Selective catalytic reduction of nitrogen oxides with ammonia in forced unsteady state reactors - Case based reasoning and mathematical model simulation reasoning

The application of forced unsteady-state reactors in case of selective catalytic reduction of nitrogen oxides (NOx) with ammonia (NH3) is sustained by the fact that favorable temperature and composition distributions which cannot be achieved in any steady-state regime can be obtained by means of unsteady-state operations. In a normal way of operation the low exothermicity of the selective catalytic reduction (SCR) reaction (usually carried out in the range of 280-350°C) is not enough to maintain by itself the chemical reaction. A normal mode of operation usually requires supply of supplementary heat increasing in this way the overall process operation cost. Through forced unsteady-state operation, the main advantage that can be obtained when exothermic reactions take place is the possibility of trapping, beside the ammonia, the moving heat wave inside the catalytic bed. The unsteady state-operation enables the exploitation of the thermal storage capacity of the catalyticbed. The catalytic bed acts as a regenerative heat exchanger allowing auto-thermal behaviour when the adiabatic temperature rise is low. Finding the optimum reactor configuration, employing the most suitable operation model and identifying the reactor behavior are highly important steps in order to configure a proper device for industrial applications. The Reverse Flow Reactor (RFR) - a forced unsteady state reactor - corresponds to the above mentioned characteristics and may be employed as an efficient device for the treatment of dilute pollutant mixtures. As a main disadvantage, beside its advantages, the RFR presents the 'wash out' phenomena. This phenomenon represents emissions of unconverted reactants at every switch of the flow direction. As a consequence our attention was focused on finding an alternative reactor configuration for RFR which is not affected by the incontrollable emissions of unconverted reactants. In this respect the Reactor Network (RN) was investigated. Its configuration consists of several reactors connected in a closed sequence, simulating a moving bed by changing the reactants feeding position. In the RN the flow direction is maintained in the same way ensuring uniformcatalyst exploitation and in the same time the 'wash out' phenomena is annulated. The simulated moving bed (SMB) can operate in transient mode giving practically constant exit concentration and high conversion levels. The main advantage of the reactor network operation is emphasizedby the possibility to obtain auto-thermal behavior with nearly uniformcatalyst utilization. However, the reactor network presents only a small range of switching times which allow to reach and to maintain an ignited state. Even so a proper study of the complex behavior of the RN may give the necessary information to overcome all the difficulties that can appear in the RN operation. The unsteady-state reactors complexity arises from the fact that these reactor types are characterized by short contact times and complex interaction between heat and mass transportphenomena. Such complex interactions can give rise to a remarkable complex dynamic behavior characterized by a set of spatial-temporal patterns, chaotic changes in concentration and traveling waves of heat or chemical reactivity. The main efforts of the current research studies concern the improvement of contact modalities between reactants, the possibility of thermal wave storage inside the reactor and the improvement of the kinetic activity of the catalyst used. Paying attention to the above mentioned aspects is important when higher activity even at low feeding temperatures and low emissions of unconverted reactants are the main operation concerns. Also, the prediction of the reactor pseudo or steady-state performance (regarding the conversion, selectivity and thermal behavior) and the dynamicreactor response during exploitation are important aspects in finding the optimal control strategy for the forced unsteady state catalytic tubular reactors. The design of an adapted reactor requires knowledge about the influence of its operating conditions on the overall process performance and a precise evaluation of the operating parameters rage for which a sustained dynamic behavior is obtained. An apriori estimation of the system parameters result in diminution of the computational efforts. Usually the convergence of unsteady state reactor systems requires integration over hundreds of cycles depending on the initial guess of the parameter values. The investigation of various operation models and thermal transfer strategies give reliable means to obtain recuperative and regenerative devices which are capable to maintain an auto-thermal behavior in case of low exothermic reactions. In the present research work a gradual analysis of the SCR of NOx with ammonia process in forced unsteady-state reactors was realized. The investigation covers the presentationof the general problematic related to the effect of noxious emissions in the environment, the analysis of the suitable catalysts types for the process, the mathematical analysis approach for modeling and finding the system solutions and the experimental investigation of the device found to be more suitable for the present process. In order to gain information about the forced unsteady state reactor design, operation, important system parameters and their values, mathematical description, mathematicalmethod for solving systems of partial differential equations and other specific aspects, in a fast and easy way, and a case based reasoning (CBR) approach has been used. This approach, using the experience of past similarproblems and their adapted solutions, may provide a method for gaining informations and solutions for new problems related to the forced unsteady state reactors technology. As a consequence a CBR system was implemented and a corresponding tool was developed. Further on, grooving up the hypothesis of isothermal operation, the investigation by means of numerical simulation of the feasibility of the SCR of NOx with ammonia in the RFRand in the RN with variable feeding position was realized. The hypothesis of non-isothermal operation was taken into account because in our opinion ifa commercial catalyst is considered, is not possible to modify the chemical activity and its adsorptive capacity to improve the operation butis possible to change the operation regime. In order to identify the most suitable device for the unsteady state reduction of NOx with ammonia, considering the perspective of recuperative and regenerative devices, a comparative analysis of the above mentioned two devices performance was realized. The assumption of isothermal conditions in the beginningof the forced unsteadystate investigation allowed the simplification of the analysis enabling to focus on the impact of the conditions and mode of operation on the dynamic features caused by the trapping of one reactant in the reactor, without considering the impact of thermal effect on overall reactor performance. The non-isothermal system approach has been investigated in order to point out the important influence of the thermal effect on overall reactor performance, studying the possibility of RFR and RN utilization as recuperative and regenerative devices and the possibility of achieving a sustained auto-thermal behavior in case of lowexothermic reaction of SCR of NOx with ammonia and low temperature gasfeeding. Beside the influence of the thermal effect, the influence of the principal operating parameters, as switching time, inlet flow rate and initial catalyst temperature have been stressed. This analysis is important not only because it allows a comparison between the two devices and optimisation of the operation, but also the switching time is the main operating parameter. An appropriate choice of this parameter enables the fulfilment of the process constraints. The level of the conversions achieved, the more uniform temperature profiles, the uniformity ofcatalyst exploitation and the much simpler mode of operation imposed the RN as a much more suitable device for SCR of NOx with ammonia, in usual operation and also in the perspective of control strategy implementation. Theoretical simplified models have also been proposed in order to describe the forced unsteady state reactors performance and to estimate their internal temperature and concentration profiles. The general idea was to extend the study of catalytic reactor dynamics taking into account the perspectives that haven't been analyzed yet. The experimental investigation ofRN revealed a good agreement between the data obtained by model simulation and the ones obtained experimentally.

What is the current state of the Multilingual Web of Data?

The Semantic Web is growing at a fast pace, recently boosted by the creation of the Linked Data initiative and principles. Methods, standards, techniques and the state of technology are becoming more mature and therefore are easing the task of publication and consumption of semantic information on the Web.

Fixed wages and bonuses in agency contracts: the case of a continuous state space

In this paper, we extend the state-contingent production approach to principal–agent problems to the case where the state space is an atomless continuum. The approach is modelled on the treatment of optimal tax problems. The central observation is that, under reasonable conditions, the optimal contract may involve a fixed wage with a bonus for above-normal performance. This is analogous to the phenomenon of "bunching" at the bottom in the optimal tax literature.

Risk premiums and benefit measures for generalized-expected-utility theories

Standard tools for the analysis of economic problems involving uncertainty, including risk premiums, certainty equivalents and the notions of absolute and relative risk aversion, are developed without making specific assumptions on functional form beyond the basic requirements of monotonicity, transitivity, continuity, and the presumption that individuals prefer certainty to risk. Individuals are not required to display probabilistic sophistication. The approach relies on the distance and benefit functions to characterize preferences relative to a given state-contingent vector of outcomes. The distance and benefit functions are used to derive absolute and relative risk premiums and to characterize preferences exhibiting constant absolute risk aversion (CARA) and constant relative risk aversion (CRRA). A generalization of the notion of Schur-concavity is presented. If preferences are generalized Schur concave, the absolute and relative risk premiums are generalized Schur convex, and the certainty equivalents are generalized Schur concave.

Production under uncertainty and choice under uncertainty in the emergence of generalized expected utility theory

This paper presents a personal view of the interaction between the analysis of choice under uncertainty and the analysis of production under uncertainty. Interest in the foundations of the theory of choice under uncertainty was stimulated by applications of expected utility theory such as the Sandmo model of production under uncertainty. This interest led to the development of generalized models including rank-dependent expected utility theory. In turn, the development of generalized expected utility models raised the question of whether such models could be used in the analysis of applied problems such as those involving production under uncertainty. Finally, the revival of the state-contingent approach led to the recognition of a fundamental duality between choice problems and production problems.

Strategic trade policy under uncertainty: Sufficient conditions for the optimality of ad valorem, specific and quadratic trade taxes

In most previous work on strategic trade policy the form of government intervention has been prescribed in advance. In this paper, we apply a solution concept discussed by Klemperer and Meyer for games in which the strategy space consists of the class of all (non state-contingent) price quantity schedules. We examine a series of specific assumptions on demand and supply conditions and derive the associated equilibrium trade policies. We derive welfare implications for all cases examined.

In Search of a theory of debt management

A growing literature integrates theories of debt management into models of optimal fiscal policy. One promising theory argues that the composition of government debt should be chosen so that fluctuations in the market value of debt offset changes in expected future deficits. This complete market approach to debt management is valid even when the government only issues non-contingent bonds. A number of authors conclude from this approach that governments should issue long term debt and invest in short term assets. We argue that the conclusions of this approach are too fragile to serve as a basis for policy recommendations. This is because bonds at different maturities have highly correlated returns, causing the determination of the optimal portfolio to be ill-conditioned. To make this point concrete we examine the implications of this approach to debt management in various models, both analytically and using numerical methods calibrated to the US economy. We find the complete market approach recommends asset positions which are huge multiples of GDP. Introducing persistent shocks or capital accumulation only worsens this problem. Increasing the volatility of interest rates through habits partly reduces the size of these simulations we find no presumption that governments should issue long term debt ? policy recommendations can be easily reversed through small perturbations in the specification of shocks or small variations in the maturity of bonds issued. We further extend the literature by removing the assumption that governments every period costlessly repurchase all outstanding debt. This exacerbates the size of the required positions, worsens their volatility and in some cases produces instability in debt holdings. We conclude that it is very difficult to insulate fiscal policy from shocks by using the complete markets approach to debt management. Given the limited variability of the yield curve using maturities is a poor way to substitute for state contingent debt. The result is the positions recommended by this approach conflict with a number of features that we believe are important in making bond markets incomplete e.g allowing for transaction costs, liquidity effects, etc.. Until these features are all fully incorporated we remain in search of a theory of debt management capable of providing robust policy insights.

Tax smoothing in a business cycle model with capital-skill complementarity

This paper undertakes a normative investigation of the quantitative properties of optimal tax smoothing in a business cycle model with state contingent debt, capital-skill complementarity, endogenous skill formation and stochastic shocks to public consumption as well as total factor and capital equipment productivity. Our main finding is that an empirically relevant restriction which does not allow the relative supply of skilled labour to adjust in response to aggregate shocks, signi cantly changes the cyclical properties of optimal labour taxes. Under a restricted relative skill supply, the government fi nds it optimal to adjust labour income tax rates so that the average net returns to skilled and unskilled labour hours exhibit the same dynamic behaviour as under fl exible skill supply.

Business Advantages, September 27, 2008

Iowa’s business climate has never been more favorable. With the second lowest cost of doing business, companies operating in Iowa benefi t from a business-friendly state government, technology transfer from world-renowned research universities, a skilled and productive labor pool and a centralized geographical location. Following is a brief description of the many business advantages companies enjoy in Iowa.

Iowa System of Bridge Deck Rehabilitation with Cathodic Protection, HR-1044, 1986

Bridge deck and substructure deterioration due to the corrosive effects of deicing chemicals on reinforcing steel is a problem facing many transportation agencies. The main concern is protection of older bridges with uncoated reinforcing steel. Many different methods have been tried over the past years to repair bridge decks. The Iowa system of bridge deck rehabilitation has proven to be very effective. It consists of scarifying the deck surface, removing any deteriorated concrete, and overlaying with low slump dense concrete. Another rehabilitation method that has emerged is cathodic protection. It has been used for many years in the protection of underground pipelines and in 1973 was first installed on a bridge deck. Cathodic protection works by applying an external source of direct current to the embedded reinforcing steel, thereby changing the electrochemical process of corrosion. The corroding steel, which is anodic, is protected by changing it to a cathodic state. The technology involved in cathodic protection as applied to bridge decks has improved over the last 12 years. One company marketing new technology in cathodic protection systems is Raychem Corporation of Menlo Park, California. Their system utilizes a Ferex anode mesh that distributes the impressed direct current over the deck surface. Ferex mesh was selected because it seemed readily adaptable to the Iowa system of bridge deck rehabilitation. The bridge deck would be scarified, deteriorated concrete removed, Ferex anode mesh installed, and overlaid with low slump dense concrete. The Federal Highway Administration (FHWA) promotes cathodic protection under Demonstration Project No. 34, "Cathodic Protection for Reinforced Concrete Bridge Decks."

Digital Exhaustion in relation to Video Games – The Consumer Perspective

This thesis regards exhaustion of copyright’s distribution right in intangible transfers of video games. It analyses whether, under the current law of the European Union, the phenomenon of digital exhaustion, especially in relation to games exists. The thesis analyses the consumers’ position in the market for copyright protected goods. It uses video games market as an example of the wider phenomenon of the effect of latest technological developments on consumers. The research conducted for the thesis is mostly legal dogmatic, although also comparative analysis, law and economics and law and technology methods are utilised. The thesis evaluates the effects of the most recent case law of the European Court of Justice to analyse the current state of digital exhaustion. In the analysis of effects that the existence of digital exhaustion has, the thesis uses the consumers’ point of view. The thesis introduces the current state of technology in the field of video games from a legal perspective. Furthermore the thesis analyses the effects on consumers of a scenario that no digital exhaustion exists in the future. Such scenario under the recent European case law at the moment seems realistic. The conclusion of my research is most importantly that the consumer position in the market for digital goods has deteriorated and that the probable exclusion of the exhaustion for digital goods is another piece of evidence of this development. Most importantly however, the state of affairs where no certainty prevails on whether digital exhaustion exists, creates injustice from the consumers’ point of view. Accordingly, acts by EU legislators of the Court of Justice of the European Union are required to clarify the issue.

Mini-trawls for Estuarine Fishing Kasargod District

Mi ni -trawls are operated by the artisanal fishermen from small wooden non-motorised canoes. Shrimp, fish and crab trawls wi th head rope length rang ing from 3.5-8 m, made of Po lyethy lene mon ofila ment (PE) twisted and Polyamide mullifilament (PA) rigged to 6-7 kll fla t rectangular wooden otter boards are common in the lower reaches of Kariango de and Chandrag iri rive rs. Since the trawling speed is less, ca tch is do minated by crus taceans. Less scope ratio also may be affecting the catching efficiency of the gear. This pape r deals with the design, operation and economics of mini traw ling carried out by a group of fisherme n in the above rivers of Kasargod district Kerala state.

Deception-detection and machine intelligence in practical Turing tests

Deception-detection is the crux of Turing’s experiment to examine machine thinking conveyed through a capacity to respond with sustained and satisfactory answers to unrestricted questions put by a human interrogator. However, in 60 years to the month since the publication of Computing Machinery and Intelligence little agreement exists for a canonical format for Turing’s textual game of imitation, deception and machine intelligence. This research raises from the trapped mine of philosophical claims, counter-claims and rebuttals Turing’s own distinct five minutes question-answer imitation game, which he envisioned practicalised in two different ways: a) A two-participant, interrogator-witness viva voce, b) A three-participant, comparison of a machine with a human both questioned simultaneously by a human interrogator. Using Loebner’s 18th Prize for Artificial Intelligence contest, and Colby et al.’s 1972 transcript analysis paradigm, this research practicalised Turing’s imitation game with over 400 human participants and 13 machines across three original experiments. Results show that, at the current state of technology, a deception rate of 8.33% was achieved by machines in 60 human-machine simultaneous comparison tests. Results also show more than 1 in 3 Reviewers succumbed to hidden interlocutor misidentification after reading transcripts from experiment 2. Deception-detection is essential to uncover the increasing number of malfeasant programmes, such as CyberLover, developed to steal identity and financially defraud users in chatrooms across the Internet. Practicalising Turing’s two tests can assist in understanding natural dialogue and mitigate the risk from cybercrime.

Government policy under price uncertainty: a source of volatility in illegal immigration

In this paper we provide an alternative explanation for why illegal immigration can exhibit substantial fluctuation. We develop a model economy in which migrants make decisions in the face of uncertain border enforcement and lump-sum transfers from the host country. The uncertainty is extrinsic in nature, a sunspot, and arises as a result of ambiguity regarding the commodity price of money. Migrants are restricted from participating in state-contingent insurance markets in the host country, whereas host country natives are not. Volatility in migration flows stems from two distinct sources: the tension between transfers inducing migration and enforcement discouraging it and secondly the existence of a sunspot. Finally, we examine the impact of a change in tax/transfer policies by the government on migration.

Characterization of geothermal reservoirs’ parameters by inverse problem resolution and geostatistical simulations

BTES (borehole thermal energy storage)systems exchange thermal energy by conduction with the surrounding ground through borehole materials. The spatial variability of the geological properties and the space-time variability of hydrogeological conditions affect the real power rate of heat exchangers and, consequently, the amount of energy extracted from / injected into the ground. For this reason, it is not an easy task to identify the underground thermal properties to use when designing. At the current state of technology, Thermal Response Test (TRT) is the in situ test for the characterization of ground thermal properties with the higher degree of accuracy, but it doesn’t fully solve the problem of characterizing the thermal properties of a shallow geothermal reservoir, simply because it characterizes only the neighborhood of the heat exchanger at hand and only for the test duration. Different analytical and numerical models exist for the characterization of shallow geothermal reservoir, but they are still inadequate and not exhaustive: more sophisticated models must be taken into account and a geostatistical approach is needed to tackle natural variability and estimates uncertainty. The approach adopted for reservoir characterization is the “inverse problem”, typical of oil&gas field analysis. Similarly, we create different realizations of thermal properties by direct sequential simulation and we find the best one fitting real production data (fluid temperature along time). The software used to develop heat production simulation is FEFLOW 5.4 (Finite Element subsurface FLOW system). A geostatistical reservoir model has been set up based on literature thermal properties data and spatial variability hypotheses, and a real TRT has been tested. Then we analyzed and used as well two other codes (SA-Geotherm and FV-Geotherm) which are two implementation of the same numerical model of FEFLOW (Al-Khoury model).