The steam reforming of hydrocarbons with special reference to methane

From an examination of the literature relating to the catalytic steam reforming of hydrocarbons, it is concluded that the kinetics of high pressure reforming, particularly steam-methane reforming, has received relatively little attention. Therefore because of the increasing availability of natural gas in the U.K., this system was considered worthy of investigation. An examination of the thermodynamics relating to the equilibria of steam-hydrocarbon reforming is described. The reactions most likely to have influence over the process are established and from these a computer program was written to calculate equilibrium compositions. A means of presenting such data in a graphica1 form for ranges of the operating variables is given, and also an operating chart which may be used to quickly check feed ratios employed on a working naphtha reforming plant is presented. For the experimental kinetic study of the steam-methane system, cylindrical pellets of ICI 46-1 nickel catalyst were used in the form of a rod catalyst. The reactor was of the integral type and a description is given with the operating procedures and analytical method used. The experimental work was divided into two parts, qualitative and quantitative. In the qualitative study the various reaction steps are examined in order to establish which one is rate controlling. It is concluded that the effects of film diffusion resistance within the conditions employed are negligible. In the quantitative study it was found that at 250 psig and 6500C the steam-methane reaction is much slower than the CO shift reaction and is rate controlling. Two rate mechanisms and accompanying kinetic rate equations are derived, both of which represent 'chemical' steps in the reaction and are considered of equal merit. However the possibility of a dual control involving 'chemical' and pore diffusion resistances is also expressed.

The separation of hydrogen and carbon monoxide using polymer membranes

This work studies the development of polymer membranes for the separation of hydrogen and carbon monoxide from a syngas produced by the partial oxidation of natural gas. The CO product is then used for the large scale manufacture of acetic acid by reaction with methanol. A method of economic evaluation has been developed for the process as a whole and a comparison is made between separation of the H2/CO mixture by a membrane system and the conventional method of cryogenic distillation. Costs are based on bids obtained from suppliers for several different specifications for the purity of the CO fed to the acetic acid reactor. When the purity of the CO is set at that obtained by cryogenic distillation it is shown that the membrane separator offers only a marginal cost advantage. Cost parameters for the membrane separation systems have been defined in terms of effective selectivity and cost permeability. These new parameters, obtained from an analysis of the bids, are then used in a procedure which defines the optimum degree of separation and recovery of carbon monoxide for a minimum cost of manufacture of acetic acid. It is shown that a significant cost reduction is achieved with a membrane separator at the optimum process conditions. A method of "targeting" the properties of new membranes has been developed. This involves defining the properties for new (hypothetical -yet to be developed) membranes such that their use for the hydrogen/carbon monoxide separation will produce a reduced cost of acetic acid manufacture. The use of the targeting method is illustrated in the development of new membranes for the separation of hydrogen and carbon monoxide. The selection of polymeric materials for new membranes is based on molecular design methods which predict the polymer properties from the molecular groups making up the polymer molecule. Two approaches have been used. One method develops the analogy between gas solubility in liquids and that in polymers. The UNIFAC group contribution method is then used to predict gas solubility in liquids. In the second method the polymer Permachor number, developed by Salame, has been correlated with hydrogen and carbon monoxide permeabilities. These correlations are used to predict the permeabilities of gases through polymers. Materials have been tested for hydrogen and carbon monoxide permeabilities and improvements in expected economic performance have been achieved.

The structural permeability of concrete at cryogenic temperatures

The thesis describes a programme of research designed to identify concretes for application at cryogenic temperature, in particular for storage of Liquefield Natural Gas which is maintained at a temperature of -165oC. The programme was undertaken in two stages. Stage 1 involved screening tests on seventeen concrete mixes to investigate the effects of strength grade (and water/cement ratio), air entrainment, aggregate type and cement type. Four mixes were selected on the basis of low temperature strength, residual strength after thermal cycling and permeability at ambient temperature. In Stage 2 the selected mixes were subjected to a comprehensive range of tests to measure those properties which determine the leak tightness of a concrete tank at temperatures down to -165oC. These included gas permeability; tensile strength, strain capacity, thermal expansion coefficient and elastic modulus, which in combination provide a measure of resistance to cracking; and bond to reinforcement, which is one of the determining factors regarding crack size and spacing. The results demonstrated that the properties of concrete were generally enhanced at cryogenic temperature, with reduced permeability, reduced crack proneness and, by virtue of increased bond to reinforcement, better control of cracking should it occur. Of the concretes tested, a lightweight mix containing sintered PFA aggregate exhibited the best performance at ambient and cryogenic temperature, having appreciably lower permeability and higher crack resistance than normal weight concretes of the same strength grade. The lightweight mix was most sensitive to thermal cycling, but there was limited evidence that this behaviour would not be significant if the concrete was prestressed. Relationships between various properties have been identified, the most significant being the reduction in gas permeability with increasing strain capacity. The structural implications of the changing properties of the concrete have also been considered.

Waste to power

ABSTRACT: There has been a growing trend towards the use of biomass as a primary energy source, which now contributes over 54% of the European pulp and paper industry energy needs [1]. The remaining part comes from natural gas, which to a large extent serves as the major source of energy for numerous recovered fiber paper mills located in regions with limited available forest resources. The cost of producing electricity to drive paper machinery and generate heat for steam is increasing as world demand for fossil fuels increases. Additionally, recovered fiber paper mills are also significant producers of fibrous sludge and reject waste material that can contain high amounts of useful energy. Currently, a majority of these waste fractions is disposed of by landspreading, incineration, or landfill. Paper mills must also pay a gate fee to process their waste streams in this way and the result of this is a further increase in operating costs. This work has developed methods to utilize the waste fractions produced at recovered fiber paper mills for the onsite production of combined heat and power (CHP) using advanced thermal conversion methods (pyrolysis and gasification) that are well suited to relatively small scales of throughput. The electrical power created would either be used onsite to power the paper making process or alternatively exported to the national grid, and the surplus heat created could also be used onsite or exported to a local customer. The focus of this paper is to give a general overview of the project progress so far and will present the experimental results of the most successful thermal conversion trials carried out by this work to date. Application: The research provides both paper mills and energy providers with methodologies to condition their waste materials for conversion into useful energy. The research also opens up new markets for gasifier and pyrolysis equipment manufacturers and suppliers.

Sustainable energy from paper industry wastes

Secondary fibre paper mills are significant users of both heat and electricity which is mainly derived from the combustion of fossil fuels. The cost of producing this energy is increasing year upon year. These mills are also significant producers of fibrous sludge and reject waste material which can contain high amounts of useful energy. Currently the majority of these waste fractions are disposed of by landfill, land-spread or incineration using natural gas. These disposal methods not only present environmental problems but are also very costly. The focus of this work was to utilise the waste fractions produced at secondary fibre paper mills for the on-site production of combined heat and power (CHP) using advanced thermal conversion methods (gasification and pyrolysis), well suited to relatively small scales of throughput. The heat and power can either be used on-site or exported. The first stage of the work was the development of methods to condition selected paper industry wastes to enable thermal conversion. This stage required detailed characterisation of the waste streams in terms of proximate and ultimate analysis and heat content. Suitable methods to dry and condition the wastes in preparation for thermal conversion were also explored. Through trials at pilot scale with both fixed bed downdraft gasification and intermediate pyrolysis systems, the energy recovered from selected wastes and waste blends in the form of product gas and pyrolysis products was quantified. The optimal process routes were selected based on the experimental results, and implementation studies were carried out at the selected candidate mills. The studies consider the pre-processing of the wastes, thermal conversion, and full integration of the energy products. The final stage of work was an economic analysis to quantify economic gain, return on investment and environmental benefits from the proposed processes.

Philosophy, theory, and practice of green operations management

This paper proposes a more profound discussion of the philosophical underpins of sustainability than currently exists in the MOT literature and considers their influence on the construction of the theories on green operations and technology management. Ultimately, it also debates the link between theory and practice on this subject area. The paper is derived from insights gained in three research projects completed during the past twelve years, primarily involving the first author. From 2000 to 2002, an investigation using scenario analysis, aimed at reducing atmospheric pollution in urban centres by substituting natural gas for petrol and diesel, provided the first set of insights about public policy, environmental impacts, investment analysis, and technological feasibility. The second research project, from 2003 to 2005, using a survey questionnaire, was aimed at improving environmental performance in livestock farming and explored the issues of green supply chain scope, environmental strategy and priorities. Finally, the third project, from 2006 to 2011, investigated environmental decisions in manufacturing organisations through case study research and examined the underlying sustainability drivers and decision-making processes. By integrating the findings and conclusions from these projects, the link between philosophy, theory, and practice of green operations and technology management is debated. The findings from all these studies show that the philosophical debate seems to have little influence on theory building so far. For instance, although ‘sustainable development’ emphasises ‘meeting the needs of current and future generation’, no theory links essentiality and environmental impacts. Likewise, there is a weak link between theory and the practical issues of green operations and technology management. For example, the well-known ‘life-cycle analysis’ has little application in many cases because the life cycle of products these days is dispersed within global production and consumption systems and there are different stakeholders for each life cycle stage. The results from this paper are relevant to public policy making and corporate environmental strategy and decision making. Most of the past and current studies in the subject of green operations and sustainability management deal with only a single sustainability dimension at any one time. Here the value and originality of this paper lies in its integration between philosophy, theory, and practice of green technology and operations management.

Assessing economically viable carbon reductions for the production of ammonia from biomass gasification

Greenhouse gas emissions from fertiliser production are set to increase before stabilising due to the increasing demand to secure sustainable food supplies for a growing global population. However, avoiding the impacts of climate change requires all sectors to decarbonise by a very high level within several decades. Economically viable carbon reductions of substituting natural gas reforming with biomass gasification for ammonia production are assessed using techno-economic and life cycle assessment. Greenhouse gas savings of 65% are achieved for the biomass gasification system and the internal rate of return is 9.8% at base-line biomass feedstock and ammonia prices. Uncertainties in the assumptions have been tested by performing sensitivity analysis, which show, for example with a ±50% change in feedstock price, the rate of return ranges between -0.1% and 18%. It would achieve its target rate of return of 20% at a carbon price of £32/t CO, making it cost competitive compared to using biomass for heat or electricity. However, the ability to remain competitive to investors will depend on the volatility of ammonia prices, whereby a significant decrease would require high carbon prices to compensate. Moreover, since no such project has been constructed previously, there is high technology risk associated with capital investment. With limited incentives for industrial intensive energy users to reduce their greenhouse gas emissions, a sensible policy mechanism could target the support of commercial demonstration plants to help ensure this risk barrier is resolved. © 2013 The Authors.

Uses of frontier efficiency methodologies and multi-criteria decision making for performance measurement in the energy sector

Guest editorial Ali Emrouznejad is a Senior Lecturer at the Aston Business School in Birmingham, UK. His areas of research interest include performance measurement and management, efficiency and productivity analysis as well as data mining. He has published widely in various international journals. He is an Associate Editor of IMA Journal of Management Mathematics and Guest Editor to several special issues of journals including Journal of Operational Research Society, Annals of Operations Research, Journal of Medical Systems, and International Journal of Energy Management Sector. He is in the editorial board of several international journals and co-founder of Performance Improvement Management Software. William Ho is a Senior Lecturer at the Aston University Business School. Before joining Aston in 2005, he had worked as a Research Associate in the Department of Industrial and Systems Engineering at the Hong Kong Polytechnic University. His research interests include supply chain management, production and operations management, and operations research. He has published extensively in various international journals like Computers & Operations Research, Engineering Applications of Artificial Intelligence, European Journal of Operational Research, Expert Systems with Applications, International Journal of Production Economics, International Journal of Production Research, Supply Chain Management: An International Journal, and so on. His first authored book was published in 2006. He is an Editorial Board member of the International Journal of Advanced Manufacturing Technology and an Associate Editor of the OR Insight Journal. Currently, he is a Scholar of the Advanced Institute of Management Research. Uses of frontier efficiency methodologies and multi-criteria decision making for performance measurement in the energy sector This special issue aims to focus on holistic, applied research on performance measurement in energy sector management and for publication of relevant applied research to bridge the gap between industry and academia. After a rigorous refereeing process, seven papers were included in this special issue. The volume opens with five data envelopment analysis (DEA)-based papers. Wu et al. apply the DEA-based Malmquist index to evaluate the changes in relative efficiency and the total factor productivity of coal-fired electricity generation of 30 Chinese administrative regions from 1999 to 2007. Factors considered in the model include fuel consumption, labor, capital, sulphur dioxide emissions, and electricity generated. The authors reveal that the east provinces were relatively and technically more efficient, whereas the west provinces had the highest growth rate in the period studied. Ioannis E. Tsolas applies the DEA approach to assess the performance of Greek fossil fuel-fired power stations taking undesirable outputs into consideration, such as carbon dioxide and sulphur dioxide emissions. In addition, the bootstrapping approach is deployed to address the uncertainty surrounding DEA point estimates, and provide bias-corrected estimations and confidence intervals for the point estimates. The author revealed from the sample that the non-lignite-fired stations are on an average more efficient than the lignite-fired stations. Maethee Mekaroonreung and Andrew L. Johnson compare the relative performance of three DEA-based measures, which estimate production frontiers and evaluate the relative efficiency of 113 US petroleum refineries while considering undesirable outputs. Three inputs (capital, energy consumption, and crude oil consumption), two desirable outputs (gasoline and distillate generation), and an undesirable output (toxic release) are considered in the DEA models. The authors discover that refineries in the Rocky Mountain region performed the best, and about 60 percent of oil refineries in the sample could improve their efficiencies further. H. Omrani, A. Azadeh, S. F. Ghaderi, and S. Abdollahzadeh presented an integrated approach, combining DEA, corrected ordinary least squares (COLS), and principal component analysis (PCA) methods, to calculate the relative efficiency scores of 26 Iranian electricity distribution units from 2003 to 2006. Specifically, both DEA and COLS are used to check three internal consistency conditions, whereas PCA is used to verify and validate the final ranking results of either DEA (consistency) or DEA-COLS (non-consistency). Three inputs (network length, transformer capacity, and number of employees) and two outputs (number of customers and total electricity sales) are considered in the model. Virendra Ajodhia applied three DEA-based models to evaluate the relative performance of 20 electricity distribution firms from the UK and the Netherlands. The first model is a traditional DEA model for analyzing cost-only efficiency. The second model includes (inverse) quality by modelling total customer minutes lost as an input data. The third model is based on the idea of using total social costs, including the firm’s private costs and the interruption costs incurred by consumers, as an input. Both energy-delivered and number of consumers are treated as the outputs in the models. After five DEA papers, Stelios Grafakos, Alexandros Flamos, Vlasis Oikonomou, and D. Zevgolis presented a multiple criteria analysis weighting approach to evaluate the energy and climate policy. The proposed approach is akin to the analytic hierarchy process, which consists of pairwise comparisons, consistency verification, and criteria prioritization. In the approach, stakeholders and experts in the energy policy field are incorporated in the evaluation process by providing an interactive mean with verbal, numerical, and visual representation of their preferences. A total of 14 evaluation criteria were considered and classified into four objectives, such as climate change mitigation, energy effectiveness, socioeconomic, and competitiveness and technology. Finally, Borge Hess applied the stochastic frontier analysis approach to analyze the impact of various business strategies, including acquisition, holding structures, and joint ventures, on a firm’s efficiency within a sample of 47 natural gas transmission pipelines in the USA from 1996 to 2005. The author finds that there were no significant changes in the firm’s efficiency by an acquisition, and there is a weak evidence for efficiency improvements caused by the new shareholder. Besides, the author discovers that parent companies appear not to influence a subsidiary’s efficiency positively. In addition, the analysis shows a negative impact of a joint venture on technical efficiency of the pipeline company. To conclude, we are grateful to all the authors for their contribution, and all the reviewers for their constructive comments, which made this special issue possible. We hope that this issue would contribute significantly to performance improvement of the energy sector.

Novel biomass conversion routes:ammonia from biomass, and marine macroalgae for energy

This thesis presents a techno-economic investigation of the generation of electricity from marine macroalgae (seaweed) in the UK (Part 1), and the production of anhydrous ammonia from synthesis gas (syngas) generated from biomass gasification (Part 2). In Part 1, the study covers the costs from macroalgae production to the generation of electricity via a CHP system. Seven scenarios, which varied the scale and production technique, were investigated to determine the most suitable scale of operation for the UK. Anaerobic digestion was established as the most suitable technology for macroalgae conversion to CHP, based on a number of criteria. All performance and cost data have been taken from published literature. None of the scenarios assessed would be economically viable under present conditions, although the use of large-scale electricity generation has more potential than small-scale localised production. Part 2 covers the costs from the delivery of the wood chip feedstock to the production of ammonia. Four cases, which varied the gasification process used and the scale of production, were investigated to determine the most suitable scale of operation for the UK. Two gasification processes were considered, these were O2-enriched air entrained flow gasification and Fast Internal Circulating Fluidised Bed. All performance and cost data have been taken from published literature, unless otherwise stated. Large-scale (1,200 tpd) ammonia production using O2-enriched air entrained flow gasification was determined as the most suitable system, producing the lowest ammonia-selling price, which was competitive to fossil fuels. Large-scale (1,200 tpd) combined natural gas/biomass syngas ammonia production also generated ammonia at a price competitive to fossil fuels.

Assessing economically viable carbon reductions for the production of ammonia from biomass gasification

Greenhouse gas emissions from fertiliser production are set to increase before stabilising due to the increasing demand to secure sustainable food supplies for a growing global population. However, avoiding the impacts of climate change requires all sectors to decarbonise by a very high level within several decades. Economically viable carbon reductions of substituting natural gas reforming with biomass gasification for ammonia production are assessed using techno-economic and life cycle assessment. Greenhouse gas savings of 65% are achieved for the biomass gasification system and the internal rate of return is 9.8% at base-line biomass feedstock and ammonia prices. Uncertainties in the assumptions have been tested by performing sensitivity analysis, which show, for example with a ±50% change in feedstock price, the rate of return ranges between -0.1% and 18%. It would achieve its target rate of return of 20% at a carbon price of £32/t CO, making it cost competitive compared to using biomass for heat or electricity. However, the ability to remain competitive to investors will depend on the volatility of ammonia prices, whereby a significant decrease would require high carbon prices to compensate. Moreover, since no such project has been constructed previously, there is high technology risk associated with capital investment. With limited incentives for industrial intensive energy users to reduce their greenhouse gas emissions, a sensible policy mechanism could target the support of commercial demonstration plants to help ensure this risk barrier is resolved. © 2013 The Authors.

The use of methane as automotive fuel – a step to sustainable economy?

The introduction of CNG (Compressed Natural Gas) as automotive fuel began in Italy as early as in mid- 1930s, and ever since the Italian market has always been highly advanced in this regard. Many other countries followed, some of them quite recently, but nevertheless with impressive results. The appeal of this automotive fuel is based on the fact that compared to gasoline, diesel and LPG (Liquefied Petroleum Gas), CNG is cleaner and cheaper; even more so, this fuel is renewable – it can be produced locally from biogas. Despite its obvious benefits, CNG is barely present in Hungary. This article provides an insight into the topic, highlights obstacles to introduction and suggests appropriate governmental steps. The information is intended to support the activities and the decision-making process of governmental officials, municipalities, car-fleet managers, car dealers and their service departments.

Analyzing interrelated stochastic trend and seasonality on the example of energy trading data

The correct modelling of long- and short-term seasonality is a very interesting issue. The choice between the deterministic and stochastic modelling of trend and seasonality and their implications are as relevant as the case of deterministic and stochastic trends itself. The study considers the special case when the stochastic trend and seasonality do not evolve independently and the usual differencing filters do not apply. The results are applied to the day-ahead (spot) trading data of some main European energy exchanges (power and natural gas).

Analyzing interrelated stochastic trend and seasonality on the example of energy trading data

The correct modelling of long- and short-term seasonality is a very interesting issue. The choice between the deterministic and stochastic modelling of trend and seasonality and their implications are as relevant as the case of deterministic and stochastic trends itself. The study considers the special case when the stochastic trend and seasonality do not evolve independently and the usual differencing filters do not apply. The results are applied to the day-ahead (spot) trading data of some main European energy exchanges (power and natural gas).

The advantage of Spanish multinational enterprises in Latin America

Multinational enterprises (MNEs) from Spain made large foreign direct investments (FDIs) in Latin America between 1990 and 2002, making Spain the second largest direct investor in this region since 1998, behind the United States. This dissertation explains the reasons that led Spanish firms to make these FDIs, as well as their operations in Latin America. Seven Spanish MNEs were included in this study, BBVA and SCH (banking), Telefónica (telecommunications), Endesa, Iberdrola and Unión Fenosa (public utilities), and Repsol-YPF (oil and natural gas). Quantitative and qualitative data were used. Data were collected from the firms' annual reports, from their archives and from personal interviews with senior executives, as well as from academic and specialized publications. ^ Results indicate that the large Spanish FDIs in Latin America were highly concentrated in a few firms from five sectors. The FDIs of these firms alone accounted for 70 percent of total Spanish FDI in Latin America in this period. The reasons for these investments were firm-specific and sector specific. A series of institutional conditions existed in Spain between the 1970s and the 1990s that allowed the employees of the firms to develop the knowledge and devise strategies to adjust to that set of conditions. First, the policies of the Spanish state favored the creation of large firms in these sectors, operating under conditions of monopoly sometimes. Secondly, the consumers put pressure on the firms to provide better and cheaper products as the Spanish economy grew and modernized. Thirdly, the employees of the firms had to adjust their services and products to the demands of the consumers and to the constraints of the state and the market. They adjusted the internal organization of the firm to be able to produce the goods and services that the market demanded. Externally, they also adopted patterns of interaction with outside agents and institutions. This patterned behavior was the “corporate culture” of each firm and the “normative framework” in which their employees operated. When the managers of the firms perceived that there were similar conditions in Latin America, they decided to operate there as well by making FDIs. ^

Modelagem e simulação da solubilidade de sais em sistemas aquosos com Monoetilenoglicol

Primary processing of natural gas platforms as Mexilhão Field (PMXL-1 ) in the Santos Basin, where monoethylene glycol (MEG) has been used to inhibit the formation of hydrates, present operational problems caused by salt scale in the recovery unit of MEG. Bibliographic search and data analysis of salt solubility in mixed solvents, namely water and MEG, indicate that experimental reports are available to a relatively restricted number of ionic species present in the produced water, such as NaCl and KCl. The aim of this study was to develop a method for calculating of salt solubilities in mixed solvent mixtures, in explantion, NaCl or KCl in aqueous mixtures of MEG. The method of calculating extend the Pitzer model, with the approach Lorimer, for aqueous systems containing a salt and another solvent (MEG). Python language in the Integrated Development Environment (IDE) Eclipse was used in the creation of the computational applications. The results indicate the feasibility of the proposed calculation method for a systematic series of salt (NaCl or KCl) solubility data in aqueous mixtures of MEG at various temperatures. Moreover, the application of the developed tool in Python has proven to be suitable for parameter estimation and simulation purposes