed. In particular, the adoption of low energy pre-treatments to enhance biomass biodegradability is needed to provide efficient digestion processes increasing profitability. To obtain these features, hydrodynamic cavitation has been evaluated as an innovative solutions for AD of waste activated sludge (WAS), food waste (FW), macro algae and grass, in comparison with steam explosion (high energy pre-treatment). The effect of these two pre-treatments on the substrates, e.g. particle size distribution, soluble chemical oxygen demand (sCOD), biochemical methane potential (BMP) and biodegradability rate, have been evaluated. After two minutes of hydrodynamic cavitation (8 bar), the mean fine particle size decreased from 489- 1344 nm to 277- 381 nm (≤77% reduction) depending of the biomasses. Similar impacts were observed after ten minutes of steam explosion (210 °C, 30 bar) with a reduction in particle size between 40% and 70% for all the substrates treated.  In terms of BMP value, hydrodynamic cavitation caused significant increment only within the A. nodosum showing a post treatment increment of 44% compared to the untreated value, while similar values were obtained before and after treatment within the other tested substrates. In contrast, steam explosion allowed an increment for all treated samples, A. nodosum (+86%), grass (14%) and S. latissima (4%). However, greater impacts where observed with hydrodynamic cavitation than steam explosion when comparing the kinetic constant K. Overall, hydrodynamic cavitation appeared an efficient pre-treatment for AD capable to compete with the traditional steam explosion in terms om kinetics and providing a more efficient energy balance (+14%) as well as methane yield for A. nodosum.
Det behövs innovativa lösningar för att utveckla anaerob rötning i syfte att öka metangasutbytet från biogassubstrat. Beroende på substratets egenskaper, kan förbehandling möjliggöra sönderdelning av bakterieflockar, uppbrytning av cellväggar, elimination av inhiberande ämnen och frigörelse av intracellulära organiska ämnen, som alla kan leda till en förbättring av den biologiska nedbrytningen i rötningen. För att uppnå detta har den lågenergikrävande förebehandlingsmetoden hydrodynamisk kavitation prövats på biologiskt slam, matavfall, makroalger respektive gräs, i jämförelse med ångexplosion. Effekten på substraten av dessa två förbehandlingar har uppmäts genom att undersöka distribution av partikelstorlek, löst organiskt kol (sCOD), biometan potential (BMP) och nedbrytningshastigheten. Efter 2 minuters hydrodynamisk kavitation (8 bar) minskade partikelstorleken från 489- 1344 nm till 277- 281 nm (≤77 % reduktion) för de olika biomassorna. Liknande påverkan observerades efter tio minuters ångexplosion (210 °C, 30 bar) med en partikelstorlekreducering mellan 40 och 70 % för alla behandlade substrat. Efter behandling med hydrodynamisk kavitation, i jämförelse med obehandlad biomassa, ökade metanproduktionens hastighetskonstant (K) för matavfall (+65%), makroalgen S. latissima (+3%), gräs (+16 %) samtidigt som den minskade för A. nodosum (-17 %). Förbehandlingen med ångexplosion ökade hastighetskonstanten för S. latissima (+50 %) och A. nodosum (+65 %) medan den minskade för gräs (-37 %), i jämförelse med obehandlad biomassa. Vad gäller BMP värden, orsakade hydrodynamisk kavitation små variationer där endast A. nodosum visade en ökning efter behandling (+44 %) i jämförelse med obehandlad biomassa. Biomassa förbehandlade med ångexplosion visade en ökning för A .nodosum (+86 %), gräs (14 %) och S. latissima (4 %). Sammantaget visar hydrodynamisk kavitation potential som en effektiv behandling före rötning och kapabel att konkurrera med den traditionella ångexplosionen gällande kinetik och energibalans (+14%) samt metanutbytet för A. nodosum.

Coalbed methane wells have been used for many years as a viable means of extracting quantities of methane gas for use as a clean and efficient energy source. However, there is a limited understanding of many of the factors involved during the extraction process. As the more easily attainable reservoirs are depleted, it is imperative to gain a greater comprehension of these factors in order to develop techniques to efficiently collect economical quantities of methane gas in the future.

For this investigation, an extensive database was compiled, consisting of a large set of parameters pertaining to the development of coalbed methane gas wells. Using the information contained in this database, a statistical analysis was performed in order to gain a better understanding of the relationships between the many factors involved in extracting quantities of methane gas from the ground. The results of this analysis showed that the majority of the parameters shown to have the greatest impact on methane production were heavily dependent upon the geology of the region. As a result, any attempt to exploit them for optimization exercises would be extremely difficult. Of the parameters shown to have the least dependence on naturally occurring phenomena, the amount of proppant sand used to hold fractures open within the well system after stimulation was shown to have the most impact

During the well stimulation procedure, the proppant sand is carried into the fractures in the strata by a foam fracturing fluid. The sand acts to support the fracture system, increasing the permeability of formation, and allowing the methane gas to flow to the wellbore. By treating the sand particles with certain reagents, it is possible to render them hydrophobic, making it possible for them to stick to the bubbles within the foam and be carried deeper into the formation. Results of an investigation of sands treated to different degrees of hydrophobicity have shown that such treatments significantly increase the amount of sand distributed over a greater distance.
Master of Science

This thesis explores the concept of displacement of sorbed methane and enhancement of methane recovery by injection of CO2 into coal, while sequestering CO2. The objective of this study was to investigate the diffusion behavior of San Juan Basin coal under single and competitive gas environments. The movement of gas in a coalbed reservoir starts in the coal matrix with diffusion towards the naturally occurring cleat network surrounding the matrix blocks. The gas production potential from coalbed reservoirs under different gas environments was, therefore, estimated by studying the diffusion behavior of the coal type. The results clearly showed that the rate of diffusion increases with decreasing reservoir pressure, the increase being exponential at low/very low pressure. As a final step, a simulation study was carried out using the experimental results to predict long-term gas production from coalbed reservoirs with and without CO2 injection. This was followed by a preliminary economic analysis in order to estimate the feasibility of enhanced recovery method by CO2 injection by calculating the net present value of a project with and without carbon credits. The results showed that it is possible to obtain significant improvement in methane recovery by CO2 injection. However, it becomes economically feasible only with carbon credits.

During the full-time of two-year research, the primary objectives are focused on coal-bed methane elimination in underground coal mines, especially for in-seam horizontal methane drainage. Firstly, this research reviewed the method of in-seam horizontal drainage within 6 controllable factors. Secondly, this research also improved the methane drainage system which applied in a coal mine in China with the basic theory. In addition, some factors of gas related disasters are investigated as preliminary work for CBM.

Methane yield of ligno-cellulosic substrates (i.e. dedicated energy crops and agricultural residues) may be limited by their composition and structural features. Hence, biomass pre-treatments are envisaged to overcome this constraint. This thesis aimed at: i) assessing biomass and methane yield of dedicated energy crops; ii) evaluating the effects of hydrothermal pre-treatments on methane yield of Arundo; iii) investigating the effects of NaOH pre-treatments and iv) acid pre-treatments on chemical composition, physical structure and methane yield of two dedicated energy crops and one agricultural residue. Three multi-annual species (Arundo, Switchgrass and Sorghum Silk), three sorghum hybrids (Trudan Headless, B133 and S506) and a maize, as reference for AD, were studied in the frame of point i). Results exhibit the remarkable variation in biomass yield, chemical characteristics and potential methane yield. The six species alternative to maize deserve attention in view of a low need of external inputs but necessitate improvements in biodegradability. In the frame of point ii), Arundo was subjected to hydrothermal pre-treatments at different temperature, time and acid catalyst (with and without H2SO4). Pre-treatments determined a variable effect on methane yield: pre-treatments without acid catalyst achieved up to +23% CH4 output, while pre-treatments with H2SO4 catalyst incurred a methanogenic inhibition. Two biomass crops (Arundo and B133) and an agricultural residue (Barley straw) were subject to NaOH and acid pre-treatments, in the frame of point iii) and iv), respectively. Different pre-treatments determined a change of chemical and physical structure and an increase of methane yield: up to +30% and up to +62% CH4 output in Arundo with NaOH and acid pre-treatments, respectively. It is thereby demonstrated that pre-treatments can actually enhance biodegradability and subsequent CH4 output of ligno-cellulosic substrates, although pre-treatment viability needs to be evaluated at the level of full scale biogas plants in a perspective of profitable implementation.

Methane yield of ligno-cellulosic substrates (i.e. dedicated energy crops and agricultural residues) may be limited by their composition and structural features. Hence, biomass pre-treatments are envisaged to overcome this constraint. This thesis aimed at: i) assessing biomass and methane yield of dedicated energy crops; ii) evaluating the effects of hydrothermal pre-treatments on methane yield of Arundo; iii) investigating the effects of NaOH pre-treatments and iv) acid pre-treatments on chemical composition, physical structure and methane yield of two dedicated energy crops and one agricultural residue. Three multi-annual species (Arundo, Switchgrass and Sorghum Silk), three sorghum hybrids (Trudan Headless, B133 and S506) and a maize, as reference for AD, were studied in the frame of point i). Results exhibit the remarkable variation in biomass yield, chemical characteristics and potential methane yield. The six species alternative to maize deserve attention in view of a low need of external inputs but necessitate improvements in biodegradability. In the frame of point ii), Arundo was subjected to hydrothermal pre-treatments at different temperature, time and acid catalyst (with and without H2SO4). Pre-treatments determined a variable effect on methane yield: pre-treatments without acid catalyst achieved up to +23% CH4 output, while pre-treatments with H2SO4 catalyst incurred a methanogenic inhibition. Two biomass crops (Arundo and B133) and an agricultural residue (Barley straw) were subject to NaOH and acid pre-treatments, in the frame of point iii) and iv), respectively. Different pre-treatments determined a change of chemical and physical structure and an increase of methane yield: up to +30% and up to +62% CH4 output in Arundo with NaOH and acid pre-treatments, respectively. It is thereby demonstrated that pre-treatments can actually enhance biodegradability and subsequent CH4 output of ligno-cellulosic substrates, although pre-treatment viability needs to be evaluated at the level of full scale biogas plants in a perspective of profitable implementation.

A mathematical modeling framework for the methane steam reforming reaction operating in steady state has been developed. Performances are compared between the classic catalytic packed bed reactor and a Pd-based catalytic membrane reactor. Isothermal simulations on MATLAB © has first been conducted and show a higher performance of the membrane reactor over the packed bed reactor. Methane conversion of 1 can be reached for lower temperatures than used with industrial PBR, and better performances are shown for an increase in the operating pressure. Optimum conditions were defined for Temperature (500-600 Celsius), reaction side pressure (16-40 bars), membrane thickness (1-7 micrometers), steam/methane ratio (3-4), reactor length (5-10 meters) and permeate sweep ratio (20 or more). This model was validated by multiple recognized sources. Adiabatic simulations were conducted in order to develop a mathematical model base for non-isothermal simulations. The membrane reactor is again showing a higher conversion of methane compared to the packed bed reactor, however the heat loss due to the membrane and the hydrogen leaving through the tube is decreasing the performances of the MR over the PBR compared to the isothermal case. Results show also that most of the reaction occurs at the very beginning of the reactor.

Volatile fatty acids (VFA) are important products of ruminal fermentation. The VFA are not only the major source of energy to the ruminant animals but also influence methane production in the rumen. Therefore it is important to understand mechanism controlling VFA production and to depict VFA production in a model. This will allow us to devise strategies to enhance energy utilization and reduce methane production in ruminant livestock. An evaluation of a mechanistic model in predicting VFA production was conducted and equations were introduced into the model to improve the predictions. Later a continuous culture experiment was conducted to test the hypothesis on which those equations were based on. A mechanistic model -" Molly, was evaluated using a dataset with reported VFA production rates. The results of residual error analysis indicated that the root mean square prediction errors (RMSPE) were 63, 63, and 49% for acetate, propionate and butyrate, respectively. An assessment from two studies reporting VFA production revealed a potential of reducing errors of prediction by representing interconversion among VFA. In the second study, equations based on thermodynamics influence of pH and VFA concentration were introduced in the model to represent interconversion among VFA. The parameters for de novo VFA production and VFA absorption were re derived with (VFAInt) and without (BASE) the new interconversion equations. There were some improvements in the VFA concentration predictions but the improvements were both in VFAInt and BASE models. The RMSPE of VFA production were still above 50% for acetate, propionate and butyrate. The larger errors of predictions were attributed to measurement variation in VFA production literature, or possible incorrect rate constants for interconversion equations. Finally, a third study was conducted to assess the effect of pH, and VFA concentration on VFA and methane production in continuous culture. The treatments consisted of control, 20 mmol/d acetate infusion (INFAC), 7 mmol/d propionate infusion (INFPR), and low pH (LOWPH). Individual isotopes of acetate, propionate and butyrate were infused in the fermenters to estimate interconversions among VFA. With LOWPH treatment methane emission was reduced whereas production of propionate was increased. Hydrogen production was higher in INFAC indicating that some of the acetate could have been degraded to CO2 and H2. It was estimated that around 3 % of de novo acetate was converted to propionate and 9 % to butyrate. Exchange between propionate and butyrate was insignificant and below 1% of de novo production of either VFA. However, treatments did not affect interconversion rates among VFA. These results indicated that pH and VFA concentration do not have thermodynamic influence on VFA interconversion as hypothesized.
Ph. D.

Natural gas hydrates are solid crystalline substances found in the subsurface. Since gas hydrates are stable at low temperatures and moderate pressures, gas hydrates are found either near the surface in arctic regions or in deep water marine environments where the ambient seafloor temperature is less than 10°C. This work addresses the important issue of geomechanical stability in hydrate bearing sediments during different perturbations. I analyzed extensive data collected from the literature on the types of sediments where hydrates have been found during various offshore expeditions. To better understand the hydrate bearing sediments in offshore environments, I divided these data into different sections. The data included water depths, pore water salinity, gas compositions, geothermal gradients, and sedimentary properties such as sediment type, sediment mineralogy, and sediment physical properties. I used the database to determine the types of sediments that should be evaluated in laboratory tests at the Lawrence Berkeley National Laboratory. The TOUGH+Hydrate reservoir simulator was used to simulate the gas production behavior from hydrate bearing sediments. To address some important gas production issues from gas hydrates, I first simulated the production performance from the Messsoyakha Gas Field in Siberia. The field has been described as a free gas reservoir overlain by a gas hydrate layer and underlain by an aquifer of unknown strength. From a parametric study conducted to delineate important parameters that affect gas production at the Messoyakha, I found effective gas permeability in the hydrate layer, the location of perforations and the gas hydrate saturation to be important parameters for gas production at the Messoyakha. Second, I simulated the gas production using a hydraulic fracture in hydrate bearing sediments. The simulation results showed that the hydraulic fracture gets plugged by the formation of secondary hydrates during gas production. I used the coupled fluid flow and geomechanical model "TOUGH+Hydrate- FLAC3D" to model geomechanical performance during gas production from hydrates in an offshore hydrate deposit. I modeled geomechanical failures associated with gas production using a horizontal well and a vertical well for two different types of sediments, sand and clay. The simulation results showed that the sediment and failures can be a serious issue during the gas production from weaker sediments such as clays.

Several heterogeneous catalysts were studied for synthesis gas production through dry reforming of methane (DRM). This process uses carbon dioxide in lieu of the steam that is traditionally used in conventional methane reforming to produce hydrogen that can then be repurposed in more chemical processes [2]. The monometallic catalysts explored were Ni/Al₂O₃ and Ni/CeZrO₂ followed by their bimetallic versions PtNi/Al ₂O₃ and PtNi/CeZrO₂ at 800°C. In addition to these catalysts, platinum supported Zeolitic Imidazolate Framework (ZIF)-8 was also investigated in comparison with PtNi/CeZrO₂ at 490°C. The studies suggest that these catalysts are suitable for promoting the dry reforming of methane for hydrogen production.

Thesis (M.S.)--West Virginia University, 2001.
Title from document title page. Document formatted into pages; contains xv, 155 p. : ill. (some col.). Includes abstract. Includes bibliographical references (p. 120-123).

Microbial production of natural gas in subsurface organic-rich reservoirs (e.g. coal, shale, oil) can be enhanced by the introduction of limiting nutrients to stimulate microbial communities to generate “new” methane resources on human timescales. The few successful field experiments of Microbial Enhancement of Coalbed Methane (MECoM) relied on relatively qualitative approaches for estimating the amount of “new” methane produced during the stimulation process (i.e. extrapolation of pre-stimulation gas production curves). We have tested deuterated water as a tracer, initially in the laboratory, to more directly quantify the amount of “new” methane generated and the effectiveness of MECoM stimulation approaches. Microorganisms, formation water, and coal obtained during a previous drilling project in the Powder River Basin, Birney, Montana were used to set up a series of benchtop stimulation experiments where we added incremental amounts of deuterated water to triplicate sets of stimulated microbes (methanogens). We hypothesized that as MECoM progresses, methanogens will incorporate the heavy water into new methane produced, as methanogens naturally uptake hydrogen during methanogenesis. The amount of hydrogen incorporated into methane from water is dependent on the methanogenic pathway (hydrogenotropic vs acetoclastic/methylotrophic). During the experiments, we saw a shift in the methanogenic pathway towards acetoclastic methanogenesis, which was indicated by a consistent shift in the enrichment of deuterium in the methane produced, methanogenic community, and a large kinetic fractionation. The enrichment of the methane as compared to the deuterium content of the water the microbes used followed a narrowly confined, predictable range of values. This predictable enrichment of the methane allows us to propose a quantification scheme for the amount of methane produced in larger field scale stimulations, as we can compare the change in the overall deuterium content of the in-situ methane with the known value before the stimulation. The success of our proof-of-concept laboratory experiments suggests that deuterium may be used as a tracer of “new” natural gas resources in field- to commercial-scale MECoM projects. In addition, additions of deuterated water may also be useful as a tracer in bioremediation projects where large background pools of contaminants or degradation products hamper traditional quantification techniques, microbial enhanced oil recovery, or other subsurface carbon cycling pathways.

In Brazil, estimate of methane (CH4) emission for the National Greenhouse Gas Inventory is carried out using the empirical Tier 2 approach published by the Intergovernmental Panel on Climate Change (IPCC). Although, IPCC recommends the use of a more specific, mechanistic Tier 3 approach, this is hampered by a lack of consolidated data for development, evaluation and application of such a Tier 3 approach. The purpose of the present modelling study was to evaluate whether a Tier 3 approach instead of the Tier 2 approach has merit in estimating the effect of improvement of diet quality by feeding supplements on CH4 emission, calculated by both a Tier 2 and an extant Tier 3 approach. Six systems of beef cattle production in Brazil were considered which differed inage at slaughter mainly due to diet quality (ranging from 14 to 44 months). The systems studied encompass most of the range of slaughter age and feeding methods observed and the differences between them can be considered realistic for variation in current Brazilian practice of beef production. Estimates of feed quality and animal performance were based on published Brazilian studies and on data from a Brazilian inventory on enteric CH4. Both Tier 2 and Tier 3 approaches estimated a large variation in CH4 emission for the six production systems. The highest level of enteric CH4 emission (168 and 145 kg per slaughtered animal, estimated with the Tier 2 and Tier 3 approach, respectively) was estimated for the system with slaughter after 44 months and the lowest with slaughter after 14 months (35 and 31 kg per slaughtered animal, estimated with the Tier 2 and Tier 3 approach, respectively). The general trend was a profound increase of CH4 emission with increase of age-at-slaughter. Methane estimates depended strongly on the modelling approach adopted. Using the Tier 3 approach in the present study with the assumptions made for the six Brazilian beef production systems indicated substantially lower estimates of enteric CH4 compared to the IPCC Tier 2 approach. The Ym values (fraction of gross energy intake emitted as CH4) estimated by the Tier 3 approach for separate growing periods (seasons) within the different systems ranged between 0.044 and 0.070, and between 0.049 and 0.058 when averaged for the whole growing period (cf. 0.065 with Tier 2). Model estimates should be confirmed by evaluation against independent in vivo data obtained under local Brazilian conditions of beef production.
No Brasil, a estimativa de emissão de metano no inventário nacional sobre a emissão de metano (CH4) é realizada pela abordagem Tier 2, recomendada pelo Painel Intergovernamental sobre Mudanças Climáticas (IPCC). Embora o IPCC recomende o uso do Tier 3, uma abordagem mais complexa, a aplicação desta no Brasil é dificultada pela falta de dados consolidados para o desenvolvimento, avaliação e aplicação do modelo. O objetivo deste trabalho foi estimar o efeito da melhoria da qualidade da dieta na emissão entérica de CH4, em sistemas de produção de gado de corte brasileiros, pelos métodos Tier 2 e Tier 3. A emissão entérica de CH4, foi estimada em seis sistemas de produção de bovinos de corte, do desmame até abate. Os sistemas estudados abrangeram os métodos de alimentação mais praticados na produção de carne bovina brasileira. A qualidade da alimentação e desempenho animal foram estimados baseados em estudos publicados na literatura. Ambas as abordagems Tier 2 e 3 estimaram efeito da suplementação sobre a emissão de CH4. As estimativas do Tier 2 e 3, no sistema de abate aos 44 meses, apresentaram maior emissão de CH4 entérico comparados aos outros sistemas, resultando em valores de 168 e 145 kg de CH4 por animal, respectivamente. Por outro lado, o sistema de abate aos 14 meses, apresentou menor emissão de CH4, comparados aos outros sistemas, em valores de 35 e 31 kg de CH4 por animal abatido, respectivamente. A tendência geral foi um aumento de emissão de CH4 com o aumento da idade de abate. Usando a abordagem Tier 3 para as condições brasileiras resultou valores menores de CH4 entérico em comparação a Tier 2. Os valores Ym (fração de ingestão de energia bruta emitido como CH4) estimados pela Tier 3, nas diferentes estações, variou entre 0,044 e 0,070, e para diferentes sistemas de produção entre 0,049 e 0,058. Por outro lado a média para todo o período de crescimento foi 0,065 para Tier 2. Essas estimativas devem ser confirmados com dados in vivo obtidos em condições locais, com intuito de melhorar o modelo Tier.

Globally agriculture and livestock producers have come under increasing pressure over the environmental impact of production systems. The objectives of this study were to re-calculate the direct methane (CH4) and nitrous oxide (N2O) emissions of livestock production systems in South Africa, taking into consideration the uniqueness of the South African scenario and to identify and evaluate possible greenhouse gas mitigation strategies for extensive production systems. It is important to generate accurate greenhouse gas (GHG) baseline figures to develop South Africa’s capacity to understand and reduce GHG emissions emitted from the livestock sector. Livestock produce GHG’s in the form of methane from enteric fermentation and nitrous oxide and methane from manure management and manure deposited on pastures and rangeland by grazing animals. Agriculture, forestry and land use (corrected for carbon sink values) emitted an estimated 4.9% of South African GHG gases in 2004, which makes it the third largest GHG contributor in South Africa after the energy industry and industrial processes. Livestock produced approximately 27% of the national methane emissions and 98% of the agricultural sector’s methane emissions in 2004. Methane is a potent GHG that remains in the atmosphere for approximately 9 to 15 years and is 28 times more effective in trapping heat in the atmosphere than carbon dioxide (CO2) over a 100-year period. Nitrous oxide has an atmospheric lifetime of 150 years and a global warming potential of 265 times that of CO2 over a 100-year period. South African livestock production is based on a unique combination of commercial (intensive and extensive) and emerging and communal (subsistence) production systems. The levels of productivity and efficiency in these production systems vary greatly in certain areas and it is important to distinguish between them when calculating GHG emissions. Previous inventories were conducted on a national scale utilizing IPCC default values (Tier 1 approach) for some or all of the emission calculations. These emission factors do not distinguish effectively between classes of animals, production efficiencies, and production systems. They are often based on assumptions of animals utilizing diets which are not representative of South African production systems. The IPCC Tier 2 methodology seeks to define animals, animal productivity, diet quality and management circumstances to support a more accurate estimate of feed intake for use in estimating methane production from enteric fermentation. It was also considered important to do separate calculations for each province as provinces differ in vegetation or biomes and production systems which may require different approaches to mitigation recommendations. Due to the heterogeneity of available feed types within South Africa it was considered important to use methodologies that could reflect such differences and was developed under similar conditions. The methodology utilized is based on the Australian national greenhouse account’s National Inventory Report, which contains Australian country-specific and IPCC default methodologies and emission factors. Emission factors specific to South African conditions and management systems were calculated where possible. A Tier 2 approach was adopted for all major livestock categories including privately owned game in accordance with the IPCC Good Practice requirements. Recently game farming has become a recognized commercial enterprise in the agricultural sector which needs to be included as an anthropogenic emissions source. Methane emissions from South African livestock were estimated at 1328 Giga gram (Gg) during 2010. Dairy and beef cattle contributed an estimated 964 Gg or 72.6% of the total livestock methane emissions in South Africa during 2010. Beef cattle in extensive systems were the largest contributor (83.3%), followed by dairy cattle (13.5%), and feedlot cattle (3.2%). The estimated direct enteric methane emission factors for dairy and beef cattle were higher than the IPCC default factors for Africa. The Eastern Cape recorded the highest dairy and beef cattle methane emissions, whereas Gauteng showed the highest feedlot methane emissions primarily due to cattle numbers. Small stock was responsible for 15.6% of the total livestock emissions contributing an estimated 207.7 Gg, with sheep producing 167 Gg and goats producing 40.7 Gg. Calculated enteric methane emission factors for both commercial and communal sheep were higher than the IPCC default values for developing countries. A similar tendency was found with goat emission factors. The highest sheep and goat methane emissions were reported for the Eastern Cape province. The pig and ostrich industry both contributed approximately 8 Gg CH4 during 2010. The North- West province produced the highest commercial pig GHG emissions with the highest communal pig emissions originating from the Eastern Cape. The poultry industry was the largest direct N2O producer of the non-ruminant livestock industries, contributing 2.3 Gg or 92.8% of the total nonruminant N2O emissions. The privately owned game industry contributed an estimated 131.9 Gg of methane emissions with the provinces of Limpopo, Eastern Cape and Northern Cape being the three largest contributors with 43.4, 37.3 and 21 Gg methane, respectively. The total privately owned game population was estimated at 2 991 370 animals, utilizing 20.5 million hectares. Beef cattle are the major contributors to livestock GHG emissions in South Africa followed by sheep, privately owned game, dairy cattle, goats, pigs, ostriches, equine, and poultry. The IPCC default values for Africa underestimate emission factors across all livestock categories. The methane emission factors calculated for commercial livestock production systems are more comparable to emission factors from developed countries and the emerging/communal production systems to those of developing countries. This emphasizes the need to develop country-specific emission factors through quantitative research for livestock in all provinces and on all types of production systems to produce accurate baseline figures, which is critical to future mitigation protocols. As part of this study fourteen tropical grass species typical of transitional rangeland regions of South Africa were characterised in terms of chemical composition, in vitro total gas and in vitro methane production. The results of the study demonstrated that in vitro methane production varied between tropical grass species typical of transitional rangeland in South Africa. The variation between species allows for the potential to identify and select species with a lower enteric methane production potential. Panicum maximum, Eragrostis curvula and Elionurus miticus were the three species which produced the lowest in vitro methane production but which also had a crude protein (CP) concentration of more than 3.5% of dry matter (DM) and with an in vitro organic matter digestibility (IVOMD) above the group average for the study. Furthermore, the results of the study revealed that in vitro methane production was higher in Decreaser species compared to Increaser species. Improving the quality of available forages through the use of cultivated pastures and fertilization is known to improve ruminant production efficiency. The effect of level of nitrogen (N) fertilization on certain qualitative parameters and in vitro total gas and methane production of improved grass species commonly utilised in South Africa was evaluated. Treatments included seven grass species divided into two photosynthetic pathways (C3 and C4) with three levels of N fertilization (0, 50 and 100 kg N/ha). No effect was found for N fertilization on in vitro total gas or methane production. The CP concentration increased (P < 0.05) and the NDF concentration tended to decrease (P < 0.1) as the level of N fertilization increased for both C3 and C4 species. Increasing the level of N fertiliser increased (P < 0.05) the methanogenic potential of Dactylis glomorata, Festuca arundinacea and Cenchrus ciliaris after the 24 hour incubation period but no effects (P>0.05) were found after the 48 hour incubation period. Results suggests that the stage of physiological development of forages might have a greater influence on the methanogenic potential of forages compared to the effect of N fertiliser application.
Thesis (PhD)--University of Pretoria, 2017.
Animal and Wildlife Sciences
PhD
Unrestricted

[EN] Climate change, a resultant effect of greenhouse gas emissions, is a worldwide concern because its continuation is having significant impacts on people, natural resources and economic conditions around the world. The root cause of this recent past and projected climate change is now recognised to be the warming potential of a number of greenhouse gases that, by absorbing terrestrial infrared radiation, raise the temperature of the troposphere and with it, global surface temperatures. The major greenhouse gases are water vapour, carbon dioxide, methane, nitrous oxide and fluorinated gases. While carbon dioxide receives the most attention as a factor which causes global warming, methane also cause significant radiative forcing. Methane is only second to carbon dioxide in its contribution to global warming and its emissions are caused by both natural and anthropogenic actions. Human activities such as intensive livestock farming are the primary cause of the increased methane concentrations in the atmosphere, being ruminants the animals which create large amounts of methane via fermentation of feeds in the rumen. During this physiological digestive process, hydrogen is released by some microbes during fermentation of forage and is used by methanogenic Archaea (methanogens) to convert carbon dioxide to methane, which is released through eructation, normal respiration and small quantities as flatus. Rumen fermentation of cattle contributes the most towards the greenhouse effect through methane emission followed by sheep, goats and buffalos, respectively. Several techniques have been developed to quantify methane emissions from ruminants - indirect calorimetry, sulphur hexafluoride tracer technique and in vitro gas production technique - and some strategies for reduction of methane emissions from the rumen have been described - defaunation treatment, vaccine and dietary composition -. The initial topics of this research were: design the experiments with goats because there are not many reports about methane emissions in these animals; investigate the influence of dietary composition (carbohydrates) as a strategy for reduction methane emissions from the rumen; and use the indirect calorimetry as method to quantify methane production. Consequently, three experiments were performed. Murciano-Granadina goats during mid or late lactation were used. Diets were mixed rations that differed in the inclusion of cereal or fibrous by-products. The effect of diet was studied on milk yield, digestibility, rumen parameters, energy partitioning, carbon and nitrogen balance, substrate oxidation and methane productions. In the first experiment, gas exchange was measured using a face mask which was fixed to the head of the goat by a rubber band; a sample of exhaled gas was stored in a gas collection bag which was connected to an analyzer, and it measured the concentration of O2, CO2 and CH4 from the air. This first experiment replaces corn grain with beet pulp and the amount of methane recovered was 19.6 and 29.7 g/day, respectively. In the other two experiments, gas exchange was measured by a head box designed for small ruminants where the goat introduced the whole head and a specific software automatically recorded concentrations of O2, CO2 and CH4 from the exhaled air continuously throughout the day. The second experiment involved two diets with high and low level of starch and no differences were found on methane emission (28.5 g/day). The experiment number three replaces ingredient by ingredient like in the experiment number one. Here, barley grain was replaced with orange pulp or soybean hulls and no differences were found, with an average methane production value of 41 g/day. The metabolizable energy intake during the three experiments was 1279 kJ/kg of BW0.75 and day on average, and the efficiency use of metabolizable energy intake for milk production was 0.6.
[ES] El cambio climático es una preocupación de ámbito mundial debido a que su perpetuación en el tiempo está teniendo un impacto significativo sobre las personas, los recursos naturales y las condiciones económicas de todo el mundo. La causa fundamental de este fenómeno es el potencial de calentamiento de una serie de gases de efecto invernadero que, mediante la absorción de la radiación infrarroja terrestre, elevan la temperatura de la troposfera y, con ella, las temperaturas superficiales de la Tierra. Los principales gases de efecto invernadero son el vapor de agua, el dióxido de carbono, el metano, el óxido nitroso y los gases fluorados. El metano, después del dióxido de carbono, es el gas que más repercusión tiene sobre el calentamiento global y sus emisiones son causadas tanto por acciones naturales como humanas. Actividades antropogénicas tales como la ganadería intensiva son la principal causa de aumento de las concentraciones de metano en la atmósfera, siendo los rumiantes los animales que mayores cantidades de metano generan a través de la fermentación de alimentos que se produce en el rumen. Las emisiones de metano del ganado vacuno son las que principalmente contribuyen al efecto invernadero seguido de las ovejas, las cabras y los búfalos, respectivamente. Se han descrito diferentes técnicas para medir las emisiones de metano de los rumiantes - la calorimetría indirecta, la técnica del marcador con hexafluoruro de azufre y la técnica de producción de gas in vitro - y, además, se han mencionado algunas estrategias para reducir las emisiones de metano - la defaunación, las vacunas y la composición de la dieta -. Los puntos clave de esta Tesis fueron: diseñar los experimentos con cabras, debido a que no hay muchas investigaciones sobre emisiones de metano en estos animales; estudiar la influencia de la composición de la dieta (hidratos de carbono) como una posible estrategia para la reducción de las emisiones de metano del rumen; y utilizar la calorimetría indirecta como método para cuantificar la producción de metano. Se realizaron tres experimentos. Se utilizaron cabras de la raza Murciano-Granadina en mitad o final de la lactación. Las dietas eran raciones mixtas que diferían en la inclusión de cereal o subproductos fibrosos. El efecto de la dieta se estudió en la producción de leche, la digestibilidad, los parámetros del rumen, la partición de energía, el balance de carbono y nitrógeno, la oxidación de nutrientes y las producciones de metano. En el primer experimento, el intercambio de gases se midió utilizando una mascarilla que se fijó a la cabeza de la cabra con una goma; se almacenó una muestra de gas exhalado en una bolsa de recogida de gas que estaba conectada a un analizador, y se midió la concentración de O2, CO2 y CH4 del aire. En este primer experimento se reemplazó el grano de maíz con pulpa de remolacha y la cantidad de metano recuperado fue del 19,6 y 29,7 g/día, respectivamente. En los otros dos experimentos, el intercambio de gases se midió mediante una urna o cajón diseñado para pequeños rumiantes, donde la cabra introducía toda la cabeza y un programa informático grababa automáticamente las concentraciones de O2, CO2 y CH4 del aire exhalado de forma continua a lo largo del día. El segundo experimento consistió en dos dietas con alto y bajo nivel de almidón y no se encontraron diferencias en la emisión de metano (28,5 g/día). En el tercer experimento se sustituyó ingrediente por ingrediente como en el experimento número uno. El grano de cebada se sustituyó por pulpa de naranja o cascarilla de soja y tampoco se encontraron diferencias, con un valor promedio de la producción de metano de 41 g/día. La energía metabolizable ingerida durante los tres experimentos fue de 1279 kJ/kg de peso metabólico (PV0.75) y día de promedio, y la eficiencia de utilización de la energía metabolizable ingerida para la producción de leche fue de
[CAT] El canvi climàtic és una preocupació d'àmbit mundial ja que la seua perpetuació en el temps està tenint un impacte significatiu sobre les persones, els recursos naturals i les condicions econòmiques de tot el món. La causa fonamental d'aquest fenòmen és el potencial d'escalfament d'una sèrie de gasos d'efecte hivernacle que, mitjançant l'absorció de la radiació infraroja terrestre, eleven la temperatura de la troposfera i, amb ella, les temperatures superficials de la Terra. Els principals gasos d'efecte hivernacle són el vapor d'aigua, el diòxid de carboni, el metà, l'òxid nitrós i els gasos fluorats. El metà, després del diòxid de carboni, és el gas que més repercussió té sobre l'escalfament global i les seues emissions són causades tant per accions naturals com humanes. Activitats antropogèniques com ara la ramaderia intensiva són la principal causa d'augment de les concentracions de metà a l'atmosfera, sent els remugants els animals que més quantitats de metà generen a través de la fermentació d'aliments que es produeix al rumen. Les emissions de metà dels bovins són les que principalment contribueixen a l'efecte hivernacle seguit de les ovelles, les cabres i els búfals, respectivament. S'han descrit diferents tècniques per mesurar les emissions de metà dels remugants - la calorimetria indirecta, la tècnica del marcador amb hexafluorur de sofre i la tècnica de producció de gas in vitro - i, a més, s'han esmentat algunes estratègies per reduir les emissions de metà - la defaunació, les vacunes i la composició de la dieta -. Els punts clau d'aquesta Tesi van ser: dissenyar els experiments amb cabres, pel fet que no hi ha moltes investigacions sobre emissions de metà en aquests animals; estudiar la influència de la composició de la dieta (hidrats de carboni) com una possible estratègia per a la reducció de les emissions de metà del rumen; i utilitzar la calorimetria indirecta com a mètode per quantificar la producció de metà. Es van realitzar tres experiments. S'utilitzaren cabres de la raça Murciano-Granadina a la meitat o final de la lactació. Les dietes eren racions mixtes que diferien en la inclusió de cereal o subproductes fibrosos. L'efecte de la dieta es va estudiar en la producció de llet, la digestibilitat, els paràmetres del rumen, la partició d'energia, el balanç de carboni i nitrogen, l'oxidació de nutrients i les produccions de metà. En el primer experiment, l'intercanvi de gasos es va mesurar utilitzant una màscara que es va fixar al cap de la cabra amb una goma; es va emmagatzemar una mostra de gas exhalat en una bossa de recollida de gas que estava connectada a un analitzador, i es va mesurar la concentració d'O2, CO2 i CH4 de l'aire. En aquest primer experiment es va reemplaçar el gra de blat de moro amb polpa de remolatxa i la quantitat de metà recuperat va ser del 19,6 i 29,7 g/dia, respectivament. En els altres dos experiments, l'intercanvi de gasos es va mesurar mitjançant una urna o calaix dissenyat per a petits remugants, on la cabra introduïa tot el cap i un programa informàtic gravava automàticament les concentracions d'O2, CO2 i CH4 de l'aire exhalat de forma contínua al llarg del dia. El segon experiment va consistir en dues dietes amb alt i baix nivell de midó i no es van trobar diferències en l'emissió de metà (28,5 g/dia). En el tercer experiment es va substituir ingredient per ingredient com en l'experiment número u. El gra d'ordi es va substituir per polpa de taronja o pellofa de soja i tampoc es van trobar diferències, amb un valor mitjà de la producció de metà de 41 g/dia. L'energia metabolitzable ingerida durant els tres experiments va ser de 1279 kJ/kg de pes metabòlic (PV0.75) i dia de mitjana, i l'eficiència d'utilització de l'energia metabolitzable ingerida per a la producció de llet va ser de 0,6.
Ibáñez Sanchis, C. (2015). INFLUENCE OF NUTRITION ON METHANE GAS PRODUCTION IN MURCIANO-GRANADINA GOATS [Tesis doctoral no publicada]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/59389
TESIS

Anaerobic digestion is a commonly used technique in treating industrial, rural effluents and sewage sludge. Methane, CH4, produced in anaerobic digestion is a valuable renewable energy source. In wastewater treatment plant (WWTP), primary and secondary sludge are produced at different stages of wastewater treatment process. They are different in terms of composition and degradability. Experiments (batch/ semi-continuous) showed that primary sludge was more degradable and produced higher methane than secondary sludge. As primary sludge is highly degradable, the possibility of increasing feeding rate was examined. This study found that the increased in feeding rate eventually leaded to massive methanogens washout and hence digester failure. In order to maintain the stability of primary sludge reactor at shorter hydraulic retention time (HRT), a biomass recycling method was investigated. It was found that the reactor remains stable at shorter HRT (16 days). However, further investigations are required for this technique. Secondary sludge is made up of microbial cells from secondary treatment in WWTP. Therefore, it is hydrolysis limited in anaerobic digestion due to the low degradability characteristics. To increase the hydrolysis rate of secondary sludge anaerobic digestion, two pre-treatments were examined and compared. Thermal pre-treatment increased the methane production of secondary sludge by 50% at the highest temperature (150°C), and 80°C was not found effective when treatment time is short (1 hour). However, the energy consumption of thermal pre-treatment was too high. Energy consumption was higher than the energy gained from anaerobic digestion. Hence, better heating technology is needed. Electrolysis is an emerging technology for secondary sludge pre-treatment. It is an adaptation from the theory of water electrolysis. During electrolysis treatment, the pH of sludge changed due to the redox activity occurring at anode and cathode. The high and low pH in the anode and cathode chambers disrupted microbial cells in the sludge, and increased methane production by 30%. Energy consumption of electrolysis was lower than the energy gained from anaerobic digestion, thus it is more energy favourable compared to thermal pre-treatment in this study.

Production of gas from shale reservoirs is governed by multiphysics mechanisms of which gas desorption is dominant. However, the actual contributions of desorption to gas production is often masked by the use of adsorption isotherms for gas production predictions. This is because it is hitherto believed that both processes are identical for methane at reservoir conditions. This research aims to quantify the effect of such a misrepresentation on gas production where sorption hysteresis is observed.

Thesis (M.S.)--West Virginia University, 2006.
Title from document title page. Document formatted into pages; contains x, 72 p. : ill. (some col.), maps. Includes abstract. Includes bibliographical references (p. 69-72).

Hydrogen can be obtained from multiple sources, renewable and fossil fuels: research and technological innovations related to production from renewables (especially biomass) have increased in the last decades. However, at present, the most diffused and the less expensive source for hydrogen production remains the reforming of hydrocarbons, in particular methane. The hydrogen produced can be used in electrochemical devices, for example fuel cells, for the production of electrical energy with only water vapor and heat as byproducts. The use of hydrogen as an alternative to traditional energy sources could cover stationary applications of electric energy production (housing, industrial plants), mobile applications (cars and motorcycles), as well as small electronic devices. Nevertheless, the adoption of particular fuel cells requires high purity of hydrogen: in fact, the carbon monoxide, even at levels of a few tens of ppm, can poison the cell resulting in a drastic reduction of the performance of the same. On the other hand, the carbon monoxide is one of the byproducts of the reforming reactions of hydrocarbons and is therefore always present (up to 10-15% of the product stream, depending on the operating conditions and catalysts used). Therefore, appropriate processes must be considered to purify the hydrogen produced by reforming. The membranes for the separation of ultra-pure hydrogen are based on metals selectively permeable to hydrogen: these devices can be implemented in small or medium scale applications. The Pd-Ag membranes, which are well known to exhibit infinite hydrogen selectivity, however, are expensive. Furthermore, the uploading of hydrogenation into the Pd-Ag system can compromise the selectivity and the lifetime of the permeator. As widely reported on literature, the issue of the cost can be approached with two strategies: the reduction of the Pd content (i.e. decrease the thickness of the Pd layer) or investigation of material alternative to noble metals. An experimental setup manufactured at ENEA Frascati laboratories and consisting of a traditional high temperature reformer coupled to a multi-membrane device (19 membrane with length about 250 mm, wall thickness 0.150 mm, diameter 10 mm) has been operated for the production of pure hydrogen by reforming reactions. Experimental test campaigns, methane steam reforming and auto-thermal reforming of methane have been carried out by varying the operative conditions such as the reforming temperature, the reaction (lumen) pressure and the feed flow rate. Up to about 3 NL min-1 of ultra-pure hydrogen have been produced, thus demonstrating that the membrane setup is capable to feed a proton exchange membrane fuel cell of some hundreds watt. Finally, a further test campaign has been performed in the same two-step process in order to investigate the effect of use diluted ethanol in the methane steam reforming. The combined methane and ethanol reforming can improve the hydrogen yield also when the ethanol concentration in the liquid phase is very low (typical, for example, of the bioethanol). The results of this work have demonstrated the applicability of the membrane process studied to produce high purity hydrogen from reforming of methane and/or biomass. Particularly, they can suggest the use of membrane reformers coupled to Polymer Electrolyte Membrane fuel cells for small- medium scale (5-10 kW) stationary or vehicular systems.

At present, more than 80% of the world’s energy consumption and production of chemicals is originated from the use of fossil resources. There is a tremendous growing interest in utilising biomass molecules for energy provision due to their carbon neutrality. Lower alcohols such as methanol and ethanol if produced from biomass as transportation fuels as well as platform chemicals, can become strategically important for many energy/chemically starved countries. Currently, they are synthesised by indirect and inefficient processes. We show for the first time in this thesis study that ethylene glycol, the simplest representative of biomass-derived polyols, can be directly converted to these two lower alcohols by selective hydrogenolysis over modified Raney Ni and Cu catalysts in hydrogen atmosphere. This work provides essential information that may lead to the development of new catalysts for carbohydrate activation to methanol, a novel but important reaction concerning the important biomass conversion to transportable form of energy. Modification of electronic structure and the adsorption properties of Raney catalysts have therefore been achieved by blending with second metal(s). It is found that the activity and selectivity of this reaction can be significantly affected by this approach. In contrast, there is no subtle effect on methanol selectivity despite a great variation in the d-band centre positions of metal catalysts which show a distinctive effect on other products. Our result suggests that methanol is produced on specific surface sites independent from the other sites at an intrinsic rate and will not be converted to other products by the d-band alteration. On the other hand, it is reported in this thesis that a dramatic improvement in the combined selectivity to methanol/ethanol reaching 80% can be obtained over a Pd/Fe₃O₄ catalyst under relatively milder conditions (20 bar and 195 oC). This direct production of the non-enzymatic bio-alcohols is established over a carefully prepared co-precipitated Pd/Fe₃O₄ catalyst which gives a metallic phase of unexpectedly high dispersion ranging from small clusters to individual metal adatoms on defective iron oxide to give the required metal-support interaction for the novel synthesis. It is demonstrated that the small PdFe clusters on iron oxide surface provide the active species responsible for methanol production. In addition, a related Rh/Fe₃O₄ catalyst synthesised by co-precipitation is also shown to be selective for CO₂ and H₂ production from a direct methane-oxygen oxidation reaction. As a result, 2.7% conversion of methane with selectivity ratio of CO₂/H₂ = 4 in a mixed gas feed stream of CH₂/O₂ = 30 at 300 ^oC is obtained. The reaction is operated in a kinetically controlled regime at 300^oC, where the CO formation from reverse water gas shift reaction is greatly suppressed. It is evident that the Rh/Fe₃O₄ acts as an interesting bifunctional catalyst for this reaction. This catalyst firstly gives a high dispersion of Rh which is expected to deliver a higher surface energy with enhanced activity. The Rh metal surface provides catalytically active sites for dissociation of methane to adsorbed hydrogen and carbon atoms effectively, and active oxygen on metal surface readily catalyses the carbon atoms to CO. Following these elementary reactions, the surface oxygen from Fe₃O₄ subsequently converts it to CO₂ selectively at the metal-support interface. As a result, the novel study of catalytic biomass conversion and the discoveries of new catalysts are reported in this thesis.

The Pampanga province is one of the largest pork-producing provinces in the Philippines. Half of the province's pigs are reared in so-called back-yard farms. At these farms, there are no regulations regarding manure management and because of this, large amounts of manure are dumped close to the stables. These actions lead to spontaneous emission of greenhouse gases, eutrophication of rivers and groundwater pollution. In addition, the spread of manure contributes to inadequate sanitation and increased risks of disease among the inhabitants of the province. LPG and wood are the most popular fuels for cooking in the Philippines. LPG is most common in the cities, while more than 60 percent of the rural population still relies on firewood for cooking. LPG is a fossil fuel that, when burned, contributes to an enhanced greenhouse effect. The use of wood increases the pressure on the local biomass and increases the risk of lung diseases for the user. Anaerobic digestion of pig manure under contributes to a more sustainable manure management. At the same time, energy in form of biogas is produced. Biogas is a renewable energy source, which is considered carbon neutral. If pig manure is co-digested with kitchen waste, a more efficient and stable digestion process may be achieved. This study aims to contribute to sustainable development at backyard pig farms in the Pampanga province by demonstrating how pig manure and kitchen waste can be utilized for biogas production. In order to develop an appropriate composition of pig manure and kitchen waste for anaerobic digestion, batch digestion of pig manure and kitchen waste was performed at laboratory scale. During a field study, the substrate composition was digested in test plants under local conditions in Pampanga. During the field study, several field trips to backyard pig farms were performed. Based on prevailing conditions and available materials in the province, a full-scale biogas digester was designed. The digester was sized to produce enough biogas to fulfil one family’s daily requirement of cooking fuel. If the daily biogas production reaches 2.5 m3 it is possible to replace 178 kg LPG or 9855 kg of firewood every year. The reduction of LPG prevents 2700 kg carbon dioxide equivalents from being emitted to the atmosphere every year. The reduction of LPG use also results in an annual saving of 9062 PHP (1672 SEK) for a family. This number corresponds to 11 procent of the total investment cost of the digester.
Pampangaprovinsen är en av de största producenterna av fläskkött i hela Filippinerna. Hälften av provinsens grisar föds upp på så kallade backayard farms. På dessa gårdar finns inga restriktioner gällande gödselhantering. Därför dumpas stora mängder gödsel i gårdarnas närområde vilket leder till spontana utsläpp av växthusgaser, övergödning i vattendrag och förorenat grundvatten. Dessutom leder spridning av gödslet till försämrad hygien och ökad sjukdomsspridning bland provinsens invånare. Gasol och ved är de mest populära bränslena för matlagning i Filippinerna. Gasol är mest utbrett i städerna medan drygt 60 procent av landsbygdens befolkning fortfarande förlitar sig på ved vid matlagning. Gasol är ett fossilt bränsle som vid förbränning bidrar till en förstärkt växthuseffekt. Användning av ved ökar trycket på den lokala biomassan och vid förbränning är risken för sjukdomar i luftvägarna hos användaren stor. Anaerob rötning av grisgödsel möjliggör en mer hållbar gödselhantering samtidigt som energi i form av biogas produceras. Biogas är en förnyelsebar energikälla som dessutom anses vara koldioxidneutral. Grisgödsel kan med fördel samrötas med matavfall för att uppnå en effektivare och mer stabil rötprocess. Den här studien syftar till att bidra till hållbar utveckling inom Pampangaprovinsens backyard pig farms genom att demonstrera hur grisgödsel tillsammans med matavfall kan användas för biogasproduktion. Under studiens inledande del utfördes satsvis rötning av grisgödsel och matavfall i laborativ skala, i syfte att ta fram en lämplig sammansättning av de båda substraten. Substratsammansättningen rötades därefter i testanläggningar vid lokala förhållanden under en fältstudie i Pampangaprovinsen. Under fältstudien genomfördes även studiebesök till olika backyard pig farms. Baserat på rådande förhållanden och tillgängliga material i provinsen designades slutligen en rötkammare. Rötkammaren dimensionerades så att den kunde förse en familj med bränsle för matlagning. Om den dagliga biogasproduktionen når 2.5 m3 är det möjligt att ersätta 178 kg gasol eller 9855 kg ved per år. Minskningen av gasol resulterar i en årlig reducering av växthusgasutsläpp med minst 2700 kg koldioxidekvivalenter. Minskningen av gasol resulterar också i en årlig besparing på 9062 PHP (1672 SEK). Denna siffra motsvarar 11 procent av den totala investeringskostnaden för rötkammaren.

In this study, incubations of sediments from three Swedish lakes, Parsen, Södra Teden, and Venasjön, were made to examine CH4 production during different temperatures. The incubations took place in two different climate rooms, one with a decreasing temperature and one with an increasing temperature with analyses made on the temperature levels around 10 and 20°C. Samples were taken and analyzed in a gas chromatograph. Results from the incubations ranged from -3,72 μmol m-2 d-1 up to 10,54 μmol m-2 d-1. A Mann Whitney test were made to test the statistical hypothesis if there were any differences in CH4 production between the temperatures. Only Venasjön were significantly different in CH4 production (P=0.01) while Södra Teden and Parsen were non-significant. Discussed points were that the lakes have potential for CH4 production, but there is several factors beside the temperature change that both favors and inhibit the production rates. Södra Teden displayed an individual measurement with a high production rate which suggest a major potential for CH4 production. The study concludes that the temperature effect is not clear in this study due to the lack of significant difference between the temperature levels. It also concludes that we need a bigger understanding of the lakes to be able to draw further conclusions of the results. A final conclusion was that it did not matter whether the sediments were exposed for a temperature increase or a decrease. The study suggested that further research is needed for similar lakes with more samples to enrich the statistical analyses and develop the knowledge about which factors that regulates CH4 production in Swedish freshwater lakes.
I denna studie genomfördes inkubationer av sediment från tre svenska sjöar, Parsen, Södra Teden, och Venasjön i syfte att undersöka CH4 produktion under olika temperaturnivåer. Inkubationerna genomfördes i två olika klimatrum, ett där temperaturen sänktes och ett där temperaturen höjdes. Temperaturperioderna som analyserades var omkring 20°C som den högre nivån och 10°C som den låga nivån. Provtagningar genomfördes och analyserades i en gaskromatograf för att kunna beräkna produktionen av CH4 under de olikatidsperioderna. Analysen gjordes utan att ta hänsyn till vilka prover som hade en sänkt temperatur eller en höjd temperatur. Resultaten från inkubationerna sträckte sig från -3,72 μmol/m-2 d-1 upp till 10,54 μmol/m-2 d-1.Från Södra Teden uppmättes ett enskilt värde som visar på att den sjön har en mycket stor potential för att producera metan. Andra diskuterade punkter är hur kvalitén och mängden organiskt material som och även hur mycket näringsämnen som finns tillgängligt i sjöarnas sediment. En av slutsatserna är att effekten av temperaturförändringen inte är tydlig på grund av bristen på signifikant skillnad mellan de båda temperaturnivåerna. Studien visar också på att vi behöver en större förståelse av sjöarna i sig för att kunna dra ytterligare slutsatser av resultaten. Sist men inte minst så hade det minimal eller ingen betydelse om sedimenten utsattes för en temperaturhöjning eller en temperatursänkning. Studien förslår att ytterligare studier behöver genomföras på liknande sjöar med fler prover för varje sjö för att berika den statistiska analysen och utveckla kunskapen om vilka faktorer som reglerar bildningen av CH4 i svenska sjöar.

Dairy processing waste (DPW) can cause many environmental problems if not treated well. Various wastewater treatment technologies have been applied to reduce the organics and inorganics in DPW. The overall objective of this research was to develop cost effective anaerobic digestion technology for hydrogen and methane production from DPW. This search included three phases of studies. In phase 1, we investigated continuous fermentations of algae, lawn grass clippings and DPW, commingled and digested in duplicate 60 L and 3,800 L Induced Bed Reactor (IBR) anaerobic digesters at mesophilic conditions in trials that went for about two years. The goal was to commingle municipal waste in such a way that no pH control chemicals would be required. The research also yielded information about solids loading rate (SLR), efficiency of chemical oxygen demand (COD) and solids removal and biogas production. Under the conditions of the study, commingling algae or grass with DPW made it possible to avoid the addition of pH control chemicals. In phase 2, we investigated the effects of pH, temperature, and hydraulic retention time (HRT) and organic loading rate (OLR) on hydrogen production from DPW in semicontinuous 60 L pilot IBR. Results show pH played a key role on hydrogen production and the optimal pH range was 4.8-5.5. Digestion under thermophilic temperatures (60 °C) had advantages of gaining higher hydrogen yield and suppressing the growth of methanogens. The optimal OLR was 32.9 g-COD/l-d at HRT of 3 days. Under optimal conditions, highest hydrogen yield was 160.7 ml/g-COD removed with 44.6% COD removal. In phase 3, a mathematic model was built and implemented in R based on Anaerobic Digestion Model No. 1 (ADM1) for predicting and describing the anaerobic hydrogen production process. The modified ADM1 was then validated by comparing the predictions with observations of anaerobic hydrogen production from dairy processing waste. The model successfully predicted hydrogen production, hydrogen content, methane content, VFA concentration, and digestion system stability. This study provides a useful mathematical model to investigate anaerobic hydrogen production process and stability.

Dark fermentation of organic wastes is considered as a promising process in terms of sustainable waste management and simultaneous biofuel production. Pre-treatment technologies are known as essentials of dark fermentation to overcome obstacles responsible for low H2 yield. The effect of aerobic pre-treatment of food wastes with different compositions (carbohydrate-rich, protein-rich and lipid-rich) prior to two-stage anaerobic digestion, on H2 and CH4 productions was investigated. The results showed that pre-aeration of food waste did not constitute an effective treatment for the purpose of improving H2 production potential during the first stage of the AD process. However, during the subsequent stage of AD, CH4 yield for protein-rich substrate, increased by 45.6%, thus revealing that carbon conversion to CH4 had an increase after pre-aeration. In case of inoculum pre-treatment, a novel method using waste frying oil (WFO) was introduced. H2 production from glucose was investigated for inoculum pre-treated with different concentrations of WFO. In the next step, a flux balance analysis model was developed to study the effect of inoculum pre-treatment on H2 producing and H2 consuming metabolic pathways. The results showed that H2 consumption by hydrogenotrophic methanogens that was accounted for about 56% of the loss in the H2 yield in untreated cultures, was negligible when the inoculum pre-treated with WFO. Moreover, optimization of H2 yield from food waste was performed in the next step of research, using a three-factor three-level Box-Behnken design method. Initial pH, pre-treatment duration and waste frying oil concentration were considered as the experimental factors. The results showed that combination of high WFO concentration, low initial pH and long pre-treatment could result in inhibition of methanogens. Furthermore, two-stage anaerobic digestion of food waste was performed using the inoculum pre-treated with WFO and total energy yield was compared with three common pre-treatments (heat shock, aeration and alkaline pre-treatment) and untreated cultures. The results showed that inoculum pre-treatment with WFO resulted in higher H2 and CH4 productions compared to alkaline, aeration and heat shock pre-treatment. Finally, microbial community of inoculum at different stages of dark fermentation (untreated, pre-treated with WFO, washed and fermented) was investigated to understand the effect of inoculum pre-treatment with WFO on H2 producing and H2 consuming microbial populations. The microbial diversity analysis showed that inoculum pre-treatment with WFO did not affect spore-forming H2 producing bacteria. However, it resulted in increased relative abundances of non-spore forming H2 producers which could be considered as an advantage in comparison with harsh pre-treatments such as heat shock.

Thesis (M.S.)--West Virginia University, 2007.
Title from document title page. Document formatted into pages; contains ix, 67 p. : ill. (some col.), col. map. Includes abstract. Includes bibliographical references (p. 64-67).

Hydrogen is considered to be an important potential energy carrier; however, its advantages are unlikely to be realized unless efficient means can be found to produce it without generation of CO₂. Sorption-enhanced steam methane reforming (SE-SMR) represent a novel, energy-efficient hydrogen production route with in situ CO₂ capture, shifting the reforming and water gas shift reactions beyond their conventional thermodynamic limits.

The use of fluidized bed reactors for SE-SMR has been investigated. Arctic dolomite, a calcium-based natural sorbent, was chosen as the primary CO₂-acceptor in this study due to high absorption capacity, relatively high reaction rate and low cost. An experimental investigation was conducted in a bubbling fluidized bed reactor of diameter 0.1 m, which was operated cyclically and batchwise, alternating between reforming/carbonation conditions and higher-temperature calcination conditions. Hydrogen concentrations of >98 mole% on a dry basis were reached at 600°C and 1 atm, for superficial gas velocities in the range of ~0.03-0.1 m/s. Multiple reforming-regeneration cycles showed that the hydrogen concentration remained at ~98 mole% after four cycles. The total production time was reduced with an increasing number of cycles due to loss of CO₂ -uptake capacity of the dolomite, but the reaction rates of steam reforming and carbonation seemed to be unaffected for the conditions investigated.

A modified shrinking core model was applied for deriving carbonation kinetics of Arctic dolomite, using experimental data from a novel thermo gravimetric reactor. An apparent activation energy of 32.6 kJ/mole was found from parameter fitting, which is in good agreement with previous reported results. The derived rate expression was able to predict experimental conversion up to ~30% very well, whereas the prediction of higher conversion levels was poorer. However, the residence time of sorbent in a continuous reformer-calciner system is likely to be rather low, so that only a fraction of the sorbent is utilized, highlighting the importance of the carbonation model at lower conversions.

A dual fluidized bed reactor for the SE-SMR system was modeled by using a simple two-phase hydrodynamic model, the experimentally derived carbonation kinetics and literature values for the kinetics of steam reforming and water gas shift reactions. The model delineates important features of the process. Hydrogen concentrations of >98 mole% were predicted for temperatures ~600°C and a superficial gas velocity of 0.1 m/s. The reformer temperature should not be lower than 540°C or greater than 630°C for carbon capture efficiencies to exceed 90%. Operating at relatively high solid circulation rates to reduce the need for fresh sorbent, is predicted to give higher system efficiencies than for the case where fresh solid is added. This finding is attributed to the additional energy required to decompose both CaCO₃ and MgCO₃ in fresh dolomite. Moreover, adding fresh sorbent is likely to result in catalyst loss in the purge stream, requiring sorbents with lifetimes comparable to those of the catalyst.

Thermo gravimetric analysis (TGA) was used to study the reversible CO₂-uptake of sorbents. In general, the multi-cycle capacity of the dolomite was found rather poor. Therefore, synthetic sorbents that maintain their capacities upon multiple reforming-calcination cycles were investigated. A low-temperature liquid phase co-precipitation method was used for synthesis of Li₂ZrO₃ and Na₂ZrO₃. Li₂ZrO₃ showed a superior multi-cycle capacity compared to Arctic dolomite in TGA, but the rate of reaction in diluted CO₂ atmospheres was very slow. The synthesized Na₂ZrO₃ proved to have both fast carbonation kinetics and stable multi-cycle performance. However, regeneration in the presence of carbon dioxide was not easily accomplished.

The findings of this thesis suggest that the bubbling fluidized bed reactor is an attractive reactor configuration for SE-SMR. Low gas throughput is the major disadvantage for this configuration, and operation in the fast fluidization regime is most likely to be preferred on an industrial scale of the process. Future work should focus on developing sorbents and catalysts that are suited for high velocity operation, with respect to reactivity and mechanical strength.

Agriculture has been reported to contribute a significant amount of greenhouse gases to the atmosphere among other anthropogenic activities. With still more than 870 million people in the world suffering from under-nutrition and a growing global food demand, it is relevant to study ways for mitigating the environmental impact of food production. The objective of this work was to identify gaps in the knowledge regarding the main factors affecting greenhouse gas (GHG) emissions from beef farming systems, to reduce the uncertainty on carbon footprint predictions, and to study the relative importance of mitigation options at the system level. A lack of information in the literature was identified regarding the quantification of the relevant animal characteristics of extensive beef systems that can impact on methane (CH4) outputs. In a meta-analysis study, it was observed that the combination of physiological stage and type of diet improved the accuracy of CH4 emission rate predictions. Furthermore, when applied to a system analysis, improved equations to predict CH4 from ruminants under different physiological stages and diet types reduced the uncertainty of whole-farm enteric CH4 predictions by up to 7% over a year. In a modelling study, it was demonstrated that variations in grazing behaviour and grazing choice have a potentially large impact upon CH4 emissions, which are not normally mentioned within carbon budget calculations at either local or national scale. Methane estimations were highly sensitive to changes in quality of the diet, highlighting the importance of considering animal selectivity on carbon budgets of heterogeneous grasslands. Part of the difficulties on collecting reliable information from grazing cattle is due to some limitations of available techniques to perform CH4 emission measurements. Thus, the potential use of a Laser Methane Detector (LMD) for remote sensing of CH4 emissions from ruminants was evaluated. A data analysis method was developed for the LMD outputs. The use of a novel technique to assess CH4 production from ruminants showed very good correlations with independent measurements in respiration chambers. Moreover, the use of this highly sensitive technique demonstrates that there is more variability associated with the pattern of CH4 emissions which cannot be explained by the feed nutritional value. Lastly, previous findings were included in a deterministic model to simulate alternative management options applied to upland beef farming systems. The success of the suggested management technologies to mitigate GHG emissions depends on the characteristics of the farms and management previously adopted. Systems with high proportion of their land unsuitable for cropping but with an efficient use of land had low and more certain GHG emissions, high human-edible returns, and small opportunities to further reduce their carbon footprint per unit of product without affecting food production, potential biodiversity conservation and the livelihood of the region. Altogether, this work helps to reduce the uncertainty of GHG predictions from beef farming systems and highlights the essential role of studies with a holistic approach to issues related to climate change that encompass the analysis of a large range of situations and management alternatives.

The main objective of this study is to investigate on the ability of a perovskite-based membrane reactor to produce hydrogen via simultaneous reforming and water splitting processes. Being able to perform such processes will confirm on the ability of the membrane system in performing an autothermal production of hydrogen. Initial experiments were conducted to evaluate the ability of two different types of hollow fibre membrane namely La0.6Sr0.4Co0.2Fe0.8O3-δ (LSCF6428) and Ba0.5Sr0.5Co0.8Fe0.2O3-δ (BSCF5582) in permeating oxygen in three different inlet configurations. All of the experiments were conducted at 900oC. The LSCF6428 membrane gives lower oxygen permeation rate comparing to BSCF5582 when inert gas argon was used as the sweep gas on the shell side of the membrane. The oxygen permeation rate into the shell side of LSCF6428 membrane reactor was at 0.24μmolO.s-1 whereas for BSCF5582 was at 1.50μmol O.s-1. The trend is similar when the shell sides were fed with 5% methane and the lumen sides were fed with 10% oxygen. In these experiments, both membranes were stable enough to perform oxygen permeation up to more than 100 hours of operation. BSCF5582 membrane however shows instability in performing oxygen permeation when the lumen side was fed with 4% water and shell side was fed with 5% methane. BSCF5582 membrane was only able to perform oxygen permeation for less than two hours before showing substantial amount of leaks upon breaking. In contrast, the iii LSCF6428 membrane shows good stability in the same condition with the shell side oxygen permeation rate of 0.04±0.01μmolO.s-1. The experiment operating time lasted for more than 90 hours. Based on its stability in performing oxygen permeation in the combination of highly reducing and highly oxidising environment, the LSCF6428 membranes were chosen to perform the simultaneous methane reforming and water splitting process in a multiple-membrane based reactor. The results obtained from this experiment proved that simultaneous methane reforming and water splitting can be achieved using a membrane reactor.