LAPPEENRANTA UNIVERSITY OF TECHNOLOGY

Department of Chemical Technology Laboratory of Process Engineering

NEURAL NETWORK FOR PREDICTION OF SUPERHEATER FIRESIDE CORROSION IN ATMOSPHERIC FLUIDIZED BED COMBUSTION

Examiners

professor Lars Nystrom, Lappeenranta University of Technology professor Mikko Hupa, bo Akademi University

Kotka 05.04.1998

Pasi Makkonen Taaplaajankatu 1 B 7 48900 SUNILA

THESIS FOR THE DEGREE OF LICENTIATE OF TECHNOLOGY

PREFACE This study has been carried out at the Foster Wheeler Karhula R&D Center between 1993 and 1997. The first four years were spent by gathering information for the corrosion database, based on which the neural network model was developed in 1997. The subject for the thesis changed several times during the study. At first, the purpose was to create a theoretical model for fouling and corrosion. However, theories of fouling and even calculation programs for estimation of fouling rates are available. Corrosion has been studied for decades, and many theories exist, leaving little room for totally new theories. Corrosion is such a complex phenomenon that whatever theoretical prediction method is used for its estimation, real life brings surprises. So why not use something that can learn the basic relations as a human can and continue learning as knowledge increases? Neural networks have such capabilities, so the thing remaining to be done was to construct a reasonably complex network and teach it to produce the desired result by using the input data available. Such a network can learn all the time, and give more reliable estimations as knowledge increases. Special thanks to Lic. Tech. Matti Hiltunen for the long conversations which made this book possible. This book is dedicated with love to my wife Eeva and my daughter Tea who both have made the life worth living.

ABSTRACT

Pasi Makkonen

Neural Network for Prediction of Superheater Fireside Corrosion in Atmospheric Fluidized Bed Combustion Lappeenranta University of Technology 89 Pages, 50 Figures, 19 Tables, 6 Appendices professor Lars Nystrm, Lappeenranta University of Technology professor Mikko Hupa, bo Akademi University neural network, fluidized bed, combustion, corrosion, fouling

Licentiate thesis

Examiners

Keywords

The theory of neural networks for determination of difficult relations has been available for several decades, but lack of computational resources has limited the commercial use of neural networks until the middle of the 1980s. During the short operating period, the neural networks have reached an indispensable status in handling of unclear correlations and large databases. Different self-organizing maps and adaptive fuzzy controls are common uses for neural networks. The large availability of neural networks is based on learning: the more data there is available, the more reliable the result will be. A neural network can learn all the time and optimize itself by using a feedback connection. Superheater corrosion causes vast annual losses for the power companies. If the corrosion could be reliably predicted, the plants could be designed accordingly, and knowledge of fuel selection and determination of process conditions could be utilized for minimization of superheater corrosion. Growing interest in using recycled fuels creates additional demands for the prediction of corrosion potential. Models depending on corrosion theories will fail, if interdependencies between inputs and the output are poorly known or even more unknown. A prediction model based on a neural network is able to learn from mistakes and improve its performance without major changes in the network structure as the amount of data increases. During this study, a corrosion database was developed based on fuel and bed material analyses and measured corrosion data. The database was used as learning input for the neural network model. The selected neural network contained two hidden layers consisting of non-linear neurons. The developed neural network predicts superheater corrosion with 80 % accuracy on the early stages of a project. This helps to recognize the risk cases and allows selection of corrosion resistant boiler designs. Furthermore, fuel and tube materials can be selected accordingly. The accuracy of the prediction will improve as the amount of data increases.

TABLE OF CONTENTS PREFACE ABSTRACT CONTENTS SYMBOLS THEORETICAL PART 1.0 INTRODUCTION................................................................................................................. 1 2.0 NEURAL NETWORKS....................................................................................................... 2 2.1 Neuron....................................................................................................................... 3 2.2 Activation Function .................................................................................................. 4 2.3 Neural Networks....................................................................................................... 6 2.4 Learning Procedures ................................................................................................. 7 2.5 Applications .............................................................................................................. 7 3.0 FLUIDIZED BED TECHNOLOGY .................................................................................... 8 3.1 Bubbling Fluidized Bed Boiler................................................................................. 9 3.2 Circulating Fluidized Bed......................................................................................... 10 4.0 SUPERHEATER FIRESIDE CORROSION....................................................................... 13 4.1 Mechanism and Kinetics of Oxidation..................................................................... 14 4.2 Sulphur Corrosion..................................................................................................... 17 4.2.1 Formation of SO3 in Fluidized Bed Combustion ..................................... 17 4.2.2 Kinetics of Sulphidation............................................................................ 18 4.2.3 Sulphur Corrosion Mechanisms ............................................................... 19 4.2.4 Sulphide Corrosion ................................................................................... 19 4.2.5 Sulphate Corrosion.................................................................................... 20 4.3 Chlorine Corrosion ................................................................................................... 20 4.3.1 Chlorine Corrosion Mechanisms .............................................................. 21 4.3.2 Kinetics of Chlorine Corrosion................................................................. 24 4.4 Other Corrosion Types ............................................................................................. 26 4.4.1 Vanadium Corrosion ................................................................................. 26 4.4.2 Erosion-Corrosion..................................................................................... 26 4.4.3 Corrosion in the Soot-Blower Region ...................................................... 27

4.5 Fouling and Deposit Formation................................................................................ 27 4.5.1 Particle Impaction ..................................................................................... 28 4.5.2 Condensation............................................................................................. 29 4.5.3 Thermophoresis......................................................................................... 30 4.5.4 Chemical Reactions................................................................................... 31 4.6 Measurement of High-Temperature Corrosion........................................................ 32 5.0 EFFECT OF FUEL CHARACTERISTICS ......................................................................... 33 5.1 Fuel Composition ..................................................................................................... 34 5.1.1 Coals .......................................................................................................... 34 5.1.2 Peat ............................................................................................................ 36 5.1.3 Biofuels...................................................................................................... 36 5.1.4 Recycled Fuels .......................................................................................... 37 5.2 Fuel Feeding.............................................................................................................. 38 6.0 EFFECT OF BED MATERIAL ........................................................................................... 39 7.0 EFFECT OF TEMPERATURES ......................................................................................... 40 7.1 Flue Gas Temperature............................................................................................... 40 7.2 Tube Material Temperature...................................................................................... 41 7.3 Combustion Temperature ......................................................................................... 43 7.4 Bed Material Temperature........................................................................................ 43 8.0 EFFECT OF SUPERHEATER DESIGN ............................................................................ 43 8.1 Tube Heat Exchangers.............................................................................................. 44 8.2 Omega-panels ........................................................................................................... 45 8.3 External (EHE) Superheaters ................................................................................... 45 8.4 Soot Removal Systems ............................................................................................. 46 9.0 WAYS OF PREVENTING SUPERHEATER CORROSION............................................ 47 9.1 Fuel Fractions............................................................................................................ 48 9.2 Superheater Materials ............................................................................................... 48 9.3 Superheater Design................................................................................................... 50 9.4 Boiler Design ............................................................................................................ 50 9.5 Process Conditions ................................................................................................... 50

EXPERIMENTAL PART 10.0 SCOPE OF THE EXPERIMENTAL PART...................................................................... 51 11.0 CORROSION EVALUATION .......................................................................................... 52 11.1 Optical Microscopy ................................................................................................ 52 11.2 Electron Microscopy............................................................................................... 53 11.3 Chemical Analyses ................................................................................................. 54 11.4 Calculations ............................................................................................................ 55 11.5 Probe Tests.............................................................................................................. 55 11.5.1 Deposit Formation Tests ......................................................................... 56 11.5.2 Corrosion Probe Tests............................................................................. 56 11.6 Tube Thickness Measurements .............................................................................. 57 12.0 CORROSION CASES........................................................................................................ 57 12.1 Corrosion in BFB Boilers....................................................................................... 57 12.2 Corrosion in CFB Boilers....................................................................................... 59 13.0 CORROSION TESTS......................................................................................................... 60 13.1 Corrosion Tests in Pilot Units ................................................................................ 60 13.2 Corrosion Tests in Commercial Units.................................................................... 60 14.0 CORROSION DATABASE............................................................................................... 61 15.0 PREDICTION OF CORROSION WITH A NEURAL NETWORK................................ 61 15.1 User Interface for the Neural Network................................................................... 61 15.2 Evaluation of The Neural Network Model ............................................................ 63 15.2.1 Test Plan for the Neural Networks ......................................................... 63 15.2.2 The Yates's Algorithm ............................................................................ 64 15.2.3 Statistical Means ..................................................................................... 65 15.3 Learning data .......................................................................................................... 65 15.4 Neural Networks Constructed ................................................................................ 66 15.4.1 Linear Feed Forward Network................................................................ 66 15.4.2 Non-Linear Feed Forward Network ....................................................... 67 15.4.3 Feed Forward Network with a Hidden Layer ......................................... 67 15.4.4 Feed Forward Network with Two Hidden Layers.................................. 68 15.4.5 Further Improved Networks.................................................................... 68 15.5 Learning Algorithms............................................................................................... 69 15.5.1 Learning of Linear Networks .................................................................. 69 15.5.2 Error Correcting Learning....................................................................... 70

15.5.3 Modified Learning Algorithms ............................................................... 72 16.0 RESULTS............................................................................................................................ 73 16.1 Evaluation of Different Neural Networks .............................................................. 76 17.0 FURTHER IMPROVEMENT OF THE MODEL............................................................. 80 18.0 SUMMARY ........................................................................................................................ 81 REFERENCES APPENDICES 1. 2. 3. 4. 5. 6. List of activation functions CFB Pilot models at the Karhula R&D Center of Foster Wheeler Neural network learning data Neural networks Residuals of the selected neural network Sensitivity analysis of the selected neural network

SYMBOLS

a A Cc Cl Co Cp Cpl Ct d(t) e e(t) EA f I j, k, p J k1 k2 kc kl ko kp kpl kv qm r R t T T0 u UT

slope parameter constant cubic constant, linear constant, logarithmic constant, parabolic rate constant, paralinear constant, correction factor desired response at time t error vector error at time t activation energy, frequency factor, unity matrix indexes jacobian matrix rate constant, rate constant, cubic rate constant, linear rate constant logarithmic rate constant, parabolic rate constant, paralinear rate constant, linear rate constant for scale vaporization, weight gain per surface area, radius of particle, molar gas constant, time, temperature, reference temperature, result of linear combiner thermophoretic velocity, m/s mol/(m s) mol/(m s) (kg/m)3 s-1 kg/(m s) kg/m (kg/m)2 s-1 kg/m m/s kg/m m J/(mol K) s K K J/mol m/s (kg/m)3 kg/m s-1 (kg/m)2 (kg/m)2

v w W x X y z

sum of input and bias synaptic weight array of synaptic weights input signal array of input signals output signal scale thickness, m

GREEK LETTERS

g p

scaler learning rate activation function mean free path, thermal conductivity of gas, thermal conductivity of particle, kinematic viscosity, threshold / bias sum of squared errors at time t Temperature gradient, K m W/(m K) W/(m K) m/s

(t)

DEFINITIONS

BFB BMP CFB EDS EHE LHV M Me RDF REF SEM SSE SSEn Stdev TIFF XRF

Bubbling fluidized bed Bitmap image Circulating fluidized bed Energy dispersive x-ray analysis External heat exchanger Lower heat value Metal catalyst Metal Refuse derived fuel Recycled fuel Scanning electron microscope Sum of squared errors Sum of squared errors, classed data Standard deviation Tagged image file format X-ray fluorescence

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1.0

INTRODUCTION

Neural networks are an effective method of prediction when the relations which correspond to the result are not fully known. The use of neural networks is based on teaching the network with existing data, and, after the sufficient prediction accuracy has been achieved, utilizing the network with new input data to achieve a solution for the problem. The decision chain behind the answer does not have to be known, and a result can be derived with little data. However, in order to create a reliable device for prediction, a large amount of data has to be available for the learning process. The material loss in superheaters is one of the most expensive phenomena concerning the maintenance costs of commercial fluidized bed boilers. Superheater corrosion is a common reason for boiler shutdown in the case of combustion of fuels containing corrosive substances. A shutdown and superheater reparation normally causes a major increase in the operating costs. The need for new methods for safe and environmentally friendly combustion of RDF and biofuels, as well as the multifuel combustion, creates a driving force for the boiler makers to create new, cost efficient solutions for the task. Fluidized bed combustion has been commercially available for several decades, but only lately it has been granted to be the most feasible solution for combustion of RDF, biofuels, and multifuel mixtures. However, knowledge about the factors which cause corrosion in fluidized bed combustion are not fully known. This study is a combination of theory and practice about the possibilities of decreasing the corrosion rate and creating longer enduring superheaters. The corrosion of steel can be described as a tendency of a metal alloy to return back to a more stable composition; in other words, the metal releases the energy it has accumulated in the steel making process. The helpers in this process can be gaseous ions, molten salts, or any other types of electrolytes, which create an electric gateway for the electrochemical phenomena taking place when the environment is right. If there is a way of preventing the electron exchange, the electrochemical corrosion could be stopped. However, a major part of the corrosion in hot environments may be caused by oxidation, which can take place without electrochemical causes. This makes the corrosion prevention a difficult task: when a metal is designed for the maximum strength, it may not be suitable for corrosive environment, or the internal oxidation rate can be too high.

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The reason for the material loss in a steam tube of a superheater can be erosion, but in most cases the main factor behind the material loss is corrosion. Often the corrosion taking place in a superheater is sulphur and/or chlorine corrosion, but other corrosion types can also be the cause of the material loss. The material loss can also be both erosion and corrosion, so that the erosion removes the protective oxide layer and the corrosion can attack the steel with full force. Experimental studies on the corrosion mechanisms exist, and the most well known theories can be used as a basis for theoretical corrosion models. The factors which have to be taken into account when creating a neural network model for the superheater corrosion taking place in a fluidized bed boiler are: fuel characteristics bed material characteristics temperatures, both in the combustion zone and in the superheater area boiler design.

The purpose of this study was to create a "handbook" for theories of the superheater corrosion in fluidized bed combustion, and a guideline for the ways of creating process conditions which decrease the risk of fireside corrosion. The experimental part consists of fireside corrosion examples and descriptions of probe tests made to evaluate the actual risks taking place in different types of fluidized bed boilers. These results have been utilized for a corrosion database and a corrosion prediction model based on a neural network.

2.0

NEURAL NETWORKS

The theory behind neural networks is an old one. The idea of neuron was introduced by Ramn y Cajl in the middle of the 20th century, but at that time, devices for utilizing the theory in practice were unavailable (Haykin /1/). The first applications utilizing neural network for prediction were adaptive linear filters in the middle of the 1980s. The idea behind neural networks is the similarity to the action of brain cells: the neural network allows complex, nonlinear, and multitasking function.

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By Haykin /1/, the properties available with neural networks can be listed as follows: nonlinearity input-output mapping adaptivity evident response contextual information fault tolerance very large scale integrated (VLSI) implementability uniformity of analysis and design neurobiological analogy.

2.1 Neuron A neuron is a simple derivation element consisting of several inputs and one output. A neuron is shown in Figure 1. The operation of the neuron in Figure 1 can be presented with two equations

uk = wkj x j
j =1

(1)

where

u j, k, p w x

result of linear combiner indexes synaptic weight input signal (2)

and y k = (uk k ) where

activation function output signal threshold / bias.

Each input x can be separately scaled with a synaptic weight w. The weighed inputs are then summed in the linear combiner as u prior to the activation function . The output y can be lowered by the threshold . It is also possible to increase the output by bias, which is the negative of the threshold. Each neuron and each input of a neuron have its own index, which can be written as a subscript. In Figure 1, k is used for indexing the neuron and p for the input.This allows a simple algorithm for the handling of neurons and their inputs.

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Figure 1.

Model of a neuron (Haykin /1/, page 8).

The output of a neuron depends on the inputs, weights, activation function, and threshold/bias. In principle, a neuron is a simple element performing a complex task.

2.2 Activation Function The activation functions can be divided into three basic types: threshold function piecewise-linear function sigmoid function.

If we leave out the effect of the threshold/bias, the threshold function acts as an on-off switch, resulting in a ramp operation, in which the output depends on the linear combiner (equation (1) - threshold) according to function (3).

1, if v 0 y= 0, if v < 0

(3)

where

v = uk - k.

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Accordingly, the piecewise-linear function may change the output as follows:

v 1, y = v + , > v > 0, v

(4)

resulting in a linear change between 0 and 1 in the output when the linear combiner changes. The sigmoid function gives out a strictly increasing function that exhibits smoothness and asymptotic properties, for example equation (5). 1 1 + exp( av ) slope parameter.

y= where a

(5)

The outputs of different activation functions are illustrated graphically in Figure 2, the value of the slope parameter in function (5) is 1. The different activation functions can be used for various purposes in neural networks. A list of typical activation functions is shown as Appendix 1.

1.2

1.0

0.8

0.6

0.4

0.2

0.0 -5 -4 -3 -2 -1 Threshold 0 1 2 Sigmoid 3 4 5 Piecewise-linear

Figure 2.

Responses of different activation functions.

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2.3 Neural Networks A neural network is a combination of one or more neurons which are connected according to the desired operation. The architectures in which the neurons are structured depend on the learning algorithms used. The simpliest approach is the linear single-layer feed-forward network, illustrated in Figure 3. This network consists of an input layer of source nodes, a single layer of neurons, and one or more outputs. If the number of neuron layers is increased, the added neuron layers are called hidden, because they are not directly visible to the user. The hidden neurons intervene between the external input and the network output, allowing higher order statistics. The multi-layer network also shown in Figure 3 is fully connected, but it is also possible to leave some connections open by setting their synaptic weights to zero. When one or more connections are connected as a feedback, the neural network type changes to recurrent. This allows the use of the network output as an input, which in many cases speed up the learning process. A lattice structure is a feed-forward neural network, in which the outputs are arranged in rows and columns, allowing a matrix-like layout. Self-organizing maps are one use of lattice structures.

Figure 3.

Two examples of feed forward neural networks (Haykin /1/, pages 18 and 19).

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2.4 Learning Procedures The learning process is the initial function when working with neural networks. In order to function as desired, a neural network has to learn with known data. It is also possible to use the output of the neural network as new input data, so that the network improves its performance as the number of learning runs increases. Undergoing changes is an essential part of the learning process. The changes can take place in the synaptic weights, biases, and even in the activation functions. However, the larger the number of neurons in the network is, the more data has to be used for the learning process. Several learning procedures exist. The theory behind these processes is omitted in this study, but the methods used for teaching of the model will be described in some detail in the experimental part.

2.5 Applications The amount of neural network applications is increasing all the time. The variety of possible subjects is vast, and only the difficulties in teaching the network and in some cases the high number of neurons required set the limits to the target applications. If the problem at hand is simple, or the relations between the variables are easy to determine, the use of neural networks provides little benefit. However, when the problem becomes more complicated, the neural networks can provide a solution for the task. Examples of the use of neural networks in Finland are listed by Bulsari and Saxn /2/, and Koikkalainen /3/. Some of these examples are included in the following list: image compression modelling: non-linear time series supermarket customer profile fault diagnostics self organizing maps conscious machines.

The variety of applications is increasing all the time.

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3.0

FLUIDIZED BED TECHNOLOGY

The fluidized bed technology has been utilized for combustion since the 1920s. Foster Wheeler has been utilizing the fluidized bed technology for combustion since the end of the 1960s. The first fluidized bed boilers were of the bubbling bed type (BFB) (Abdulally and Moore /4/) in which the fuel was fed on top of a sand bed, which was kept in fluidized state by primary air. The operating principle is shown in Figure 4. This technology is still competitive in combustion of biofuels and sludges.

Figure 4.

Bubbling fluidized bed boiler (Foster Wheeler Energia Oy /5/).

The first commercial fluidized bed boilers utilizing a solids separator for solids recirculation were constructed in the 1970's by Lurgi /6/. The idea is to use a higher fluidization velocity and return most of the escaping bed material back to the furnace with a cyclone, the principle is shown in Figure 5. The benefit of the CFB (Circulating Fluidized Bed) technology is that the residence time of the solid fuel in the boiler is longer, because most of the unburned fuel is returned back to the furnace. The bed can also be utilized for sulphur capture by adding limestone. The sulphur can be taken out as gypsum mixed with the bottom and fly ashes.

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Figure 5.

Circulating fluidized bed boiler (Foster Wheeler Energia Oy, /5/).

3.1 Bubbling Fluidized Bed Boiler The bubbling fluidized bed boiler operates with fluidization velocities less than 3 m/s. In atmospheric combustion, this fluidization velocity allows 3 MW/m of net effect per cross section area of the furnace (Hyppnen and Raiko /7/). About half of the combustion air is brought through the grid into the furnace as primary air, the rest of the combustion air can be introduced as secondary and tertiary air. The variety of fuels used in commercial size bubbling bed boilers is large, from coal to RDF and sludges. The fuel is usually fed on the surface of the bubbling bed, some air can be used to distribute the fuel evenly on the bed surface. The large fuel scale can be both a curse and a blessing: if the mainly used fuel contains no harmful components, it is easy to think that no corrosion will take place. On some occasions it is easy to create severe corrosive environment with an accessory fuel which contains some harmful element. If the corrosion attack starts, the change back to normal fuel may not be sufficient for stopping the initial attack: the corrosion may continue under the protective metal oxide layer.

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In BFB boilers, the superheaters are normally located behind a peak to protect them from the radiation of the bed region. In older designs, some superheaters were located inside the furnace so that the superheater tubes were exposed to the radiation from the combustion zone. This design has been proven to be unuseful for waste and biofuel combustion due to excessive corrosion, if the steam temperature is higher than 400 C. The bubbling fluidized bed boiler is commercially available in a large scale. At the moment, the largest bubbling bed boiler ever built is in the United States. The unit is combusting subbituminous coal, and the thermal input of the unit is 387 MW. The design values for the steam produced by the unit are 105 bar and 540 C (Foster Wheeler /8/).

3.2 Circulating Fluidized Bed The circulating fluidized bed boilers operate with higher fluidization velocities than BFBs. With coal, the net effect per cross section area of the furnace can be as high as 6 MW/m (Hyppnen and Raiko /7/). The main benefits of a CFB boiler over the bubbling fluidized bed are in the solids recirculation. The solids circulation allows very uniform temperature distribution in the boiler furnace, while in a bubbling fluidized bed the combustion takes place partially in the gas above the bed region, and the gas temperature in the furnace can be over 1200 C. This may lead to high NOx emissions (Pels et al. /9/). Due to the solids recirculation, the combustion efficiency of coal in CFB boilers is higher than in BFB boilers. The novel Foster Wheeler CFB design utilizes a Compact separator, in which the walls of the solids separator are straight, see Figures 6 and 7.

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Figure 6.

A modern Foster Wheeler Compact boiler with straight walls in the solids separators (Foster Wheeler Energia Oy, /5/).

Figure 7.

Operating principle of Compact separators of the Foster Wheeler Compact boiler (Foster Wheeler Energia Oy, /5/).

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The solids recirculation allows effective sulphur capture by using limestone as an additive in the bed material. According to Leckner and Amand /10/, and Newby and Dale /11/, the optimum temperature range for sulphur capture with limestone is between 800 and 850 C, so if the temperature in the furnace can be maintained within these limits, the reaction of SO2 to CaSO4 can take place in the whole furnace instead of a small region. In order that the solids separator could operate properly, no gas backflow through the solids return line can take place (EPRI /12/). The pressure barrier for preventing the gas upflow is created by a gas seal, the operating principle of a gas seal is shown in Figure 8. The gas seal area can be efficiently utilized as a location for external heat exchangers.

Figure 8.

Operating principle of the gas seal for CFB boilers (Hill, Mallory and McKinsey /13/, page 865).

The circulating solids increase the heat transfer rate in the furnace, but the risk of erosion caused by the bed material increases. Together with water wall corrosion this may cause very rapid material loss in the furnace. This is one of the risks which have to be noticed when designing a CFB boiler for fuels containing corrosive components.

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The superheaters in a CFB boiler can be located after the solids separator as convective heat exchangers, or inside the furnace as Omega panels, which are exposed to both radiative and convective heat transfer. The heat transfer rate in the furnace is much higher than in the convective pass due to radiation and particle convection (Basu /14/). The rate of erosion in the Omega panel is higher, so the panel edges have to be protected from vertical solids flow. The circulating fluidized bed combustion represents relatively new technology. However, an increasing percentage of the new boilers constructed all over the world are based on circulating fluidized bed. The largest circulating fluidized bed boiler so far is the Gardanne coal combustion unit in Provence, France. The thermal input of the boiler is 600 MW, and the steam values produced by the unit are 163 bar and 565 C (Jestin et al. /15/).

4.0

SUPERHEATER FIRESIDE CORROSION

Fireside corrosion is often a very complicated process. Superheater metal wastage can occur due to oxidation, sulphidation, erosion-corrosion, or a combination of these. Chlorine containing deposits can also be the main cause of metal loss. In order to evaluate the risk of superheater fireside corrosion, one has to be aware of the main corrosion types and their effects. The risk evaluation is often done by examining the fuel characteristics, but the role of bed material and combustor type must not be neglected (Jia-Sheng /16/). Many corrosion types are speeded up by a reducing gas environment. Different corrosion types have been widely studied, the first papers on the subject date back to the end of the 1800s (Evans /17/). Quite often the corrosion taking place is a mixture of at least two different corrosion mechanisms. This makes it difficult to predict the corrosion rate and material lifetime in the superheater region. There are various studies of the corrosion kinetics, both in laboratory and field scale, but few of these can directly be used for estimation of superheater material endurance.

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4.1 Mechanism and Kinetics of Oxidation The most common metal degradation mechanism encountered in combustion is oxidation. Oxidation takes place when the oxygen in the flue gas gets in contact with the superheater steel surface. Due to the need for elevated strength at high temperatures, the steels used in superheaters are often chromium and/or nickel containing alloys. The oxidation of the alloy surface creates a protective iron or chromium oxide layer which prevents diffusion of oxygen. Because of the decreased diffusion, the oxidation rate slows down, and a stable oxide layer is formed on the steel surface. This type of oxidation is called selective, and the mechanism is widely used for protection against corrosion. However, if the protective layer is not sufficient for preventing diffusion, the rate of oxidation can be linear or even exponential, ending up with a very high metal loss rate. The different oxidation equations have been presented by Fontana and Greene /18/. The equations are presented graphically in Figure 9. Parabolic oxidation

qm = k p t + C p where qm kp t Cp Logarithmic oxidation q m = k o log( Co t + A) where ko Co A logarithmic rate constant logarithmic constant constant. weight gain per surface area parabolic rate constant time parabolic constant.

(6)

(7)

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Linear oxidation qm = k l t + Cl where kl Cl Cubic oxidation linear rate constant linear constant. (8)

q m = k c t + Cc where kc Cc Paralinear oxidation cubic rate constant cubic constant.

(9)

q m + k pl qm = k p t + C pl where kpl Cpl paralinear rate constant paralinear constant.

(10)

The oxidation rate constants are usually reported to depend on the temperature according to the Arrhenius expression
EA

k = f e RT where f EA R T

(11) frequency factor activation energy molar gas constant temperature.

Oxidation can seldom be presented with only one equation, combinations of rate laws are common. The oxidation rate constants depend on metal, temperature, and diffusion coefficient of oxygen through the oxide layer. If the diffusion rate through the oxide layer is low, the oxide forms a protection against further oxidation. This protective oxide layer can also protect the metal from chemical corrosion caused by corrosive contaminants. Some parabolic oxidation and sulphidation rate constants are listed in Table 1.

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2.0

1.8

1.6

1.4

1.2

qm, g/m

1.0

0.8

0.6

0.4

0.2

0.0 0 0.5 parabolic 1 1.5 linear cubic 2

TIME
logaritmic

Figure 9. TABLE 1.

Oxidation equations, weight gain per unit area. Oxidation and sulphidation rate constants for parabolic oxidation and sulphidation (Mrowec /19/, page 373).

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Oxidation can become a problem if the metal temperature rises too high, or there are corrosive contaminants present in the gas atmosphere. These contaminants (sulphur, chlorine, fluorine, vanadium) can generate very high oxidation and metal wastage rates (Birks and Meier /20/).

4.2 Sulphur Corrosion Sulphur corrosion, often referred to as sulphidation, is a very common phenomenon in coal combustion, but it can also occur with other fuels. In the combustion process, the sulphur in fuel reacts with oxygen in the combustion air forming SO2, and, if the residence time and O2 content are sufficient, also SO3. The SO2 and SO3 can react with calcium in the bed material forming CaSO4, but other sulphides and sulphates are also possible. The formed sulphides and sulphates may deposit on a superheater surface, after which the corrosion takes place on the interface between the metal oxide and the deposit.

4.2.1 Formation of SO3 in Fluidized Bed Combustion The formation of SO3 in combustion systems can be presented with the following mechanism: S + O 2 SO 2 SO 2 + O 2 SO 3 + O
k 1 k1

(12)

M + SO 2 + O SO 3 + M
k 2

k2

where

k1, k2 M

rate constants metal catalyst.

The formation of SO3 can be accelerated by various catalysts, but the maximum SO3 concentration is always limited by the thermodynamical equilibrium. If reaction (12) takes place without a catalyst, Burdett et al. /21/ have measured for the rate constant a value of (2.61.3)1012 e((-230001200)/T) mol-1cm3s-1 at a temperature range of 900-1350 K.

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Burdett et al. /22/ have studied the effect of bed material on the SO3 formation in combustion of coal in the fluidized bed. A major fraction of the SO2 can be captured by adding limestone to the fluidized bed, but despite the reduced SO2 level, some SO3 can still be found in the flue gas. They reported that approximately 1.5 % of the total sulphur oxide in the flue gas is present as SO3. This free SO3 can be considered as the main initiator of superheater metal sulphidation.

4.2.2 Kinetics of Sulphidation Metal sulphidation is a much faster reaction than metal oxidation, see Table 1. However, the reaction seldom continues so as to result in internal sulphidation of the metal. By Mrowec /19/, the reasons for this can be listed as follows: solubility of sulphur into most metals is low diffusion of sulphur in metals is slow due to high sulphidation rate, the sulphur does not have time to penetrate into the metallic phase.

Sulphidation does not normally create similar protective layer as oxidation. The formed layer has a more pronounced defect structure in the sulphide lattice. The formed sulphide can be scaled off more easily, leaving the base metal vulnerable to further oxidation and sulphidation. The sulphidation rate depends on temperature according to the Arrhenius expression, equation (11). Some activation energies for sulphidation are shown in Table 2. TABLE 2. Activation energies of sulphidation of Fe, Ni, Cr and alloys (Mrowec /19/, page 379). Temperature range, C 600-950 450-620 600-1100 700-1000 520-900 Activation energy, kJ/mol 80 88 130 Activation energy, Range I Range II 80-110 230-310 88-92 170-280 kJ/mol Range III 130 120

Metal / alloy Fe Ni Cr Fe-Cr Ni-Cr

In Table 2, ranges I, II, and III correspond to low-percent, intermediate-percent and highpercent alloys. It can be noted that the activation energies are at highest in range II. This is due to the heterogeneous double-layer scale formed in the sulphidation reaction.

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4.2.3 Sulphur Corrosion Mechanisms The sulphur corrosion is hardly ever due to diffusion of SO2 or SO3 from the flue gas straight to the tube surface, unless the concentrations are very high. In most cases the diffusion occurs from the flue gas to the deposit and then from the deposit to the metal oxide. The sulphur corrosion mechanism depends on the composition of the sulphur containing component and gas atmosphere. The sulphur corrosion mechanism can occur in reducing environment, where the reaction products are sulphides, or in oxidizing environment, where the corrosion products are sulphates. The reducing environment can be caused by formation of H2 or CO in the combustion process due to undesired chemical reactions. The reason for the high CO content in the flue gas is in many cases in the unstable fuel feeding, which occasionally causes the air to fuel ratio to be lower than unity.

4.2.4 Sulphide Corrosion Sulphide corrosion occurs in reducing environments. According to Plumley et al. /23/, sulphides are formed from alkali metals and sulphur oxides in the presence of CO as follows: Na 2 SO 4 + CO Na 2SO 3 + CO 2 6Na 2 SO 3 4Na 2 SO 4 + 2Na 2 S + O 2 Na 2S + MeO MeS + (Na 2 O) where Me Cr, Fe, Ni...

(13)

Reaction (13) produces MeS, which can react further to volatile compositions, resulting in high metal wastage rates. For iron, the initiation of this reaction can occur by reduction of Fe2O3 to Fe3O4 by CO, while FeO is formed as a side product.

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4.2.5 Sulphate Corrosion Sulphate corrosion can take place in oxidizing environment, when the SO3 concentration is high. At a temperature range from 320 to 480 C, the alkali sulphates form pyrosulphates Na 2 SO 4 + SO 3 Na 2S2 O 7 (14)

which decompose and react with the protective oxide layer, an example for iron oxide: Na 2S2 O 7 + Fe 2 O 3 2Na 3 Fe(SO 4 )3

2Na 3 Fe(SO 4 )3 3Na 2 SO 4 + Fe 2 O 3 + 3SO 3

(15)

resulting in degradation of the protective oxide layer. The reaction (15) accelerates when the temperature is increased over 490 C (Barniske /24/). The reaction mechanism can also involve alkali trisulphates, which are formed according to equation (16) (Reid /25/). 3Na 2 SO 4 + Fe 2 O 3 + 3SO 3 2Na 3 Fe(SO 4 ) 3 (16)

It may be noted that in equations (14) to (16), potassium can be used instead of sodium.

4.3 Chlorine Corrosion Chlorine induced corrosion is a common corrosion type in waste combustion. This type of corrosion can also take place in combustion of other chlorine containing fuels, for example biofuels and high-chlorine coals. Chlorine corrosion is often accelerated by alkaline components in the fuel. At low temperatures, chlorine corrosion can take place as hydrochloric acid corrosion, but in the case of superheater corrosion, the mechanism is initiated when the fuel contains sufficient amounts of chlorine, and the superheater tube temperature is sufficient for chlorides to form molten eutectics. If there are sulphur containing components present, the chlorine corrosion can cause very high metal loss rates.

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The highest superheater tube degradation rates reported have been about 3 mm/1000 hours of operation. Chlorine corrosion has been mostly studied in connection with waste combustion.

4.3.1 Chlorine Corrosion Mechanisms Chlorine corrosion can take place as gas phase corrosion (Hupa et al. /26/) in which the HCl in the flue gas gets in contact with unprotected metal, for example iron. The formed Fe (II) chloride reacts further to Fe (III) chloride, which is very volatile. The Fe (III) chloride is vaporized, leaving the surface vulnerable to further reactions. Fe(s) + 2HCl(g) FeCl 2 (s) + H 2 (g)
3 Fe(s) + 3HCl(g) FeCl 3 (s, volatile) + 2 H 2 (g)

(17) (18)

This mechanism is illustrated in Figure 10. In waste combustion, the mechanism is often more complicated due to the high CO and H2O content in the flue gas.

Figure 10.

Corrosion of iron due to high HCl concentration in waste incineration (Nieminen /27/, page 57).

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Chlorine corrosion has been widely studied, and some corrosion mechanisms have been proposed, one of the most widely agreed on is the mechanism presented by Krause (/28/ and /29/). These reactions take place in the region between the deposit and the metal oxide, Figures 11 and 12. The reactions in chlorine corrosion mechanism in Figures 11 and 12 take place in the molten phase, which explains the high metal wastage rates. The liquid phase is formed of salts with low melting points, some of which are listed in Tables 3 and 4.

Figure 11.

Chlorine and sulphur corrosion mechanisms, cyclic corrosion (Krause /28/, page 91).

Figure 12.

Different scales on top of superheater tube and their compositions, chlorine corrosion (Krause /28/, page 89).

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TABLE 3. Composition NaVO3 CrVO4 FeVO4 MgV2O6 CoV2O6 NiV2O6 V2O4 V2O3 Na2OV2O5 Na2O3V2O5 2Na2O3V2O5 2Na2OV2O5 3Na2O3V2O5

Common salts with low melting points (Elliot /30/, page 65). Melting Composition point C 630 Na2S2O7 810 816 700 705 720 >1750 690 630 621 620 640 850 573 625 535 835 1190 550 645 940 988 877 250 K2S2O7 3K2S2O7 Na2S2O7 Na3Fe(SO4)3 K3Fe(SO4)3 Na3Fe(SO4)3 K3Fe(SO4)3 Na3Al(SO4)3 K3Al(SO4)3 ZnSO4 decomp. Na2SO4 K2SO4 MgSO decomp. Al2(SO)3 Al2O3 CaSO4 decomp. => Melting point C 400 335 280 624 618 552 646 655 740 884 1076 1124 770 1450 480 783 194 205 282 625 800 776 772 820

10Na2O7V2O5 Na2OV2O45V2O5 5Na2OV2O411V2O5 2MgOV2O5 3MgOV2O5 Na2O/MoO3 Ni-Ni3S2 FeO-FeS eutectic Fe-FeS eutectic Co-CoS NaHSO4 decomp. => Na2S2O7 + H2O

Fe2(SO4)3 decomp. => Fe2O3 NiSO4 decomp. => NiO MoCl5 NbCl5 FeCl3 Na2SO4-NaCl eutectic NaCl KCl CaCl2 CrCl2

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TABLE 4.

Eutectic chloride mixtures with low melting points (Krause /29/, table 2). Composition Melting point
mol % F C

mol %

25 37 60 70 70 20 55 70 60 58 70 52 72 90 80 49

NaCl PbCl2 SnCl2 SnCl2 ZnCl2 ZnCl2 ZnCl2 ZnCl2 KC1 NaCl PbCl2 PbCl2 PbCl2 PbCl2 PbCl2 NaCl

75 63 40 30 30 80 45 30 40 42 30 48 28 10 20 51

FeCl3 FeCl3 KC1 NaCl FeCl3 SnCl2 KC1 NaCl FeCl2 FeCl2 NaCl KC1 FeCl2 MgC12 CaCl2 CaCl2

313 347 349 361 392 400 446 504 671 698 770 772 790 860 887 932

156 175 176 183 200 204 230 262 355 370 410 411 421 460 475 500

4.3.2 Kinetics of Chlorine Corrosion The chlorine corrosion rate depends on the chlorine concentration in the flue gas, tube metal temperature, and tube steel composition (Brooks and Meadowcroft /31/). It has been reported that the increase in chlorine concentration at low temperatures accelerates corrosion vastly. When the temperature is increased, the role of concentration decreases, and the temperature increase becomes a more important factor. Around a metal temperature of 500 C, a temperature increase of 15 C approximately doubles the chloride corrosion rate.

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The rate of corrosion can be presented as thickening of the corrosion product scale (Elliot, Ansari and Nabovi /32/): dz k p = kv dt z where z kv scale thickness linear rate constant for scale vaporization.

(19)

Equation (19) results in the behaviour illustrated in Figure 13. At low temperatures, the scale thickens according to the parabolic rate law. If the temperature is sufficient, the vaporization rate of the scale may become higher than the scale growth, and the metal is rapidly degraded.

Figure 13.

Chlorine corrosion rate law (Elliot, Ansari and Nabovi /32/, page 446).

The problem with chlorine corrosion is that the kinetic parameters depend on the steel characteristics, flue gas composition, and the presence of alkali and sulphur components. In addition to these, the corrosion resistance of steels usually decreases at elevated temperatures. The temperature increase may actually have two separate effects, both of which increase the chlorine corrosion rate.

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4.4 Other Corrosion Types In addition to the corrosion mechanisms described earlier, there are several other corrosion types mentioned in the literature, including vanadium corrosion and erosion-corrosion. These mechanisms alone can seldom create rapid material losses, but together with oxidation and/or sulphidation, they can seriously accelerate the material wastage.

4.4.1 Vanadium Corrosion Vanadium, and especially vanadium pentoxide (V2O5) can cause a fast increase in the material loss rate in sulphur corrosion environment. The role of vanadium in this corrosion case is not fully agreed on: some researchers claim that the vanadium pentoxide acts as a catalyst, while others think that the role of vanadium is more complex (Evans /33/). Table 3 presents several vanadium containing salts with low melting points. However, significant concentrations of these salts require high amounts of vanadium in the fuel. Some petroleum cokes and refinery tars may contain sufficient amounts of vanadium for the corrosion attack to initiate.

4.4.2 Erosion-Corrosion In erosion-corrosion, the protective oxide layer, or the created corrosion product, is removed from the tube surface by erosion. The erosion is due to particles colliding with the metal surface. The erosion rate depends on the particle velocity and characteristics, as well as the metal surface properties (Barkalow, Goebel and Pettit /34/). The erosion-corrosion is considered to be the main reason for superheater material wastage in the vicinity of soot-blowers. The erosion-corrosion rates in the furnace are often high, and for this reason the lower edges of the Omega panels used in CFB boilers have to be protected with shields.

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4.4.3 Corrosion in the Soot-Blower Region In the case of steam soot-blowers, the corrosion in the soot-blower area can be due to erosioncorrosion. On the other hand, the corrosion can also take place due to the highly reducing environment. The reason for the low-oxygen zone may be in the water gas reaction C(s) + H 2 O(g) CO(g) + H 2 (g) (20)

which can occur if there exists unburned carbon on the tube surface, and the carbon gets in contact with steam or water spray from the steam soot-blowers. The resulting CO and H2 react rapidly with the O2 in the flue gas, resulting in low-oxygen atmosphere. Reaction (20) is very rapid when the temperature is over 650 C.

4.5 Fouling and Deposit Formation When solid fuel is combusted in a fluidized bed, some ash will be carried with the flue gas out from the furnace. Part of the ash can deposit inside the furnace, and cause an event called slagging. If the ash is deposited in the flue gas duct after the furnace, the phenomenon is called fouling. In most cases, the superheaters are located outside the furnace, and fouling is the main concern connected with the reduced heat transfer rate in the superheater region. If the ash contains harmful impurities, the previously mentioned corrosion mechanisms can take place in the superheater tubes. In order to remove the deposit from the superheater tubes, different soot removal systems have been developed. Some of the commercial soot removal apparatus will be described later in the context of superheater design. Deposit formation is a key factor in the study of sulphur and chlorine corrosion, some existing theories and studies of deposit formation are described in this chapter. The deposits which are formed on the surface of a superheater are often considered to be the main initiator of a fireside corrosion attack.

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The main deposit formation mechanisms are: particle impaction condensation thermoporesis diffusion and chemical reactions.

One or more of these mechanisms can cause superheater fouling and thus initiate a corrosion attack. One of the worst properties of the components that cause fouling is that they are often also corrosive. By Miles et al. /35/, the compounds containing potassium, sulphur and chlorine are often the initial bonding agents. Jokiniemi and Kauppinen /36/ have listed the fouling meachanisms and the size of gas component as follows: fumes and gases aerosols small particles, 0.05 - 0.5 m coarse particles, 0.5 - 50 m => => => => condensation and surface reactions diffusion, thermophoresis vortex impaction direct impaction.

In general, the tube temperature is the main factor influencing the fouling rate of gases, aerosols and small particles. When the particle size increases, the flue gas velocity starts to increasingly affect the deposit formation rate.

4.5.1 Particle Impaction Fouling in the superheater tubes can be caused by particle impaction, so that the deposit is formed by particles of size 0.5 - 50 m, which due to inertia cannot follow the flue gas flow but hit the surface with high velocity, and get deposited on the surface, Figure 14. These particles can be partially condensed aerosols, molten salts, or silicates. The deposits formed by direct impaction can be found on the surface facing the gas flow. Smaller particles may collide with the sides and back of the surfaces due to gas vortex impaction. These deposits are normally less dense than the deposits formed by direct impaction. However, chemical reactions in the deposit can create very hard scales which cannot be removed with soot removal systems.

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Figure 14.

Difference between fouling by diffusion and impaction (Skrifars and Hupa /37/, page 216).

4.5.2 Condensation Gas and fume condensation intensity on the surfaces depends mostly on three factors: surface temperature, gas temperature, and partial pressure of vapour. An example of the temperature effect can be seen in Figure 15, where dew points and condensing intensities of four substances are shown. It can be noted that KCl can condensate at as high a surface temperature as 650 C, which corresponds to a live steam temperature of approximately 620 C.

Figure 15.

Condensing intensity and dew points of selected substances (Ots /38/, Figure 6.).

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In order to minimize the condensation rate, the flue gas temperature should be reduced to minimize the temperature difference between gas and the heat exchange surface. In waste combustion, 700 C is considered to be a critical flue gas temperature. The partial pressures of gas components are important as regards the condensation characteristics, because the dew point of a gas component depends on the partial pressure of the component.

4.5.3 Thermophoresis Thermophoresis is the term describing the phenomenon wherein small particles, such as soot particles, aerosols and the like, when suspended in gas in which there exists a temperature gradient T, experience a force in the direction opposite to that of T (Talbot et al. /39/). This force can correspond to the deposition of superheater tubes, because in such a case, the direction of T is always from the tube surface to flue gas. The thermophoretic velocity can be presented by an empirical formula

U T = 2.2

( T ) x T0 1 + 2 g + 2Ct p r

g + Ct r p

(21)

where

UT

thermophoretic velocity kinematic viscosity reference temperature thermal conductivity of gas thermal conductivity of particle correction factor mean free path radius of particle.

T0

g p
Ct

The equation (21) was first presented by Derjaguin et al. /40/. This equation, although empirical, can be used for estimating the particle velocities caused by the thermophoretic force in the vicinity of superheater tubes.

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4.5.4 Chemical Reactions Chemical reactions seldom are the only fouling mechanism. However, after the initial deposit has been formed by one of the primary fouling mechanisms, the deposit can react with the flue gas components. This may lead to a vast change in the initial deposit composition. As an example, Ots /38/ has presented a figure illustrating the Cl and SO3 content change depending on time in the combustion of Estonian oil shale, Figure 13.

Figure 16.

Cl and SO3 content change in ash deposits from combustion of Estonian oil shale (Ots /38/, Figure 7.).

The change is mainly due to transformation of Cl-containing components to sulphates by chemical reactions, and most of the released chlorine is vaporized as alkali chlorides. The formed sulphates (K2SO4, CaSO4) act as binding agents, forming a dense and hard deposit. The problem with the release of chlorine lies in the tendency of chlorine to form iron and chromium chlorides. This mechanism may lead to a rapid chlorine corrosion.

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4.6 Measurement of High-Temperature Corrosion Several high-temperature corrosion measurement methods have been developed to be used in a laboratory scale (Haynes and Baboian /41/). However, few of these give results which could be directly applied to field use. The problem lies in the changing flue gas atmosphere, which is very hard to create in a laboratory. Results achieved in metal tests at laboratories can only be used with caution for material selection, and that is why field tests are considered to be the only reliable method for achieving a basis for material lifetime estimation. The superheater corrosion can be evaluated directly by measuring the material loss on a time basis. This, however, requires a boiler shutdown. The other ways of measuring the corrosion rate and determining the corrosion mechanism are more or less indirect. The corrosion rate can be evaluated by measuring the material loss by using a special probe. The corrosion probe can be of a type that utilizes electrical phenomenon taking place in a corrosion attack (Barrett /42/), or a type which contains several cooled coupons which are weighed and analysed. The principle of a lance-type corrosion probe is shown in Figure 17. The probe can be cooled with air or air and water. The coupon temperatures are measured according to demand, and the temperature can be adjusted with the cooling fluid flow. A probe of this type has been successfully used at the Foster Wheeler Karhula R&D Center for several years, and the majority of the test results referred to in the experimental part have been measured by using such a probe.

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AIR OUT

TI

STEEL COUPONS

TI

AIR IN

50 mm

38 mm

28 mm

Figure 17.

Lance-type corrosion probe and a test coupon.

5.0

EFFECT OF FUEL CHARACTERISTICS

Fuel characteristics and composition have a major role in the superheater corrosion. The amount of corrosive components and other harmful impurities is one of the main factors related to the corrosion behaviour of a particular fuel. The task of predicting the corrosion behaviour becomes more difficult when two or more fuels are combusted as co-combustion. Several aspects have to be taken into account in the estimation of corrosion rate by the fuel characteristics. According to Miles et al. /34/, at least the following analyses have to be made in order to evaluate the fuel characteristics: proximate analysis (moisture, volatile matter, fixed carbon, ash) ultimate analysis (C, H, N, S, O, Cl...) heating value chlorine a direct measure of oxygen elemental ash analysis.

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If it is possible, some special analyses should be made to evaluate the fuel ash behaviour. These include sintering tendency, water soluble and volatile alkali, and tendency to form chlorides and sulphides. The fuel analyses can be utilized for theoretical modelling of deposition (Jokiniemi et al. /43/) and modelling of corrosion. However, in order to achieve reliable results of corrosion rates by theoretical modelling, the calculations must be checked against known cases.

5.1 Fuel Composition The fuel composition is important at the design state. The amounts of sulphur, chlorine, potassium, sodium, vanadium etc. have to be known prior to the final decision on the boiler type and superheater design. If, according to the fuel analyses, there seems to be a risk of corrosion, this risk has to be noted before any decisions on the final design are made. The following chapters list some fuels and their characteristics, some fuels with known corrosion risks have been highlighted. A database of fuel characteristics was constructed during the study, and this database was utilized as a basis for the corrosion model.

5.1.1 Coals Coals are the most important solid fuels in energy production. Coal types can roughly be divided into five main gategories: anthracite bituminous lignite char brown coals.

Different classification systems have been developed for coal quality, but the existing systems make it difficult to determine the coal qualities just by the main type. A comparison of different coal classification systems is shown in Figure 18. Some compositions of different coals are listed in Table 5.

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Figure 18.

Coal classification systems (Skorupska /44/, page 28).

Table 5.

Compositions of various coals, measured at the Karhula R&D Center of Foster Wheeler Energia Oy. The statistics are from all samples analyzed.
LHV Volatile MJ/kg w-% 29.7 18.2 29.7 25.8 21.3 42.9 19.4 36.4 13.9 48.1 19.5 6.7 6.4 5.7 25.3 32.0 31.8 52.9 5.3 9.6 Ash w-% 10.1 17.1 17.2 30.6 51.9 41.4 4.0 19.4 79.1 14.3 C w-% 77.7 72.3 54.7 47.2 28.4 53.7 16.8 62.3 77.7 13.0 H w-% 3.0 4.2 3.9 4.0 3.0 1.2 0.6 4.1 5.7 0.9 N w-% 1.4 1.1 0.6 0.7 0.1 0.7 0.3 1.2 2.1 0.4 O w-% 6.9 4.8 22.2 16.1 15.1 2.4 0.7 11.2 23.6 5.1 S w-% 1.0 0.5 1.5 1.4 1.5 0.8 0.3 1.3 5.7 1.1 Cl w-% 0.0 0.0 0.0 0.0 0.1 0.0 0.0 0.1 0.5 0.1 Ca Na, K w-% w-% 0.2 0.0 0.0 0.4 0.4 0.0 0.0 0.0 14.2 0.1 0.0 0.0 0.1 0.0 0.7 0.3 10.7 1.9 1.6 0.3

Coal type Anthracite Bituminous Lignite Brown coal Oil shale Coal residue Min Average Max Stdev

Moilanen and ijl /45/ have presented a large database of various coal types and their specifications, similar databases are also available from other sources.

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5.1.2 Peat Peat is a very important fuel in Finland, because it is considered a renewable source of energy (Alakangas, Kanervirta and Kallio /46/), although the formation of peat takes thousands of years. The peat used for combustion contains considerable amounts of sulphur, so it has to be regarded as a corrosive fuel. However, the corrosion type encountered in combustion of peat is sulphur corrosion, which in most cases can be handled with superheater materials selection. In some cases cold-end chloride corrosion has been reported due to an occasionally high chlorine content of peat. Some compositions of different peats are listed in Table 6. Table 6. Compositions of various peats, measured at Karhula R&D Center of Foster Wheeler Energia Oy. The statistics are from all samples analyzed.
LHV Volatile MJ/kg w-% 19.4 65.4 20.8 65.1 23.3 67.9 22.0 68.3 21.8 69.3 22.1 59.9 23.1 64.7 19.0 59.9 21.7 68.1 23.8 74.6 1.3 3.3 Ash w-% 5.1 8.0 4.9 4.4 3.7 3.0 1.1 1.1 4.4 8.0 1.6 C w-% 53.2 51.6 56.2 53.7 54.4 58.0 58.9 48.7 54.4 58.9 2.2 H w-% 5.2 5.5 6.0 6.0 5.8 4.7 5.4 4.7 5.7 6.4 0.4 N w-% 1.9 2.1 2.1 2.8 1.7 1.5 0.7 0.7 1.8 2.8 0.5 O w-% 34.0 32.6 30.6 32.9 34.3 32.6 33.8 29.4 33.2 39.2 2.8 S w-% 0.6 0.2 0.2 0.2 0.2 0.2 0.1 0.1 0.2 0.7 0.1 Cl w-% 0.0 0.0 0.0 0.0 0.0 0.1 0.0 0.0 0.0 0.1 0.0 Ca Na, K w-% w-% 0.0 0.1 0.4 0.2 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.1 0.0 0.0 0.1 0.0 0.4 0.1 0.8 0.2 0.2 0.1

Peat Type 1 Type 2 Type 3 Type 4 Type 5 Type 6 Type 7 Min Average Max Stdev

5.1.3 Biofuels Biofuels may be the most important renewable source of energy, in Finland about 15 % of primary energy is produced by combustion of bioenergy (Sipil, Kurkela and Solantausta /47/). However, because the heating value of biofuels is low compared to fossil fuels, fuel mass flow rates are high. Most biofuels contain potassium and chlorine, which together cause boiler fouling and corrosion in superheaters. In worst cases, combustion of biofuels is close to waste incineration at superheater corrosion rates, for example, one CFB for co-combustion of straw and coal has suffered from fast corrosion, not only in the hottest tubes but also on relatively cool heat transfer surfaces.

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This is due to high chlorine content of the straw combusted: the worst samples have been detected to contain about 2 w % of chlorine. Presently, the chlorine content considered to be risky is 0.1 w-%. Some biofuel compositions are shown in Table 7. Table 7. Compositions of various biofuels, measured at Karhula R&D Center of Foster Wheeler Energia Oy. The statistics are from all samples analyzed.
LHV Volatile MJ/kg w-% 19.0 70.2 20.4 78.0 20.3 81.5 18.0 77.4 19.4 73.5 18.8 73.2 22.0 76.5 20.0 73.6 12.8 57.9 19.6 76.3 22.2 86.8 1.7 6.0 Ash w-% 8.8 1.7 1.1 3.7 5.1 7.2 11.8 8.8 0.3 5.0 35.7 6.8 C w-% 48.5 51.1 50.0 46.3 49.5 47.4 49.5 48.7 33.0 49.3 53.6 3.9 H w-% 5.4 6.2 6.1 5.5 5.7 5.5 6.1 6.1 4.3 5.9 6.5 0.4 N w-% 0.4 0.5 0.2 0.3 0.6 0.6 2.3 0.9 0.0 0.6 7.3 1.0 O w-% 36.8 40.5 42.5 43.9 39.0 39.2 29.3 35.4 16.1 38.5 44.2 4.9 S w-% 0.0 0.0 0.0 0.0 0.1 0.1 0.4 0.1 0.0 0.1 1.4 0.2 Cl w-% 0.0 0.0 0.0 0.2 0.0 0.1 0.5 0.0 0.0 0.1 0.9 0.2 Ca Na, K w-% w-% 0.0 0.3 0.0 0.0 0.3 0.1 0.0 0.3 0.0 0.3 0.0 0.4 0.0 5.0 0.0 0.9 0.1 0.0 0.6 0.4 2.9 5.0 0.7 0.8

Fuel Wood 1 Wood 2 Wood 3 Bark 1 Bark 2 Bagasse Nut shell Olive residue Min Average Max Stdev

5.1.4 Recycled Fuels Due to the increasing demand for package and waste recirculation, the recycled fuels, such as REF (Recycled Fuel) and RDF (Refuse Derived Fuel) have become important. Both of these fuel types have a relatively high heat value, and in some cases REF can be a very good fuel, for example pure polyethylene (Fire /48/). In most cases, though, there are varying amounts of impurities and harmful substances in the recycled fuels. These can create a very damaging environment in the superheater vicinity (Campbell et al. /49/). In most cases, the RDF and REF combustion require special measures for corrosion prevention. Some approximate elementary analyses of recycled fuels are listed in Table 8. In addition to the aforementioned recycled fuels, the wood processing industry has started to burn different sludges from waste-water treatment in utility boilers. These sludges may contain high amounts of alkalis and chlorides, thus even low fractions of these sludges in combustion may cause fouling and chloride induced corrosion in the superheater region. Analyses of several sludges are also included in Table 8.

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Table 8.

Compositions of various recycled fuels, measured at Karhula R&D Center of Foster Wheeler Energia Oy. The statistics are from all samples analyzed.
LHV Volatile MJ/kg w-% 22.7 72.2 18.2 76.8 13.5 84.4 15.1 62.1 20.7 74.8 34.3 88.3 41.0 93.7 3.2 17.0 19.4 70.3 41.0 93.7 6.6 14.7 Ash w-% 18.1 7.1 32.9 27.9 6.4 9.2 1.6 1.1 18.7 76.5 16.3 C w-% 49.8 44.9 33.0 36.4 50.4 65.0 75.0 5.7 44.7 75.0 11.7 H w-% 6.8 5.8 4.4 4.8 6.2 10.4 12.0 2.3 5.9 12.0 1.8 N w-% 0.3 1.7 0.3 0.9 1.1 0.1 0.7 0.1 1.1 6.6 1.3 O w-% 23.6 39.5 29.3 29.5 35.6 15.2 9.4 2.0 27.6 43.0 9.4 S w-% 0.1 0.8 0.1 0.2 0.1 0.1 0.1 0.0 0.3 1.4 0.3 Cl w-% 1.3 0.2 0.0 0.5 0.1 0.0 1.3 0.0 0.6 9.4 1.4 Ca Na, K w-% w-% 0.0 0.2 0.6 0.0 0.0 0.0 0.0 0.0 0.0 1.3 0.0 0.0 0.0 0.1 0.6 0.0 4.1 0.5 9.7 2.8 3.2 0.6

Fuel type Sludge 1 Sludge 2 Sludge 3 Waste 1 Waste 2 Waste 3 Waste 4 Min Average Max Stdev

5.2 Fuel Feeding Together with the fuel characteristics, the importance of the fuel feeding has to be noted. If the fuel feeding system can provide the boiler with a constant, homogenous fuel flow, the combustion will be stable, and variations in the flue gas composition will be minimized (Andrews et al. /50/). As mentioned earlier in the Chapter 4.2.1 about sulphur corrosion, fluctuation in the fuel feeding can cause a high CO content in the flue gas, thus increasing the corrosion rate. The effect of fuel feeding on corrosion in fluidized bed combustion has not been extensively studied. It is also possible to create reducing combustion zones in the furnace by feeding the fuel only into one side of the boiler. This situation, especially in BFB boilers, can with very poor fuel mixing in the furnace, result in one-sided combustion, i.e. one side of the furnace is gasifying and the other is combusting with excessive air. In the worst case, this will cause afterburning in the superheater section. This afterburning can increase the tube material and deposit temperatures, causing an accelerated corrosion rate. In the CFB boilers, the fuel can be fed into the solids return. This allows the fuel to be dried prior to entering the furnace region. The fuel will also be mixed with the hot recirculating solids, which in turn will be further mixed in the furnace.

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6.0

EFFECT OF BED MATERIAL

The bed material, both in the BFB and the CFB, can have a major effect on fouling and hence on the superheater corrosion. In a fluidized bed boiler, the bed material has three main roles: heat storage temperature stabilator catalyst or sorbent.

The most often used bed materials are silica based sands, and limestones. Limestones are mainly used for sulphur capture in CFB boilers. Different sorbents and additives can be added for alkali metal capture and emission control (Ylipahkala and Orjala /51/). Kaolin based sands are used when the potassium content of the fuel used is high, because potassium and silica can form compositions with low melting points. It has been reported by Baxter et al. /52/ that in the case of high-potassium fuels, the silica based sands will adsorb the potassium and react by forming potassium silicates with low sticky temperatures. This will lead to sintering in the bed. If such fuel is used, the bed has to be regenerated sufficiently by introducing new bed material and simultaneously taking out the used bed. Evans /32/ and Keairns et al. /53/ have referred to several tests with magnesia (MgO) based bed materials. These tests point out that the magnesia can reduce fouling and corrosion. The problem is that MgO is more expensive than silica based sand. Other bed materials such as aluminium oxide have also been tested, but the problem always seems to be the costs: the materials are expensive, and their consumption is high. Some of these materials are also very erosive. Table 9 shows some analysis results of different sorbents. Table 10 contains information about different sands used as the bed material.

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Table 9.

Compositions of sorbents, measured at Karhula R&D Center of Foster Wheeler Energia Oy. The statistics are from all samples analyzed.
Sorbent Limestone 1 Limestone 2 Dolomite 1 Dolomite 2 Min Average Max Stdev Ca w-% 37.3 36.3 11.6 20.8 11.6 36.3 69.4 5.5 Mg w-% 0.5 0.8 6.1 11.5 0.1 1.3 12.0 2.3 C w-% 11.5 11.1 5.4 12.0 0.3 10.9 12.8 1.8 S w-% 0.0 0.0 0.3 0.0 0.0 0.1 3.2 0.2

Table 10.

Compositions of sands, measured at Karhula R&D Center of Foster Wheeler Energia Oy. The statistics are from all samples analyzed.
Al w-% 5.6 7.1 1.5 3.1 0.0 3.7 9.3 3.0 Ca w-% 1.2 1.2 0.4 9.5 0.0 5.3 30.1 9.1 Fe w-% 1.9 2.0 0.3 0.8 0.3 1.2 2.5 0.8 K w-% 1.7 2.4 1.0 2.1 0.1 1.9 4.0 1.2 Mg w-% 0.7 0.4 0.1 1.4 0.0 0.5 1.4 0.4 Na w-% 2.3 1.5 0.4 0.8 0.0 0.9 2.3 0.7 S w-% 0.0 0.0 0.1 0.0 0.0 0.0 0.1 0.0 Si w-% 34.6 35.3 43.5 33.4 22.1 50.4 98.8 24.5

Sand 1 Sand 2 Sand 3 Sand 4 Min Average Max Stdev

7.0

EFFECT OF TEMPERATURES

Flue gas temperature and tube material temperature are very important parameters in superheater fireside corrosion, because they directly affect the corrosion rate. The combustion temperature and bed material temperature also affect the corrosion rate, but the mechanisms are more indirect.

7.1 Flue Gas Temperature The flue gas temperature acts in two ways: The higher the flue gas temperature near the superheater is, the higher the tube material temperature will be. The higher the flue gas temperature near the superheater is, the more partially molten particles there will be in the flue gas.

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The effect of flue gas temperature has been illustrated by curves created by VDI /54/, an example is shown in Figure 19. These curves have been developed for coal combustion, but they are also useful for combustion of biofuels. The curves show an increase in the corrosion rate as the flue gas temperature increases . The increase in the corrosion rate can be explained by the fact that the higher the flue gas temperature is, the greater the risk of fouling will be. The formed deposit will then contain more corrosive components, and the risk of metal corrosion will be increased.

Figure 19.

Dependence of corrosion rate on the flue gas temperature (VDI /54/).

7.2 Tube Material Temperature The tube material temperature is a very important design parameter in connection with fireside corrosion. The tube material temperature depends on several aspects: steam temperature steam flow tube material heat transfer rate flue gas temperature.

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An increase in the tube material temperature will often cause two things: The material endurance will decrease. The corrosion reaction rate will increase.

In most cases, the corrosion rate will increase fast, if the metal temperature is increased. The corrosion rate can be presented as a curve showing material loss versus temperature. An example curve is shown in Figure 20. The corrosion rate can also be shown as decrease in thickness per time, i.e. mm/h. The corrosion rate depends on the steel used for the superheater. The oxidation rate of the steel will often increase if the temperature is increased. Together with the increased corrosion reaction rate the material loss may increase exponentially.

Figure 20.

Corrosion rate of selected steels versus metal temperature (Sumitomo Metal Industries, Ltd. /55/).

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7.3 Combustion Temperature The combustion temperatures, and especially in BFB boilers, the freeboard temperature of the flue gas are very important as regards the alkali and chlorine release. It has been reported by Baxter et al. /52/ that the alkali release increases greatly when the combustion temperature is increased. The sulphur capture rate will be reduced when the combustion temperature is increased over 900 C, resulting in high SO2 and SO3 concentrations in the flue gas.

7.4 Bed Material Temperature The bed material temperature affects two mechanisms: fuel decomposition bed material decomposition

The bed material decomposition becomes a problem, if the bed is used for sulphur or alkali capture, because the captured components may be released in the process, resulting in the aforementioned problems.

8.0

EFFECT OF SUPERHEATER DESIGN

The superheater design and placement affects the corrosion rate. Often the affect of the design will be related to the temperature, but in some cases the flue gas velocity in the superheater area will contribute to the corrosion, especially in the case of erosion-corrosion. The superheaters should be designed so that fouling could be minimized, but the need for sufficient heat effect often sets the boundary criteria for the location. There are some ways of preventing corrosion of the superheater by the superheater lay-out. The superheater tubes can be partially protected by shields; these are used especially in the soot-blowing region to protect the first tube rows from the erosion caused by steam. The superheater tubes can also be protected by metal coatings, but unfortunately, most of the commercially available coatings are still at development stage.

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8.1 Tube Heat Exchangers The tube heat exchangers are the most common type of superheaters. The tubes can be vertically or horizontally aligned, supported or hanging bundles, through which the steam flows. The tubes can also be welded to plate-like constructions. Tube-type superheaters can be located in the furnace (in BFB boilers) or in the back pass. The tube configuration can be linear or staggered, and the distance between the tubes can be used as a design parameter: the denser the bundle is, the more vulnerable to fouling it will be. The tube diameter and wall thickness can be selected according to the need. Some oxidation and corrosion allowance must be included in the wall thickness. The tube superheaters are often fouled according to Figure 21. The corrosion is usually at worst between 30 and 90 of the gas-particulate streamline. This is due to several reasons. The deposit is formed on the front and back sides of the tube, and hence the heat transfer through the deposit and the tube wall creates higher temperatures in the area where the deposit thickness is the lowest. If there are molten salts or eutectic mixtures in the deposit, the molten phase will diffuse in the high temperature region. Also, the volatile corrosion products are most easily released in the area where the deposit thickness is the lowest.

Figure 21.

Tube deposition pattern (Allan, Erickson and McCollor /56/, Figure 2).

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8.2 Omega-panels In CFB boilers, superheaters have been located in the furnace as Omega-panels to achieve a high heat flux. These provide a considerable amount of heat with a moderate heat transfer area, but they are exposed to unburned fuel, and erosion caused by the fast fluidized bed. The Omega-panel is shown in Figure 22. The lower edge of an Omega-panel has to be protected against erosion by a welded plate. The material used for the plate is often AISI 253 MA or some other hi-Cr hi-Ni alloy.

Omega tubes Weld

Figure 22.

An illustration of an Omega-panel (Foster Wheeler /5/).

8.3 External (EHE) Superheaters External heat exchanger (EHE) superheaters have been used for several years. An example of the EHE design is shown in Figure 23. The idea of external heat exchangers is in the thermodynamics. Due to the high temperature in the bed region, the harmful components are volatalised and removed with the flue gas. The material getting in contact with the heat exchange surfaces is bed material which is almost clean from impurities like potassium, sulphur and chlorine, or the impurities are captured by the bed, such as CaSO4. In theory this works, but due to the high metal temperature, the corrosion reactions are accelerated, and the metal oxidation rate is also increased. This can cause a rapid material loss, if the heat exchanger material has been selected incorrectly. The problems encountered with the external heat exchangers are erosion and high metal temperatures due to the high heat transfer rate, which can be as high as 500 W/(m K). The steel to be used in an EHE superheater should be austenitic, if the steam temperature is over 500 C.

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Figure 23.

Principle of Lurgi external superheater (Bunzemeier /57/, Bild 6.2).

8.4 Soot Removal Systems Different soot removal systems have been developed to regenerate the heat transfer after the superheater surfaces have been covered with deposits. The main idea is to release as much as possible of the deposit without damaging the superheater tubes (Huhtinen et al. /58/). The existing soot removal methods rely on the following principles: jet momentum thermal shock mechanical shock vibration controlled erosion.

The steam soot-blowers are common in coal combustion. The idea is to utilize steam for soot removal. The steam works in two ways: the jet momentum of the steam flow will remove the loose deposits, and the thermal shock will loosen the dense deposits. The problem with steam soot-blowers is in erosion and in the possible water-gas reaction, presented in equation (20). Mechanical soot removal systems are used in heavily fouling conditions, because the steam soot-blowers can seldom be used continuously. The soot removal is based on the movement and vibration of the tube caused by a mechanical impact. The equipment can be a hammer or a bar which hits the tube bank. The main problems with the mechanical soot removal systems lie in the constant need for maintenance and high noise level.

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The tube vibration can be caused by an ultrasonic transmitter, which is inexpensive to use and brings no unfavourable gases into the process like the steam soot-blowers do. The weakness of the ultrasonic soot removal systems is their incapability to loosen dense deposits. Controlled erosion is utilized in external heat exchangers, where the fluidized sand constantly removes the deposit. The problem in the process is in balancing the fluidization so that it would be sufficient for the deposit removal without causing erosion on the tube material.

9.0

WAYS OF PREVENTING SUPERHEATER CORROSION

The superheater corrosion can seldom be totally prevented, if the fuel is harmful enough. However, there are ways to reduce the corrosion rate. The previously mentioned factors can be taken into account in the superheater design. The concentration of harmful impurities in the flue gas can be reduced by limiting the fraction of the worst fuel component. The boiler can be designed so that the corrosion risk is reduced. The superheater materials can be selected according to the presumed corrosion risk. The superheaters can be placed so that the fouling and corrosion are minimized. Hein /59/ has presented several possible means for reducing high temperature corrosion: avoiding slagging and fouling keeping flue gas O2-lean avoiding unburnt carbon in deposits diluting sulphur oxides changing tube material changing tube temperatures shielding tubes changing fuel or blend reducing concentrations of harmful components via additives.

The aforementioned means are often more or less limited, and the available methods can be reduced to the following: fuel fractions superheater materials and protection design issues process conditions.

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9.1 Fuel Fractions The difficult fuels are seldom combusted alone. In many cases, the corrosive fuel is only one of many, and the fraction of the harmful fuel can be reduced. Especially in the case of recycled fuels, the fraction of the worst component can be limited so that the chlorine and potassium mass flow into the boiler is minimised. This needs to be considered in the fuel preparation, because a corrosion attack can be initiated by a short period of combustion of a fuel mixture containing substantial amounts of chlorine. Presently, the maximum chlorine content allowed in the fuel mixture is 0.05 %. The slagging and fouling can also be reduced by fuel selection. By limiting the percentage of the slagging and/or fouling fuel component, the superheater fouling can be minimized. In addition to the reduced fouling rate, the removability of the deposit can be improved by fuel selection.

9.2 Superheater Materials The steels used in superheaters have in principle been similar for several decades. Highchromium alloys have been used for a long time. Addition of nickel for corrosion resistance has been known, and substrates like Ce, Cu, Nb and Ta have been used for improved strength and durability (Skrifars and Hupa /60/). However, when the environment is corrosive enough, and the material temperature is sufficiently high, even the most expensive materials have been noticed to fail. This is due to the fact that corrosion seldom is due to one component only, but it is a very complicated phenomenon involving several contributing factors. Figure 24 shows results from a test series in Germany. The most interesting result is that the same steel can have a very good and very bad operating record depending on the conditions. This indicates that the material selection is seldom on a solid base: an expensive high-chromium alloy may have lower corrosion resistance than a common low-chromium steel. In field tests, it has been noticed that some steels exist which have better characteristics for corrosion resistance than the others.

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Some typical superheater steels for corrosive environments have been listed in Table 11. These steels have been used in several units, and the results of their endurance have been widely reported.

Figure 24.

Performance of selected steels in highly corrosive environment (Cerjack and Mayrhuber /61/).

Table 11.
10CrMo910 9Cr1Mo X20CrMoV121 AISI304 AISI310 253MA Sanicro 28 Alloy 600 Alloy 800HT AC66 Nicrofer 45TM HR11N

Typical steels for superheaters.

Cr 2.25 9.00 9.00 19.00 25.00 21.00 27.00 15.50 21.00 27.00 27.00 28.50 Ni Mo 1.00 1.00 1.00 Si Cu Al Mn Nb C Other

0.50 9.50 20.50 11.00 31.00 9 Fe 32.50 32.00 23 Fe 40.00

0.50 0.50 1.70

0.50

0.23 0.08

N, Ce 1.00 0.26 0.40 0.50 0.75 <1 0.07 Ni bal. 0.05 Ti 0.06 Ce 0.08 Re, Ni bal. N

3.50 0.25 0.50 <0.3 2.70 1.00

0.40 <0.025 0.20

0.80

Some typical rules of steel selection according to composition are: Cr improves corrosion resistance in general. Ni is good against chlorine corrosion, but poor for sulphur corrosion. Al is good against chlorine corrosion and creates good oxide protection, but expensive. Si is good against chlorine corrosion, but may be affected by alkali metals.

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9.3 Superheater Design Superheater design can be utilized as a method for reducing corrosion. The superheater locations, how the steam flows are connected, and how the surfaces are protected can make a great difference to the corrosion rate. If the fuel is considered to be corrosive, the superheaters have to be located so that the risk of corrosion is decreased. This can be achieved by locating the hottest superheater or reheater in the bed region as an external heat exchanger and connecting the superheaters in the flue gas so that the high tube temperatures take place where the flue gas temperatures are sufficiently low. If the superheaters are to be exposed to direct radiation, the metal temperatures can be higher than estimated due to the higher outside heat transfer. The material temperatures may also increase due to disturbances in steam flow.

9.4 Boiler Design The whole boiler design contributes to superheater corrosion. All the main rules are not fully understood, but in general, the fuel and flue gas residence times in the furnace have to be sufficient. This requirement is also necessitated by the need for certain combustion efficiency and emission minimization. The grid design and fluidization velocities have some influence on the bed attrition and fly ash composition. In CFB boilers, the solids separator can be designed to create the desired fly ash particle size distribution, thus allowing reduced fouling or controlled erosion in the convective pass.

9.5 Process Conditions The combustion conditions are typically set by the fuel and boiler design. In order to achieve maximum efficiency, the amount of excess air should be minimized, typically the air coefficient is controlled between 1.1 and 1.2. In normal operation, the bed and combustion temperatures greatly depend on the boiler load. The region where combustion takes place can be altered by air distribution, but it is recommended that the maximum combustion temperatures are kept as low as possible to minimize emissions.

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10.0

SCOPE OF THE EXPERIMENTAL PART

This study comprises existing corrosion theories and field measurements, based on which a model for prediction of corrosion potential was generated. A neural network was selected as the method for prediction, because the factors contributing to superheater corrosion in atmospheric fluidized bed combustion are not evident. Some relations have been described in the earlier chapters, but many influences remain unknown. Development of a theoretical calculation model for the phenomenon necessitates several assumptions. However, a neural network which is taught with existing field data provides a solution which gives a good estimate with a few input parameters. To find out the usability of such a tool for prediction of superheater corrosion, a neural network model was constructed and taught. The teaching of the neural network was based on the data achieved from field studies and laboratory measurements of superheater corrosion. The methods used for the measurements and analyses included metal thickness measurements, microscopic and SEM/EDS studies, as weel as probe tests. The corrosion database created during the study contains not only information about the corrosion rates, but also information about several fuels, boiler types, bed materials and process conditions. This data was used for the learning process of the neural network. Several neural networks were tested and evaluated. The final model was evaluated by statistical means and by comparing it to new corrosion cases not included in the learning data.

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11.0

CORROSION EVALUATION

Means used for corrosion evaluation during this work can be listed as follows: SEM/EDS analyses optical microscopy chemical analyses of deposits and corrosion products both thermodynamical and thermochemical calculations probe tests tube thickness measurements.

11.1 Optical Microscopy The primary equipment used for the sample analyses and corrosion research were an optical microscope and a SEM/EDS (Scanning Electron Microscope/Energy Dispersive Xray Analysis System). The optical microscope used was a Wild Heerbrugg M8-Zoom + MPS12/05, equipped with a Leica kinofilm camera. The optical microscope was used for surface photographs and cross-sectional evaluation of corrosion samples. The maximum magnification available was 55 X, which is sufficient for preliminary evaluation of corrosion. The optical microscopy was mainly used as a basis for the electron microscopy. Two examples of a corroded tube sample are shown in Figures 25 and 26.

Figure 25.

Photograph of a pitted steel surface, steel 10CrMo910, taken from a probe test during combustion of high-chlorine fuel.

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Figure 26.

Photograph of a cross-section of a heavily corroded steel tube, steel 10CrMo910, sample taken from a probe test during combustion of highchlorine fuel.

11.2 Electron Microscopy The electron microscopy was used for detailed corrosion analyses. SEM photographs combined with EDS results provide enough information for the detection of the corrosion type, and in many cases also the corrosion rate. The metal oxidation and sulphidation are easy to detect, and in most cases, other corrosion products can also be identified. The maximum magnification during the study has been about 10 000 X, which is sufficient for providing detailed information of any of the local corrosion phenomena. Two different SEM/EDS systems were used for the analyses. The system used until the end of 1996 was a Jeol JSM 25 SII with EDAX 9100. After this, the system was updated into Jeol JSM-5800 with Link Isis 6841. The SEM photographs were normally scanned for reporting, but scanning also allowed the use of the scanned files for image processing to highlight the interesting areas. The new EDS system allowed saving of pictures directly to TIFF and BMP formats, which provided a better resolution and made the image processing easier. The principle of electron microscopy is shown in Figure 27. Examples of SEM photographs and EDS results of the analyses are shown later in the context of corrosion in different boilers.

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Figure 27.

Comparison of three methods of microscopy (Jeol /62/).

11.3 Chemical Analyses Chemical analyses were mainly performed at the Foster Wheeler Karhula R&D Center. The XRF analyses were done by the Ahlstrom Glass Laboratory in Karhula. The main interest focused on the fuel and fly ash alkali, sulphur and chlorine contents. Deposits found at different power plants were also analyzed. The used analysis methods are listed in Table 12. Table 12. Analysis methods used. Method AAS XRF HCN LECO Sulfur LECO TGA EDS Purpose Cl, Na, K Mineral composition as oxides H, C, N S, CO3 Volatiles, Fixed C composition as elements

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11.4 Calculations In order to determine the possible chemical compositions in different process conditions, several calculation methods were used. A most useful tool for chemical calculations was a computer program called HSC by Roine /63/. The program allows calculation of thermochemical stability diagrams, as well as equilibrium compositions. An example of a phase stability diagram is shown in Figure 28. The built-in database for substances is sufficient for high-temperature corrosion chemistry. Other calculation methods used were more simple, spreadsheet-based programs, which were used for mass and energy balances, and temperature calculations.
log p O 2 (g ) 40 30 C rO 3 20 10 0 -1 0 -2 0 -3 0 -4 0 -5 0 -6 0 -2 5 -1 5 -5 5 15 25 log p C l2 (g ) Cr C r C l2 C r2O 3 C r C l3 C r C l4 C rO 2 C r O 2 C l2 P h a se S ta b ility D ia g r a m at 550 C

Figure 28.

Phase stability diagram of Cr at 550 C and 1 bar in the presence of Cl2 and O2, calculated by the HSC program by Roine /63/.

11.5 Probe Tests The probe tests had two main purposes: deposit formation research corrosion research.

The probe used for corrosion testing has been shown in Figure 17. The same probe design could be used for both deposit formation and corrosion tests.

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11.5.1 Deposit Formation Tests Deposit formation tests were done in order to find out the deposition rates in different process conditions with different fuels and boiler designs. Deposits were collected after varying exposure times, and the deposition rates and chemical compositions of the deposits were evaluated. The deposit formation tests provided useful information about the corrosion potential caused by the fuel combusted. The deposit formation data could be further developed by calculating the most probable chemical compositions by taking into account the gas atmosphere, and comparing the results with the corresponding results from known corrosion cases.

11.5.2 Corrosion Probe Tests Corrosion probe tests were performed with different fuels and operating conditions to find out the corrosion mechanism, and in some cases, the corrosion rate. The test temperatures were varied according to the boiler type and test purpose. The materials were selected on the basis of the desired steam temperature and estimated corrosion risk. The deposit formation tests focused on the deposit, whereas the focus of the corrosion tests was set on the steel coupon. The main evaluation of a corrosion probe test was done by comparing the measured corrosion rates with known cases, and estimating the initial oxidation rates according to the test temperature and data provided by the steel manufacturer. An example of the outlook of a corrosion probe after a test is shown in Figure 29.

Figure 29.

Corrosion probe after one week of operation during a test combustion at Foster Wheeler Karhula R&D Center.

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11.6 Tube Thickness Measurements The tube thickness measurement is one of the most convenient ways of determining the possible material loss in a boiler. However, in order to obtain a thorough picture of the corrosion rate, a large number of measurements has to be performed. The measurements can only be done during a boiler shutdown. Furthermore, the measurements do not tell about increased oxidation, if the oxide layer is dense. A reliable way of determining corrosion mechanism is to take a tube sample, but in most cases, this can only be done during repairs. The equipment normally used for the tube thickness measurement is a combined ultrasonic transmitter/receiver. The tube thickness measurement data used in the corrosion database was gathered from the archives of Foster Wheeler Service Oy, where data from several commercial boilers was available. The device presently used by FWS Oy is Panametrics 26 DL, which has an internal accuracy of 0.05 mm.

12.0

CORROSION CASES

The superheater corrosion has been monitored and reported in a large number of boilers combusting coals, biofuels, recycled fuels and sludges. These boilers include BFBs and CFBs. The corrosion has been monitored with thickness measurements and analyses from samples taken from damaged tubes. The locations mostly suffering from corrosion are often in the hottest superheater, and especially at the hot end of the steam loop. The corrosion detected has mostly been local chlorine and sulphur induced corrosion. The main differences between BFB and CFB boilers regarding the superheater corrosion has been in the attrition of the bed material and different flue gas residence times in the combustion zone.

12.1 Corrosion in BFB Boilers The BFB boilers have mainly been constructed for the pulp and paper industry. The fuels are biofuels from wood handling and sludges from waste water treatment, and peat. The locations mostly suffering from corrosion are superheaters located inside the furnace so that they are

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exposed to direct radiation of the bed region. The radiation causes a higher outside heat transfer coefficient, thus increasing the temperature of the tube material. However, low flue gas residence times in the combustion zone prior to the superheater section result in partially combusted fuel particles and high amounts of unburnt carbon in the deposits. An example of a SEM photograph of a corroded superheater tube sample taken from a BFB boiler is shown in Figure 30. Corresponding EDS analysis results are shown in Table 13.

Figure 30. Table 13.

Elmt Na K Si K P K S K Cl K K K Ca K Cr K Mn K Fe K Pb M Total

Sample taken from a damaged tube of a BFB boiler combusting biomass. EDS analysis results of the sample shown in Figure 30.

Spect. Element Atomic Type % % ED 2.76 5.36 ED 0.48 0.77 ED 0.27 0.39 ED 7.17 9.99 ED 8.97 11.31 ED 24.85 28.41 ED 1.02 1.14 ED 3.46 2.98 ED 0.35 0.28 ED 46.35 37.09 ED 2.72 0.59 100.00 100.00

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12.2 Corrosion in CFB Boilers Most of the CFB boilers have been built for coal combustion due to the need for efficient sulphur capture. Several applications exist where the fuel is biofuel or co-combustion of biofuel and coal or peat. The units may also use recycled fuels as an accessory fuel. The corrosion in CFB boilers mostly takes place in the back pass where the hottest superheaters are located. Sulphur corrosion in Omega panels located inside the furnace has also been detected. Material wastage in the soot-blowing region has been reported in several boilers. In some cases, the reason for the material loss has been erosion-corrosion combined with reducing environment. An example of a corroded superheater tube sample taken from a CFB boiler is shown in Figure 31. Corresponding EDS results are shown in Table 14.

Figure 31. Table 14.

Elmt O K Na K Al K Si K S K Cl K K K Ca K Cr K Fe K Ni K Pb M Total

Sample taken from a damaged tube of a CFB boiler combusting REF. EDS analysis results of the sample shown in Figure 31.

Spect. Element Atomic Type % % ED 25.95 60.04 ED 2.75 4.43 ED 0.33 0.46 ED 0.30 0.39 ED 9.21 10.63 ED 3.35 3.50 ED 6.01 5.69 ED 1.72 1.59 ED 0.44 0.32 ED 8.18 5.42 ED 0.13* 0.08* ED 41.60 7.43 100.00 100.00

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13.0

CORROSION TESTS

Several tests have been carried out on different corrosion types at the Foster Wheeler Karhula R&D Center. These tests have been performed during test burns of a variety of fuels, from high-grade coals to recycled fuels. The test units have been the two CFB pilots in Karhula, and several commercial BFB and CFB boilers. Test periods have varied from one week to one year, and some tests have included co-operation with the representatives of the customer.

13.1 Corrosion Tests in Pilot Units Corrosion testing is a standard procedure, if the fuel to be combusted is suspected to be corrosive. Several test series have been performed with less aggressive fuels to ensure the reliability of the test method. The fuels have been analyzed at the Foster Wheeler Karhula R&D Center, and the combustion tests have been reported by the responsible project manager. In some cases the corrosion and deposit formation tests have been carried out as separate test projects. Usually, some results have been included in the test reports, but in some cases, a separate corrosion report has also been prepared. A description of the two pilot units at Karhula is presented as Appendix 2.

13.2 Corrosion Tests in Commercial Units Several corrosion tests have been done in commercial boilers by the Foster Wheeler Karhula R&D Center. In commercial boilers, the testing automatically involves cooperation with the owner of the boiler. Few tests have been published due to the proprietary nature of the information achieved from the tests. However, some test results have been included in the corrosion database.

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14.0

CORROSION DATABASE

In order to be able to utilize the information achieved from the field and laboratory tests, a database of corrosion cases was constructed. The database was built upon an existing fuel database. Fuel analyses used in the database were mostly performed at the Karhula R&D Center. The fuel database was supplemented with corrosion and process data so that the factors contributing to superheater corrosion could be evaluated. The first version of the database was developed with Microsoft Excel 5.0 /64/ due to the need for modifications during the development. The database consisted of boiler type, size, steam parameters, bed and tube material, fuel characteristics, and corrosion data. The parameters used for the prediction model were normalized so that the maximum and minimum values of each parameter were used as the boundary conditions for that parameter. These maximum and minimum values were also transferred to the user interface in order to inform the user about the limits of the data used for the learning process. This helps to limit the cases where the user accidentally gives input parameters which are outside the boundaries, which in turn may lead to unexpected results.

15.0

PREDICTION OF CORROSION WITH A NEURAL NETWORK

The corrosion database was further developed by creating a neural network program, which was taught to provide an estimate of the predicted corrosion potential of a known fuel and bed material with certain flue gas and steam temperatures.

15.1 User Interface for the Neural Network The user interface for the model was developed with Microsoft Visual Basic 5.0 /65/ due to easy programming and high amount of pre-defined tools available. The outlook of the user interface is shown in Figure 32.

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The fuel data for the interface was provided from the fuel database, and the tube material and bed characteristics were gathered from separate databases. After the user had given the necessary input parameters, a normalized input array was constructed and transmitted to the neural network. The number of inputs was limited to 10, and one output was used as the estimated corrosion rate. The output was translated into the corresponding corrosion rate in the user interface. The outlook of the output window is shown in Figure 33. Several types of networks were constructed and evaluated. The different neural networks were taught with a Matlab neural network toolbox (Demuth and Beale /66/). A Fortran program for neural network learning and testing developed by Palosaari and Bulsari /67/ was also tested during the study.

Figure 32.

Data input window for the corrosion prediction model.

Figure 33.

Result output window for the corrosion prediction model.

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15.2 Evaluation of The Neural Network Model The constructed neural networks were evaluated by statistical means and sensitivity studies. The results were compared to the measured data, and the most reliable model was further developed to be used as a tool for prediction of corrosion rate in the evaluation of commercial projects at the Foster Wheeler offices in Varkaus and Kaarina.

15.2.1 Test Plan for the Neural Networks The prediction accuracy of the neural networks constructed had to be evaluated in order to find the most reliable way of estimating the corrosion risk. The evaluation was done according to Blackett-Burmann test plan constructed according to the criteria presented by Box, Hunter and Hunter /68/. The idea behind the Blackett-Burmann test plan is in the use of 2n factorial design. The 2n factorial design is based on using two levels for each variable, the number of which is n. The levels can be HIGH and LOW, or ON and OFF, etc. The idea is to have two different values for each variable, and generate a test plan based on these values. The number of tests required is given by the factor 2n, i.e. for 3 variables there will be 8 tests. It is also possible to generate half fractions, so that for 5 variables only 16 test are made. However, it is recommended to use the full test matrix so as to enable the use of effective means for the data analyses. The test matrix can be generated easily. The idea is illustrated in Figure 34. The matrix is generated for three parameters, T, C and K, so the number of runs is 8. The - represents the LOW level and + the HIGH level. It is also possible to use -1 and +1 for the two levels. This notation has one major advantage: the level indications can be directly used as factors representing positive and negative effects.

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Figure 34.

2n test matrix for three parameters, three different notations (Box, Hunter and Hunter /68/, page 308).

15.2.2 The Yates's Algorithm The test results can be analyzed with several methods, one of which is the Yates's algorithm. The Yates's algorithm is based on adding and subtracting the measured data values to and from one another in a specific order. The randomized test matrix has to be resetted to standard order (see Figure 34.) before the Yates's algorithm can be utilized. The test results, which are in the standard order, can be evaluated with the algorithm shown in Figure 35. The resulting estimates tell the effect of each parameter, as well as the interaction effects. This way of data analysis is a fast and reliable means for finding out which parameters have the largest effect on the results.

Figure 35.

The Yates's algorithm for data achieved from tests carried out according to a 2n experiment design (Box, Hunter and Hunter /68/, page 342).

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15.2.3 Statistical Means Along with the Yatess algorithm, the outputs of different networks were evaluated by statistical means. Standard deviations, maximum errors and sums of squared errors for the differences between the predicted values and the actual values were calculated, and parameters for F deviation were determined for each model. The number of learning datasets was maintained constant, so it was relatively easy the find the most suitable neural network for prediction of corrosion with the calculated statistical parameters.

15.3 Learning data There are several rules about the amount of learning data corresponding to the size of a neural network. One of the most important rules is that the number of weights in a network should not exceed the number of inputs multiplied with the number of datasets. This means that if we have 75 datasets and 10 inputs, the number of weights should be less than 750. In general, the number of neurons should be sufficient for the task, but low enough to avoid over-learning. Over-learning (or overfitting) means that the network fit for the learning data is good, but the network error increases if data is supplied to the network between the learning data points, an example is illustrated in Figure 36.

Figure 36.

An example of over-learned neural network (Demuth and Beale /66/, page 557).

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The normalized data used for the learning process of neural networks is shown in Appendix 3. The number of datasets was 92, evenly distributed between laboratory and field tests, and commercial projects. Only the most reliable datasets were selected to act as the learning data. One of the most common reasons for not using a certain dataset was the unreliable fuel analyses, especially in the cases where the corrosion was suspected to be due to one fuel component, the fraction of which was not known with certainty. Each data point in the datasets was also divided into ten classes to test fuzzy filtering prior to teaching the networks. This classed data was used as one mean of determining the possible overfitting, because if the generated network gives wrong results with the classed data, the network must be overfitting. The filtered data is also shown in Appendix 3.

15.4 Neural Networks Constructed Several different networks were constructed for the task. The testing was started with a simple approach, and the complexity of the solution was increased as the knowledge about the system behaviour increased. The generated networks were improved by testing different activation functions during the study in order to find the optimal solution for the problem at hand. The neural networks were tested against the data gathered during the summer of 1997, i.e. data which was not included in the learning data. The statistical parameters of each network were compared and according to these criteria, the most suitable network was selected. The networks were taught with both tools available. The effectiveness of the tools was also evaluated during the study. Several basic networks are described as examples in the following sections. The network combinations are listed in Appendix 4.

15.4.1 Linear Feed Forward Network The first test was made with a linear single-layer neural network. The number of inputs was selected to be 10, and only one output was used (=one neuron). The activation function was selected to be a piecewise-linear type providing a linear change in the output according to the input. A schematic presentation of the constructed neuron is shown in Figure 37. The number of parameters required by the network is relatively low: one weight per input and one bias.

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In addition to these, the limits of the linear activation function have to be defined. The amount of learning data necessary for such a network is low, but the capability of the simple network of defining high-order cross-correlations is also low.

15.4.2 Non-Linear Feed Forward Network The first neural network was altered by changing the activation function to a sigmoid function. This provided more non-linear action for the model. Two sigmoid function types available in Matlab were tested: logsig and tansig (see Appendix 1). The idea of a non-linear neuron is also shown in Figure 37.

Figure 37.

Schematic presentation of linear and non-linear feed forward neural network with one neuron.

15.4.3 Feed Forward Network with a Hidden Layer In the next phase, the linear network was improved by adding a hidden layer of first one and then more neurons. The added neurons provided better flexibility, but required more learning data, and increased the risk of over-learning. The number of parameters was thus increased by more weights and biases. The network is illustrated in Figure 38.

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Figure 38.

Fully connected neural network with one hidden layer of two neurons.

15.4.4 Feed Forward Network with Two Hidden Layers The neural network with a hidden layer of two neurons was further improved by adding a second hidden layer and increasing the number of neurons in the hidden layers. This allowed higher order non-linearity, but also increased the number of parameters. The risk of overlearning increased, as the number of parameters was increased.

15.4.5 Further Improved Networks The basic networks described earlier were improved by adding neurons and changing the combinations of activation functions. The learning data available limited the maximum number of neurons to 15, so the possible combinations were somewhat limited. However, with 15 neurons, it was possible to generate a prediction tool which was sufficient for the task at hand.

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15.5 Learning Algorithms Haykin /1/ has presented a taxonomy of the learning rules used for teaching neural networks, shown in Figure 39.

Figure 39.

Taxonomy of the learning rules (Haykin /1/, page 47).

The learning algorithms used during this study can be separated in three categories: linear algorithms error correcting algorithms modified and improved algorithms.

15.5.1 Learning of Linear Networks The simpliest case, a neuron with linear activation function, can be solved by matrix operations, if all the input and target vector pairs are known. However, this may in some cases lead to a singular matrix, in which case the network parameters will have to be solved by other means. In principle, if the linear solving is possible, the neural network will quickly provide an accurate model for the task. If we consider one linear neuron, the network operation can be presented with matrix operations y = WX + where W X array of network weights array of network inputs. (22)

If it is possible to determine X-1, W can easily be solved.

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15.5.2 Error Correcting Learning By Haykin /1/, for each neuron it is possible to write an equation ek ( t ) = d k ( t ) y k ( t ) where ek ( t ) dk (t ) error of neuron k at time t desired response of neuron k at time t. (23)

The network error can then be minimized according to the sum of squared errors 1 ek2 ( t ) 2 k sum of squared errors at time t

(t ) =
where

(24)

(t )

by adjusting the synaptic weights according to equation wkj ( t ) = ek ( t ) x j ( t ) where (25)

learning rate.

The principle of error correcting learning and signal-flow graph is shown in Figure 40.

Figure 40.

Error correction learning (backpropagation) (Haykin /1/, page 48).

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The Matlab Neural Network Toolbox contains three basic versions of error correction algorithms (learnbp, learnbm and learnbpx) which are all based on gradient descent method. The principle of the gradient descent method is shown in Figures 41 and 42.

Figure 41.

Schematic presentation of an error surface graph and corresponding error contour plot (Demuth and Beale /66/, page 5-12).

Figure 42.

Black line shows the progress of the learning process on the error contour plot, + refers to the start and x to the end (Demuth and Beale /66/, page 513).

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15.5.3 Modified Learning Algorithms The modified and improved learning algorithms are either based on gradient descent and improved by another algorithm, or on other methods. One of the most often used algorithms is the Levenberg-Marquardt approximation based on Newtons method, in which the weights are updated by rule w = ( J T J + I ) 1 J T e where J Jacobian matrix of error derivative scaler unity matrix error vector.

(26)

I e

The Levenberg-Marquardt approximation is faster than the gradient descent method, but problems occur when the number of neurons is large compared to the amount of learning data. The networks taught by the Levenberg-Marquardt approximation give good fit for the learning data, but may be overfitting, so the method has to be used with caution. The method in matlab (trainbplm) uses more memory than the more simple algorithms. Palosaari and Bulsari /67/ have improved the network approximation by adding a MonteCarlo method into the algorithm. The method is based on the use of a random number method in the selection of a set of starting values of the weights. The best values of the random set are permutated as a genetic method. Finally, the best candidates undergo a short preliminary minimization by powell conjugate method with cubione dimensional search. The best of these is chosen for the final, accurate minimization by the Powell conjugate method (Bulsari /69/). This improvement is more likely to find the real minimum of SSE without that much risk of overfitting, because the weight minimums and maximums are limited. This tool was also tested during the learning process.

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16.0

RESULTS

The first, simple neural networks were taught only with Matlab 5.0 Neural Network Toolbox. The more complicated networks were taught both with Matlab and the Fortran code by Palosaari and Bulsari /67/. The quality of learning was evaluated by monitoring the calculated sum of squared errors for both the learning data and the classed learning data. The first squared error, marked as SSE, gives an estimate of the accuracy of the networks, and the second, marked as SSEn represents a relative quantity of possible over-learning. Some generated networks and corresponding sums of squared errors are shown in Tables 15 and 16. Results of all the networks tested are shown in Appendix 4. The residuals of test data for the best network configuration are shown in Appendix 5. The use of Yatess algorithm for sensitivity analysis is described in Appendix 6, some sensitivity charts are also included. The dependence of the SSE on the number of neurons as calculated with 5000 epochs and adaptive backpropagation is shown in Figure 43. From Figure 43, it may be noticed that the increase in the number of neurons decreases the SSE until the number of neurons is 6, after which the SSE is almost constant, if a sufficient amount of epochs is used for the learning. However, by increasing the number of maximum epochs, the larger networks give better fits, but the risk of overfitting increases, as can be seen from Figure 44. The role of the activation function in the first hidden layer can be seen from Figure 45, where tansig and logsig functions are compared. It may be noted that although the difference is small if evaluated with statistical parameters, the tansig -type gives generally better results.

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Table 15.

Several neural networks and corresponding sums of squared errors, learning by adaptive backpropagation, max 5000 epochs.
First Layer Linear Logsig Tansig Logsig Tansig Logsig Tansig Logsig Tansig Logsig Tansig Logsig Tansig Logsig Tansig Logsig Tansig Logsig Tansig Logsig Tansig Neurons 1 1 1 2 2 3 3 4 4 5 5 6 6 3 3 4 4 5 5 6 6 Second Layer None None None Linear Linear Linear Linear Linear Linear Linear Linear Linear Linear Tansig Logsig Tansig Logsig Tansig Logsig Tansig Logsig Neurons 0 0 0 1 1 1 1 1 1 1 1 1 1 3 3 4 4 5 5 6 6 Third Layer None None None None None None None None None None None None None Linear Linear Linear Linear Linear Linear Linear Linear Neurons 0 0 0 0 0 0 0 0 0 0 0 0 0 1 1 1 1 1 1 1 1 Total Neurons 1 1 1 3 3 4 4 5 5 6 6 7 7 7 7 9 9 11 11 13 13 SSE 1.73 1.47 1.78 1.39 1.01 1.31 1.09 1.29 0.94 1.45 1.01 1.20 1.03 1.36 0.90 0.63 0.75 0.62 0.47 0.60 0.46 SSEn 1.73 1.55 1.78 1.36 1.39 1.35 1.33 1.34 1.10 1.45 1.31 1.33 1.30 1.49 1.04 1.41 2.98 0.91 1.89 1.25 1.04

Network ID 1 2 3 10 11 16 17 22 23 28 29 34 35 50 51 54 55 58 59 62 63

Table 16.

Several neural networks and corresponding sums of squared errors, learning by the Levenberg-Marquardt approximation, max 1000 epochs.
First Layer Linear Logsig Tansig Logsig Tansig Logsig Tansig Logsig Tansig Logsig Tansig Logsig Tansig Logsig Tansig Logsig Tansig Logsig Tansig Logsig Tansig Neurons 1 1 1 2 2 3 3 4 4 5 5 6 6 3 3 4 4 5 5 6 6 Second Layer None None None Linear Linear Linear Linear Linear Linear Linear Linear Linear Linear Tansig Logsig Tansig Logsig Tansig Logsig Tansig Logsig Neurons 0 0 0 1 1 1 1 1 1 1 1 1 1 3 3 4 4 5 5 6 6 Third Layer None None None None None None None None None None None None None Linear Linear Linear Linear Linear Linear Linear Linear Neurons 0 0 0 0 0 0 0 0 0 0 0 0 0 1 1 1 1 1 1 1 1 Total Neurons 1 1 1 3 3 4 4 5 5 6 6 7 7 7 7 9 9 11 11 13 13 SSE SSEn

Network ID 1 2 3 10 11 16 17 22 23 28 29 34 35 50 51 54 55 58 59 62 63

1.73 1.73 1.44 1.64 1.79 1.78 0.88 1.38 0.95 1.19 0.87 2.05 0.47 17.76 0.72 1.44 0.64 14.68 0.57 29.11 0.28 2.85 0.82 67.26 0.57 29.11 1.44 55.78 0.68 2.69 0.56 4.88 0.36 12.44 0.43 51.73 0.13 4.05 0.16 120.86 0.34 23.82

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2.00

1.80

1.60

1.40

1.20 SSE

1.00

0.80

0.60

0.40 1 Layer 2 Layers 3 Layers

0.20

0.00 0 2 4 6 Total Neurons 8 10 12 14

Figure 43.

Dependence of SSE on the number of neurons, amount of neuron layers as a parameter, Matlab, adaptive backpropagation, 5000 epochs.
140

2.50

120 2.00 Matlab, Levenberg-Marguardt SSE SSEn Expon. (SSEn) Power (SSE) 100

1.50 SSE

80 SSEn 60 40 20 0 14

1.00

0.50

0.00 0 2 4 6 8 10 12 NUMBER OF NEURONS

Figure 44.

Dependence of SSE and SSEn on the number of neurons, Matlab, LevenbergMarquardt learning algorithm.

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2.00 Matlab, adaptive backpropaganation, 5000 epochs 1.80 Logsig 1.60 Tansig Log. (Logsig) 1.40 Log. (Tansig)

1.20 SSE

1.00

0.80

0.60

0.40

0.20

0.00 0 2 4 6 8 10 12 14 NUMBER OF NEURONS

Figure 45.

Difference between logsig and tansig activation functions.

It may be noted that some networks taught by the Lewenberg-Marquardt algorithm give a low SSE but they are heavily overfitting, which can be seen from the parameter SSEn derived by using the classified data as the network input. The networks 51, 55, 59, and 63 were selected for further analysis, because the purpose of the study was to find the most suitable network size and layout for the corrosion model, while the network was to be as large as possible.

16.1 Evaluation of Different Neural Networks The evaluation of different neural networks was performed according to calculated statistical criteria. The data used for further evaluation was gathered during the summer of 1997 by field measurements. The selected networks 51, 55, 59, and 63 were taught with backpropagation and tested against this test data. The data calculated with the networks is shown against the learning data and test data in Figures 46, 47, 48 and 49. The network 59 with 11 neurons was selected for the model, and taught with the classed data to improve the learning process. The result is shown in Figure 50.

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1.00

0.90

0.80

0.70 CALCULATED CORROSION

y = 0.8596x + 0.0282 R2 = 0.862

0.60

0.50

0.40

0.30

0.20 Learning data Test data

0.10

0.00 0.00

0.10

0.20

0.30

0.40

0.50

0.60

0.70

0.80

0.90

1.00

MEASURED CORROSION

Figure 46.

Calculated corrosion versus measured corrosion, normalized values. Network contains three tansig neurons in the first layer, three logsig neurons in the second layer and one linear neuron in the output layer.

1.00

0.90

0.80

0.70 CALCULATED CORROSION

y = 0.8735x + 0.025 R2 = 0.8787

0.60

0.50

0.40

0.30

0.20 Learning data 0.10 Test data

0.00 0.00

0.10

0.20

0.30

0.40

0.50

0.60

0.70

0.80

0.90

1.00

MEASURED CORROSION

Figure 47.

Calculated corrosion versus measured corrosion, normalized values. Network contains four tansig neurons in the first layer, four logsig neurons in the second layer and one linear neuron in the output layer.

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1.00

0.90

0.80

0.70 CALCULATED CORROSION

y = 0.9267x + 0.0152 R2 = 0.9176

0.60

0.50

0.40

0.30

0.20 Learning data 0.10 Test data

0.00 0.00

0.10

0.20

0.30

0.40

0.50

0.60

0.70

0.80

0.90

1.00

MEASURED CORROSION

Figure 48.

Calculated corrosion versus measured corrosion, normalized values. Network contains five tansig neurons in the first layer, five logsig neurons in the second layer and one linear neuron in the output layer.

1.00

0.90

0.80

0.70 CALCULATED CORROSION y = 0.9067x + 0.0165 R2 = 0.9172

0.60

0.50

0.40

0.30

0.20 Learning data 0.10 Test data

0.00 0.00

0.10

0.20

0.30

0.40

0.50

0.60

0.70

0.80

0.90

1.00

MEASURED CORROSION

Figure 49.

Calculated corrosion versus measured corrosion, normalized values. Network contains six tansig neurons in the first layer, six logsig neurons in the second layer and one linear neuron in the output layer.

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1.00

0.90

0.80

0.70 CALCULATED CORROSION y = 0.9417x + 0.0072 R2 = 0.955 0.60

0.50

0.40

0.30

0.20 Learning data 0.10 Test data

0.00 0.00

0.10

0.20

0.30

0.40

0.50

0.60

0.70

0.80

0.90

1.00

MEASURED CORROSION

Figure 50.

Calculated corrosion versus measured corrosion, normalized values. The network contains five tansig neurons in the first layer, five logsig neurons in the second layer and one linear neuron in the output layer. The network was taught with 184 datasets. This configuration was selected for the model.

The weights and biases of the network selected for the model are shown in Tables 17 to 19. Table 17. Weights and biases for the first hidden layer.
Neuron 13 -1.33 -3.72 1.27 -0.48 0.27 0.49 0.62 0.95 1.38 -1.28 -0.04

INPUT

A B C D E F G H I J Bias

11 3.58 2.41 -0.52 -0.54 -2.85 -1.17 0.22 1.14 -0.04 3.85 -3.24

12 -2.94 -3.05 3.24 1.16 -2.29 -0.89 2.15 -0.28 -2.27 0.20 1.84

14 0.51 1.94 1.38 0.46 -5.31 0.44 2.74 -1.51 0.92 -0.89 1.64

15 1.90 -2.42 1.42 -0.77 -1.72 0.01 0.96 -1.14 0.22 -0.26 -0.22

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Table 18.

Weights and biases for the second hidden layer.

Neuron 23 5.59 2.31 -1.76 3.87 1.31 2.23

INPUT

11 12 13 14 15 Bias

21 0.82 1.02 1.41 4.02 0.52 2.62

22 -1.00 1.58 -4.27 -0.64 -1.52 4.36

24 4.50 1.50 -2.68 3.20 3.26 3.98

25 1.58 4.93 0.34 -3.20 1.06 -3.08

Table 19.

Weights and bias for the linear output layer.

Neuron 31 1.01 -1.07 -2.97 3.31 1.88 -0.25

INPUT

21 22 23 24 25 Bias

17.0

FURTHER IMPROVEMENT OF THE MODEL

The generated model for corrosion prediction is based on the data gathered from field and laboratory measurements. The first aim of the study was to test the suitability of a neural network for prediction of superheater corrosion on the early stage of a project. At the beginning of a project, only little information of the fuel characteristics is available. Also, the boiler design is known only in principle. However, with this small amount of information a skilled professional can say if there is a corrosion risk or not. The challenge was to put this information into a form that can be used in a computer program. The generated neural network is based on two non-linear hidden layers and a linear output layer. The total number of neurons was selected to be 11, five in both hidden layers and one for the output. The network was implemented into the user interface developed with Visual Basic so that the weight and bias arrays can easily be changed as the amount of learning data increases and the network can be re-taught.

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The generated corrosion prediction tool can be further improved by generating more reliable methods for fuel, bed material, and boiler quality evaluation. All these input parameters are more or less discrete, and the task for the future is to create criteria according to which the quality of the input data can be ensured and thus the model accuracy improved.

18.0

SUMMARY

This study comprises corrosion theory and practice, providing a prediction model for the risk of superheater corrosion in atmospheric fluidized bed combustion. The model is based on a neural network, which can be further taught as the amount of corrosion data increases. This approach gives an option of improving the prediction accuracy without any major efforts in the model improvement. A total of 92 learning datasets were used for the learning process. The data was gathered from pilot and field tests during 1993 - 1997. A corrosion data-base was formed from the data. The data was normalized between 0 and 1 prior to the learning process. The network design for the model was selected by calculating several different designs shown in Appendix 4, best of which were selected for further evaluation. The evaluation was based on the sum of squared errors between the learning data and calculated data. The final networks were tested against test data gathered during the summer of 1997 by field measurements. The selected network layout for the model contained two hidden layers, the first layer was formed by five tansig neurons, the second had five logsig neurons and the output layer had one linear neuron. The initial learning data contained some data sets where the output differed considerably from the value calculated by the model. These data sets were investigated to find out the possible causes for the difference, and it was noticed that there are two types of superheater steel than may behave unexpectedly, if the gas environment changes. This knowledge was implemented in the user interface of the corrosion prediction model.

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The developed neural network model can estimate the corrosion risk in a project with approximately 80 % accuracy, which is only little worse than an estimate given by a skilled professional. The model will be improved in the near future by ensuring the validity of the new input data and developing new methods for estimation of fuel, bed material, and boiler qualities.

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Haykin S., Neural Networks, a Comprehensive Foundation, Macmillan Publishing Company, New York, 1994, ISBN 0-02-352761-7 Neural Network Research in Finland, Bulsari A. and Saxn B. (Ed.), Publications of the Finnish Artificial Intelligence Society - no 10, bo Akademi, Turku, 1993, ISBN 951-650-188-5 Neurolaskennan mahdollisuudet, Koikkalainen P. (Ed.), TEKES julkaisu 43/94, Paino-Center Oy, Helsinki, 1994, ISBN 951-47-1950-6, in Finnish Abdulally I. F. and Moore S., Design Update of the Foster Wheeler Bubbling Bed Boiler, in 1989 International Conference on Fluidized Bed Combustion, FBC-Technology for Today, Volume One, Manaker A. M. (Ed.), The American Society of Mechanical Engineers, New York, 1989 Presentation Material, Foster Wheeler Energia Oy, 1996 Reh L., Hirsch M., Collin P. H. and Flink S. N., Process for Burning Carbonaeous Materials, United States Patent 4.165.171, 1979 Hyppnen T. and Raiko R., Leijupoltto, in Poltto ja Palaminen, Raiko R., Kurki-Suonio I., Saastamoinen J. and Hupa M. (Ed.), International Flame Research Foundation, Jyvskyl 1995, ISBN 951-66-448-2, in Finnish Reference List, Bubbling Bed Boilers, Foster Wheeler, 1997 Pels J. R., Wjtowicz M. A., Kapteijn F. and Moulijn J. A., The Trade-off Between NOx and N2O Formation in fluidized-Bed Combustion of Coal, in Proceedings of the 6th International Workshop on Nitrous Emissions, Hupa M. and Matinlinna J., (Ed.), bo Akademi, Turku, 1994, ISBN 951-650-430-2 Leckner B. and Amand E., Emissions from a Circulating and Stationary Fluidized Bed Boiler: a Comparison, in 1987 International Conference on Fluidized Bed Combustion, Volume Two, Mustonen J. P., (Ed.), New York, 1987 Newby R.A. and Keairns D.L., FBC Sulfur Removal - Do We Know Enough?, in 1991 Fluidized Bed Combustion, Clean Energy for the World, Anthony, E.J. (Ed.) The American Society of Mechanical Engineers, New York, 1991, ISBN 0-7918-0619-7

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APPENDIX 1 1/2 03.02.1998

Activation Functions in the Matlab 5.0 Neural Network Toolbox (Demuth and Beale /66/, pages 13-10 and 13-11)

The output of the Tan-Sigmoid activation function can be calculated from equation tan sig ( n ) = tanh( n )

APPENDIX 1 2/2 03.02.1998

Activation Functions in the Matlab 5.0 Neural Network Toolbox (Demuth and Beale /66/, pages 13-10 and 13-11)

The output of the Log-Sigmoid activation function can be calculated from equation log sig ( n ) = 1 1 + e n

APPENDIX 2 1/2 03.02.1998 CFB Pilot Units at the Foster Wheeler Karhula R&D Center
Probe location Water boiler Reactor Cyclone Filter Scrubber

Fuel bin Fuel sample Fly ash sample Filter ash silo

Bed material sample

Bottom ash sample

Figure 51. Table 1.

Illustration of the PF-600 combustion pilot at the Karhula R&D Center. Process data of the PF-600 combustion pilot at the Karhula R&D Center. Up to 1 MW 600 mm diameter x 10 m height Up to 200 mbar at gas distributor Up to 1000 C Fabric filter baghouse Infinite variation on cyclone Continuous on-line analysis of O2, SO2, CO, NOx, CO2, HCl, SO3, CxHx Temperatures, pressures, gas compositions, solids and gas flow rates Water cooled tubes are used to remove energy both in the combustion chamber and in the convective cage

Thermal rating: Size: Pressure rate: Combustor temperature: Flue gas cleanup: Ash recycle capabilities: Flue gas analyses: Instrumentation: Heat transfer surfaces:

APPENDIX 2 2/2 03.02.1998 CFB Pilot Units at the Foster Wheeler Karhula R&D Center

PF650 compact pilot plant Probe location

Boiler

Multicyclone

Baghouse

ID fan

Fuels Multicyclone ash sample Baghouse ash sample Silo Silo

Make-up / Additive Bed sample Bottom ash sample

Secondary airs Primary air

Figure 52. Table 2.

Illustration of the PF-650 combustion pilot at the Karhula R&D Center. Process data of the PF-650 combustion pilot at the Karhula R&D Center. Up to 1.5 MW 650 mm x 650 mm x 13 m height Up to 200 mbar at gas distributor Up to 1000 C Multicyclone and fabric filter baghouse Compact separator, fly ash from multicyclone Continuous on-line analysis of O2, SO2, CO, NOx, CO2, HCl, SO3, CxHx Temperatures, pressures, gas compositions, solids and gas flow rates Water cooled Omega panels in the combustion chamber, INTREX heat exchanger for recycled solids, water tube boiler in the convective cage

Thermal rating: Size: Pressure rate: Combustor temperature: Flue gas cleanup: Ash recycle capabilities: Flue gas analyses: Instrumentation: Heat transfer surfaces:

APPENDIX 3 1/5 03.02.1998 Neural network learning data

# 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 A 0.15 0.15 0.15 0.15 0.15 0.15 0.15 0.15 0.15 0.15 0.15 0.15 0.15 0.15 0.15 0.15 0.15 0.15 0.15 0.15 0.15 0.15 0.15 0.15 0.15 0.15 0.15 0.65 0.65 0.65 0.65 0.65 0.65 0.65 0.65 0.65 0.65 0.15 0.65 0.15 0.15 0.15 0.15 0.15 0.15 0.15 B 0.15 0.05 0.05 0.05 0.25 0.25 0.25 0.05 0.35 0.45 0.45 0.45 0.45 0.45 0.45 0.45 0.25 0.05 0.85 0.85 0.85 0.85 0.85 0.75 0.75 0.75 0.25 0.35 0.35 0.25 0.65 0.65 0.15 0.15 0.15 0.15 0.15 0.65 0.65 0.65 0.65 0.25 0.05 0.35 0.35 0.35 C 0.17 0.39 0.39 0.39 0.11 0.11 0.11 0.42 0.08 0.07 0.07 0.07 0.07 0.07 0.07 0.07 0.11 0.43 0.04 0.04 0.04 0.04 0.04 0.04 0.04 0.04 0.12 0.08 0.08 0.11 0.05 0.05 0.16 0.16 0.16 0.16 0.16 0.06 0.05 0.05 0.06 0.12 0.41 0.08 0.08 0.08 D 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 1.00 1.00 1.00 1.00 1.00 0.80 0.80 0.80 0.25 0.22 0.22 0.22 0.28 0.27 0.26 0.26 0.26 0.26 0.26 0.07 0.18 0.06 0.05 0.29 0.05 0.33 0.41 0.31 E 0.15 0.15 0.15 0.15 0.45 0.45 0.15 0.15 0.45 0.15 0.15 0.45 0.45 0.15 0.15 0.45 0.15 0.45 0.45 0.45 0.45 0.45 0.45 0.45 0.45 0.45 0.15 0.15 0.15 0.15 0.45 0.15 0.15 0.15 0.15 0.15 0.15 0.15 0.15 0.15 0.15 0.15 0.15 0.45 0.45 0.45 F 0.31 0.31 0.31 0.31 0.31 0.31 0.31 0.31 0.31 0.31 0.31 0.31 0.31 0.31 0.31 0.31 0.31 0.31 0.36 0.36 0.36 0.36 0.36 0.42 0.42 0.42 0.13 0.13 0.13 0.13 0.13 0.22 0.24 0.24 0.24 0.24 0.24 0.03 0.11 0.02 0.36 0.19 0.11 0.28 0.32 0.19 G 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.80 0.20 0.80 0.80 0.80 0.80 0.80 H 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.48 0.48 0.48 0.48 0.48 0.12 0.12 0.12 0.48 0.48 0.48 0.48 0.33 0.38 0.17 0.17 0.17 0.17 0.17 0.17 0.48 0.17 1.00 0.22 0.22 0.22 0.22 0.22 I 0.38 0.38 0.38 0.38 0.38 0.38 0.38 0.38 0.38 0.38 0.38 0.38 0.38 0.38 0.38 0.38 0.38 0.38 1.00 1.00 1.00 1.00 1.00 0.53 0.53 0.53 1.00 1.00 1.00 1.00 0.47 0.87 0.33 0.33 0.33 0.33 0.33 0.33 1.00 0.33 1.00 0.00 0.33 1.00 1.00 1.00 J 0.56 0.76 0.76 0.76 0.76 0.76 0.56 0.56 0.76 0.56 0.56 0.76 0.76 0.56 0.56 0.76 0.56 0.76 0.78 0.78 0.78 0.78 0.78 0.76 0.76 0.76 0.45 0.56 0.56 0.56 0.76 0.70 0.59 0.59 0.59 0.59 0.59 0.28 0.64 0.50 0.28 0.45 0.62 0.78 0.78 0.78 OUT 0.10 0.31 0.31 0.21 0.10 0.11 0.14 0.27 0.14 0.05 0.07 0.03 0.04 0.06 0.03 0.03 0.05 0.26 0.01 0.01 0.01 0.01 0.01 0.01 0.02 0.02 0.09 0.02 0.02 0.05 0.02 0.02 0.34 0.01 0.02 0.02 0.01 0.01 0.01 0.01 0.01 0.17 0.51 0.17 0.17 0.09

APPENDIX 3 2/5 03.02.1998 Neural network learning data

# 47 48 49 50 51 52 53 54 55 56 57 58 59 60 61 62 63 64 65 66 67 68 69 70 71 72 73 74 75 76 77 78 79 80 81 82 83 84 85 86 87 88 89 90 91 92 A 0.15 0.15 0.15 0.15 0.15 0.15 0.15 0.65 0.65 0.15 0.15 0.15 0.15 0.65 0.65 0.65 0.65 0.65 0.65 0.65 0.65 0.65 0.65 0.65 0.65 0.65 0.65 0.15 0.15 0.15 0.15 0.15 0.65 0.65 0.65 0.65 0.15 0.15 0.15 0.15 0.15 0.15 0.85 0.15 0.15 0.65 B 0.35 0.25 0.25 0.05 0.25 0.25 0.25 0.15 0.15 0.25 0.25 0.25 0.25 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.25 0.25 0.15 0.15 0.25 0.25 0.25 0.25 0.25 0.25 0.05 0.05 0.15 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.25 C 0.08 0.12 0.10 0.45 0.12 0.12 0.11 0.17 0.18 0.11 0.10 0.10 0.11 0.37 0.40 0.41 0.44 0.47 0.56 0.50 0.45 0.43 0.43 0.11 0.12 0.18 0.16 0.13 0.14 0.15 0.15 0.15 0.11 0.46 1.00 0.93 0.51 0.56 0.57 0.39 0.43 0.44 0.40 0.40 0.40 0.09 D 0.10 0.31 0.17 0.13 0.38 0.26 0.32 0.27 0.27 0.25 0.07 0.50 0.50 0.26 0.26 0.26 0.26 0.26 0.26 0.26 0.26 0.26 0.26 0.22 0.22 0.22 0.22 0.29 0.29 0.29 0.29 0.29 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 E 0.15 0.15 0.15 0.15 0.15 0.15 0.15 0.15 0.45 0.15 0.15 0.15 0.45 0.15 0.45 0.65 0.75 0.65 0.15 0.45 0.65 0.75 0.65 0.15 0.45 0.45 0.45 0.15 0.45 0.55 0.85 0.85 0.15 0.15 0.15 0.15 0.15 0.45 0.65 0.15 0.45 0.65 0.15 0.45 0.45 0.15 F 0.29 0.84 0.52 0.36 1.00 0.68 0.84 0.22 0.22 0.13 0.31 0.31 0.31 0.24 0.24 0.24 0.24 0.24 0.24 0.24 0.24 0.24 0.24 0.13 0.13 0.13 0.13 0.19 0.19 0.19 0.19 0.19 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.09 0.00 G 0.20 0.20 0.20 0.20 0.20 0.20 0.20 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.80 0.80 0.80 0.80 0.80 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.20 0.50 H 1.00 1.00 1.00 1.00 1.00 1.00 1.00 0.33 0.33 0.69 0.07 0.22 0.22 0.17 0.17 0.17 0.17 0.17 0.17 0.17 0.17 0.17 0.17 0.33 0.33 0.33 0.33 0.22 0.22 0.22 0.22 0.22 0.59 0.33 0.48 0.48 0.38 0.38 0.38 0.38 0.38 0.38 0.12 0.22 0.48 0.38 I 1.00 1.00 1.00 1.00 1.00 1.00 1.00 0.87 0.87 0.47 0.47 0.33 0.33 0.33 0.33 0.33 0.33 0.33 0.33 0.33 0.33 0.33 0.33 0.13 0.13 0.40 0.40 0.00 0.00 0.00 0.00 0.00 0.67 0.53 0.67 0.67 0.67 0.67 0.67 0.67 0.67 0.67 0.67 0.33 0.67 0.53 J 0.62 0.45 0.63 0.45 0.45 0.39 0.62 0.56 0.56 0.62 0.84 0.84 0.84 0.92 0.96 1.00 0.79 0.59 0.20 0.42 0.70 0.87 0.81 0.56 0.56 0.56 0.84 0.28 0.28 0.28 0.28 0.28 0.56 0.39 0.00 0.00 0.28 0.28 0.28 0.73 0.73 0.73 0.64 0.95 0.95 0.95 OUT 0.17 0.02 0.17 0.03 0.02 0.03 0.02 0.34 0.17 0.17 0.09 0.17 0.09 1.00 0.37 0.55 0.95 0.55 0.37 0.23 0.22 0.23 0.25 0.01 0.00 0.01 0.01 0.17 0.14 0.10 0.02 0.02 0.09 0.69 0.86 0.86 0.69 0.69 0.34 0.69 0.34 0.34 0.17 0.86 0.51 0.09

APPENDIX 3 3/5 03.02.1998 Neural network learning data, classed data

# 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 A 0.15 0.15 0.15 0.15 0.15 0.15 0.15 0.15 0.15 0.15 0.15 0.15 0.15 0.15 0.15 0.15 0.15 0.15 0.15 0.15 0.15 0.15 0.15 0.15 0.15 0.15 0.15 0.65 0.65 0.65 0.65 0.65 0.65 0.65 0.65 0.65 0.65 0.15 0.65 0.15 0.15 0.15 0.15 0.15 0.15 0.15 B 0.15 0.05 0.05 0.05 0.25 0.25 0.25 0.05 0.35 0.45 0.45 0.45 0.45 0.45 0.45 0.45 0.25 0.05 0.85 0.85 0.85 0.85 0.85 0.75 0.75 0.75 0.25 0.35 0.35 0.25 0.65 0.65 0.15 0.15 0.15 0.15 0.15 0.65 0.65 0.65 0.65 0.25 0.05 0.35 0.35 0.35 C 0.15 0.35 0.35 0.35 0.15 0.15 0.15 0.45 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.15 0.45 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.15 0.05 0.05 0.15 0.05 0.05 0.15 0.15 0.15 0.15 0.15 0.05 0.05 0.05 0.05 0.15 0.45 0.05 0.05 0.05 D 0.55 0.55 0.55 0.55 0.55 0.55 0.55 0.55 0.55 0.55 0.55 0.55 0.55 0.55 0.55 0.55 0.55 0.55 0.95 0.95 0.95 0.95 0.95 0.85 0.85 0.85 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.05 0.15 0.05 0.05 0.25 0.05 0.35 0.45 0.35 E 0.15 0.15 0.15 0.15 0.45 0.45 0.15 0.15 0.45 0.15 0.15 0.45 0.45 0.15 0.15 0.45 0.15 0.45 0.45 0.45 0.45 0.45 0.45 0.45 0.45 0.45 0.15 0.15 0.15 0.15 0.45 0.15 0.15 0.15 0.15 0.15 0.15 0.15 0.15 0.15 0.15 0.15 0.15 0.45 0.45 0.45 F 0.35 0.35 0.35 0.35 0.35 0.35 0.35 0.35 0.35 0.35 0.35 0.35 0.35 0.35 0.35 0.35 0.35 0.35 0.35 0.35 0.35 0.35 0.35 0.45 0.45 0.45 0.15 0.15 0.15 0.15 0.15 0.25 0.25 0.25 0.25 0.25 0.25 0.05 0.15 0.05 0.35 0.15 0.15 0.25 0.35 0.15 G 0.55 0.55 0.55 0.55 0.55 0.55 0.55 0.55 0.55 0.55 0.55 0.55 0.55 0.55 0.55 0.55 0.55 0.55 0.55 0.55 0.55 0.55 0.55 0.55 0.55 0.55 0.55 0.55 0.55 0.55 0.55 0.55 0.55 0.55 0.55 0.55 0.55 0.55 0.55 0.85 0.25 0.85 0.85 0.85 0.85 0.85 H 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.45 0.45 0.45 0.45 0.45 0.15 0.15 0.15 0.45 0.45 0.45 0.45 0.35 0.35 0.15 0.15 0.15 0.15 0.15 0.15 0.45 0.15 0.95 0.25 0.25 0.25 0.25 0.25 I 0.35 0.35 0.35 0.35 0.35 0.35 0.35 0.35 0.35 0.35 0.35 0.35 0.35 0.35 0.35 0.35 0.35 0.35 0.95 0.95 0.95 0.95 0.95 0.55 0.55 0.55 0.95 0.95 0.95 0.95 0.45 0.85 0.35 0.35 0.35 0.35 0.35 0.35 0.95 0.35 0.95 0.05 0.35 0.95 0.95 0.95 J 0.55 0.75 0.75 0.75 0.75 0.75 0.55 0.55 0.75 0.55 0.55 0.75 0.75 0.55 0.55 0.75 0.55 0.75 0.75 0.75 0.75 0.75 0.75 0.75 0.75 0.75 0.45 0.55 0.55 0.55 0.75 0.65 0.55 0.55 0.55 0.55 0.55 0.25 0.65 0.55 0.25 0.45 0.65 0.75 0.75 0.75 OUT 0.15 0.35 0.35 0.25 0.05 0.15 0.15 0.25 0.15 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.25 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.35 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.15 0.55 0.15 0.15 0.05

APPENDIX 3 4/5 03.02.1998 Neural network learning data, classed data

# 47 48 49 50 51 52 53 54 55 56 57 58 59 60 61 62 63 64 65 66 67 68 69 70 71 72 73 74 75 76 77 78 79 80 81 82 83 84 85 86 87 88 89 90 91 92 A 0.15 0.15 0.15 0.15 0.15 0.15 0.15 0.65 0.65 0.15 0.15 0.15 0.15 0.65 0.65 0.65 0.65 0.65 0.65 0.65 0.65 0.65 0.65 0.65 0.65 0.65 0.65 0.15 0.15 0.15 0.15 0.15 0.65 0.65 0.65 0.65 0.15 0.15 0.15 0.15 0.15 0.15 0.85 0.15 0.15 0.65 B 0.35 0.25 0.25 0.05 0.25 0.25 0.25 0.15 0.15 0.25 0.25 0.25 0.25 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.25 0.25 0.15 0.15 0.25 0.25 0.25 0.25 0.25 0.25 0.05 0.05 0.15 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.25 C 0.05 0.15 0.15 0.45 0.15 0.15 0.15 0.15 0.15 0.15 0.05 0.05 0.15 0.35 0.35 0.45 0.45 0.45 0.55 0.45 0.45 0.45 0.45 0.15 0.15 0.15 0.15 0.15 0.15 0.15 0.15 0.15 0.15 0.45 0.95 0.95 0.55 0.55 0.55 0.35 0.45 0.45 0.45 0.35 0.35 0.05 D 0.15 0.35 0.15 0.15 0.35 0.25 0.35 0.25 0.25 0.25 0.05 0.55 0.55 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 E 0.15 0.15 0.15 0.15 0.15 0.15 0.15 0.15 0.45 0.15 0.15 0.15 0.45 0.15 0.45 0.65 0.75 0.65 0.15 0.45 0.65 0.75 0.65 0.15 0.45 0.45 0.45 0.15 0.45 0.55 0.85 0.85 0.15 0.15 0.15 0.15 0.15 0.45 0.65 0.15 0.45 0.65 0.15 0.45 0.45 0.15 F 0.25 0.85 0.55 0.35 0.95 0.65 0.85 0.25 0.25 0.15 0.35 0.35 0.35 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.15 0.15 0.15 0.15 0.15 0.15 0.15 0.15 0.15 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 G 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.55 0.55 0.55 0.55 0.55 0.55 0.55 0.55 0.55 0.55 0.55 0.55 0.55 0.55 0.55 0.55 0.55 0.55 0.55 0.55 0.85 0.85 0.85 0.85 0.85 0.55 0.55 0.55 0.55 0.55 0.55 0.55 0.55 0.55 0.55 0.55 0.55 0.25 0.55 H 0.95 0.95 0.95 0.95 0.95 0.95 0.95 0.35 0.35 0.65 0.05 0.25 0.25 0.15 0.15 0.15 0.15 0.15 0.15 0.15 0.15 0.15 0.15 0.35 0.35 0.35 0.35 0.25 0.25 0.25 0.25 0.25 0.55 0.35 0.45 0.45 0.35 0.35 0.35 0.35 0.35 0.35 0.15 0.25 0.45 0.35 I 0.95 0.95 0.95 0.95 0.95 0.95 0.95 0.85 0.85 0.45 0.45 0.35 0.35 0.35 0.35 0.35 0.35 0.35 0.35 0.35 0.35 0.35 0.35 0.15 0.15 0.45 0.45 0.05 0.05 0.05 0.05 0.05 0.65 0.55 0.65 0.65 0.65 0.65 0.65 0.65 0.65 0.65 0.65 0.35 0.65 0.55 J 0.65 0.45 0.65 0.45 0.45 0.35 0.65 0.55 0.55 0.65 0.85 0.85 0.85 0.95 0.95 0.95 0.75 0.55 0.15 0.45 0.65 0.85 0.85 0.55 0.55 0.55 0.85 0.25 0.25 0.25 0.25 0.25 0.55 0.35 0.05 0.05 0.25 0.25 0.25 0.75 0.75 0.75 0.65 0.95 0.95 0.95 OUT 0.15 0.05 0.15 0.05 0.05 0.05 0.05 0.35 0.15 0.15 0.05 0.15 0.05 0.95 0.35 0.55 0.95 0.55 0.35 0.25 0.25 0.25 0.25 0.05 0.05 0.05 0.05 0.15 0.15 0.15 0.05 0.05 0.05 0.65 0.85 0.85 0.65 0.65 0.35 0.65 0.35 0.35 0.15 0.85 0.55 0.05

APPENDIX 3 5/5 03.02.1998 Method used in this study for dividing data into ten classes:
1

0.9

0.8

0.7

CLASSED VALUE

0.6

0.5

0.4

0.3

0.2

0.1

0 0 0.1 0.2 0.3 0.4 0.5 INPUT 0.6 0.7 0.8 0.9 1

Figure 53.

Illustration of the principle of dividing normalized input data into 10 classes.

As Excel Visual Basic Macro:

Function Fuzzy10(Inp As Single) As Single Select Case Inp Case Is < 0.1 Fuzzy10 = 0.05 Case Is < 0.2 Fuzzy10 = 0.15 Case Is < 0.3 Fuzzy10 = 0.25 Case Is < 0.4 Fuzzy10 = 0.35 Case Is < 0.5 Fuzzy10 = 0.45 Case Is < 0.6 Fuzzy10 = 0.55 Case Is < 0.7 Fuzzy10 = 0.65 Case Is < 0.8 Fuzzy10 = 0.75 Case Is < 0.9 Fuzzy10 = 0.85 Case Else Fuzzy10 = 0.95 End Select End Function

APPENDIX 4 1/2 03.02.1998 Neural Networks

TABLE 1.
Network ID 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 61 62 63

Generated neural networks and their statistical parameters. Training with Matlab, adaptive backpropaganation, 5000 epochs.
Neurons Third Layer 0 None 0 None 0 None 1 None 1 None 1 None 1 None 1 None 1 None 1 None 1 None 1 None 1 None 1 None 1 None 1 None 1 None 1 None 1 None 1 None 1 None 1 None 1 None 1 None 1 None 1 None 1 None 1 None 1 None 1 None 1 None 1 None 1 None 1 None 1 None 1 None 1 None 1 None 1 None 1 Linear 1 Linear 1 Linear 1 Linear 2 Linear 2 Linear 2 Linear 2 Linear 3 Linear 3 Linear 3 Linear 3 Linear 4 Linear 4 Linear 4 Linear 4 Linear 5 Linear 5 Linear 5 Linear 5 Linear 6 Linear 6 Linear 6 Linear 6 Linear Neurons Total Neurons 0 1 0 1 0 1 0 2 0 2 0 2 0 2 0 2 0 2 0 3 0 3 0 3 0 3 0 3 0 3 0 4 0 4 0 4 0 4 0 4 0 4 0 5 0 5 0 5 0 5 0 5 0 5 0 6 0 6 0 6 0 6 0 6 0 6 0 7 0 7 0 7 0 7 0 7 0 7 1 3 1 3 1 3 1 3 1 5 1 5 1 5 1 5 1 7 1 7 1 7 1 7 1 9 1 9 1 9 1 9 1 11 1 11 1 11 1 11 1 13 1 13 1 13 1 13 SSE 1.73 1.47 1.78 1.35 1.30 1.23 1.30 1.34 1.22 1.39 1.01 0.98 1.21 1.31 1.00 1.31 1.09 0.68 1.23 1.23 0.79 1.29 0.94 0.88 1.00 1.16 0.54 1.45 1.01 0.81 1.09 1.33 0.58 1.20 1.03 1.88 1.07 1.10 0.46 1.29 1.33 1.33 1.29 1.14 0.94 1.07 1.59 1.45 0.93 1.36 0.90 0.90 1.23 0.63 0.75 0.67 0.64 0.62 0.47 1.17 0.57 0.60 0.46 SSEn 1.73 1.55 1.78 1.41 1.35 1.49 1.36 1.37 1.48 1.36 1.39 1.33 1.41 1.40 1.31 1.35 1.33 1.12 1.44 1.31 1.32 1.34 1.10 1.30 1.17 1.42 0.91 1.45 1.31 0.98 1.28 1.56 0.77 1.33 1.30 2.06 1.25 1.27 0.95 1.40 1.41 1.42 1.38 1.29 1.30 1.44 1.79 1.52 1.16 1.49 1.04 1.12 3.51 1.41 2.98 1.01 2.19 0.91 1.89 1.20 1.18 1.25 1.04 StDev 0.138 0.125 0.140 0.122 0.120 0.116 0.120 0.121 0.116 0.124 0.105 0.104 0.115 0.120 0.105 0.120 0.110 0.086 0.116 0.116 0.093 0.119 0.100 0.098 0.105 0.113 0.077 0.126 0.105 0.094 0.109 0.121 0.080 0.115 0.106 0.143 0.109 0.110 0.071 0.119 0.119 0.121 0.119 0.112 0.101 0.108 0.132 0.126 0.101 0.122 0.099 0.100 0.116 0.082 0.091 0.086 0.084 0.083 0.072 0.113 0.079 0.081 0.071 Max C.Coeff. Error 0.54 0.828 0.62 0.870 0.53 0.822 0.63 0.869 0.63 0.874 0.69 0.881 0.63 0.874 0.61 0.870 0.70 0.882 0.61 0.864 0.65 0.904 0.49 0.907 0.51 0.884 0.63 0.872 0.69 0.905 0.62 0.873 0.58 0.895 0.35 0.937 0.49 0.881 0.51 0.881 0.53 0.925 0.48 0.875 0.50 0.914 0.59 0.917 0.60 0.905 0.64 0.889 0.42 0.950 0.59 0.860 0.62 0.905 0.49 0.924 0.61 0.896 0.51 0.871 0.46 0.946 0.55 0.884 0.56 0.901 0.62 0.870 0.53 0.897 0.53 0.895 0.40 0.958 0.62 0.875 0.57 0.874 0.59 0.871 0.62 0.875 0.65 0.891 0.67 0.912 0.70 0.898 0.48 0.843 0.59 0.858 0.64 0.912 0.58 0.867 0.62 0.915 0.47 0.914 0.58 0.881 0.46 0.942 0.60 0.929 0.41 0.937 0.63 0.940 0.42 0.942 0.87 0.956 0.52 0.888 0.58 0.947 0.48 0.944 0.39 0.958 F Test 0.075 0.992 0.046 0.171 0.190 0.304 0.212 0.239 0.288 0.161 0.301 0.336 0.185 0.182 0.415 0.185 0.279 0.734 0.185 0.221 0.480 0.201 0.366 0.600 0.284 0.222 0.532 0.131 0.172 0.554 0.278 0.162 0.515 0.242 0.289 0.000 0.227 0.192 0.576 0.199 0.173 0.187 0.190 0.259 0.254 0.284 0.108 0.141 0.364 0.169 0.401 0.398 0.206 0.579 0.457 0.514 0.660 0.598 0.721 0.221 0.469 0.524 0.573

First Layer Neurons Second Layer Linear 1 None Logsig 1 None Tansig 1 None Logsig 1 Linear Tansig 1 Linear Logsig 1 Logsig Tansig 1 Tansig Logsig 1 Tansig Tansig 1 Logsig Logsig 2 Linear Tansig 2 Linear Logsig 2 Logsig Tansig 2 Tansig Logsig 2 Tansig Tansig 2 Logsig Logsig 3 Linear Tansig 3 Linear Logsig 3 Logsig Tansig 3 Tansig Logsig 3 Tansig Tansig 3 Logsig Logsig 4 Linear Tansig 4 Linear Logsig 4 Logsig Tansig 4 Tansig Logsig 4 Tansig Tansig 4 Logsig Logsig 5 Linear Tansig 5 Linear Logsig 5 Logsig Tansig 5 Tansig Logsig 5 Tansig Tansig 5 Logsig Logsig 6 Linear Tansig 6 Linear Logsig 6 Logsig Tansig 6 Tansig Logsig 6 Tansig Tansig 6 Logsig Logsig 1 Logsig Tansig 1 Tansig Logsig 1 Tansig Tansig 1 Logsig Logsig 2 Logsig Tansig 2 Tansig Logsig 2 Tansig Tansig 2 Logsig Logsig 3 Logsig Tansig 3 Tansig Logsig 3 Tansig Tansig 3 Logsig Logsig 4 Logsig Tansig 4 Tansig Logsig 4 Tansig Tansig 4 Logsig Logsig 5 Logsig Tansig 5 Tansig Logsig 5 Tansig Tansig 5 Logsig Logsig 6 Logsig Tansig 6 Tansig Logsig 6 Tansig 6 Logsig Tansig

APPENDIX 4 2/2 03.02.1998 Neural Networks

TABLE 2.

Generated neural networks and their statistical parameters. Training with Matlab, Levenberg-Marqurdt, max 1000 epochs.
Neurons Third Layer 0 None 0 None 0 None 1 None 1 None 1 None 1 None 1 None 1 None 1 None 1 None 1 None 1 None 3 Linear 3 Linear 4 Linear 4 Linear 5 Linear 5 Linear 6 Linear 6 Linear Neurons Total Neurons 0 1 0 1 0 1 0 3 0 3 0 4 0 4 0 5 0 5 0 6 0 6 0 7 0 7 1 7 1 7 1 9 1 9 1 11 1 11 1 13 1 13 SSE 1.73 1.44 1.79 0.88 0.95 0.87 0.47 0.72 0.64 0.74 0.28 0.82 0.57 1.44 0.68 0.56 0.36 0.43 0.13 0.16 0.34 SSEn 1.73 1.64 1.78 1.38 1.19 2.05 17.76 1.44 14.68 2.26 2.85 67.26 29.11 55.78 2.69 4.88 12.44 51.73 4.05 120.86 23.82 StDev 0.138 0.122 0.140 0.098 0.102 0.098 0.072 0.089 0.084 0.090 0.055 0.092 0.067 0.126 0.086 0.079 0.062 0.068 0.038 0.042 0.060 Max C.Coeff. Error 0.53 0.828 0.67 0.874 0.52 0.822 0.58 0.916 0.52 0.909 0.55 0.918 1.84 0.956 0.66 0.932 1.46 0.940 0.54 0.931 0.71 0.975 3.57 0.932 1.87 0.963 5.06 0.875 0.63 0.938 0.88 0.949 2.67 0.968 4.04 0.962 1.38 0.988 6.11 0.985 3.57 0.973 F Test 0.095 0.825 0.059 0.466 0.385 0.648 0.534 0.594 0.642 0.567 0.689 0.776 0.887 0.707 0.330 0.941 0.477 0.927 0.999 0.871 0.619

Network ID 1 2 3 10 11 16 17 22 23 28 29 34 35 50 51 54 55 58 59 62 63

First Layer Neurons Second Layer Linear 1 None Logsig 1 None Tansig 1 None Logsig 2 Linear Tansig 2 Linear Logsig 3 Linear Tansig 3 Linear Logsig 4 Linear Tansig 4 Linear Logsig 5 Linear Tansig 5 Linear Logsig 6 Linear Tansig 6 Linear Logsig 3 Tansig Tansig 3 Logsig Logsig 4 Tansig Tansig 4 Logsig Logsig 5 Tansig Tansig 5 Logsig Logsig 6 Tansig 6 Logsig Tansig

TABLE 3.

Generated neural networks and their statistical parameters. Training by Fortran program developed by Palosaari and Bulsari, /67/.
Network Hidden Total Neurons ID Layers PL1 0 1 PL2 0 1 PL3 1 2 PL4 1 2 PL5 1 3 PL6 1 3 PL7 1 4 PL8 1 4 PL9 1 5 PL10 1 5 PL11 1 6 PL12 1 6 PL13 3 4 PL14 3 4 PL15 3 6 PL16 3 6 PL17 3 8 PL18 3 8 PL19 3 10 PL20 3 10 PL21 3 12 PL22 3 12 PL23 3 14 PL24 3 14 Last Layer Linear Sigmoid Linear Sigmoid Linear Sigmoid Linear Sigmoid Linear Sigmoid Linear Sigmoid Linear Sigmoid Linear Sigmoid Linear Sigmoid Linear Sigmoid Linear Sigmoid Linear Sigmoid SSE 6.91 5.74 4.19 3.57 3.63 3.14 3.57 3.04 2.44 1.87 1.44 1.00 4.74 7.56 3.79 8.45 5.31 4.04 1.25 2.30 1.25 2.95 1.85 2.18 StDev 0.19 0.16 0.16 0.14 0.14 0.15 0.12 0.10 0.11 0.08 0.06 0.03 0.16 0.16 0.14 0.19 0.14 0.13 0.04 0.11 0.04 0.13 0.08 0.10 Max Error C.Coeff. 1.10 1.15 1.18 1.12 1.11 1.15 1.00 0.77 1.02 0.72 0.67 0.53 1.19 0.96 1.10 1.06 0.82 0.98 0.53 1.00 0.55 1.11 0.77 0.92 0.828 0.875 0.900 0.916 0.914 0.926 0.915 0.928 0.943 0.957 0.967 0.977 0.886 0.810 0.910 0.785 0.871 0.903 0.971 0.946 0.971 0.931 0.957 0.949 F Test 0.074 0.808 0.312 0.469 0.391 0.456 0.401 0.552 0.576 0.787 0.748 0.775 0.248 0.047 0.369 0.022 0.190 0.331 0.792 0.573 0.779 0.493 0.678 0.735

Higher values of SSEs in Table 3 compared to Tables 1 and 2 are due to the scaling of the learning data between -1 and 1 instead of 0 and 1. This helps the learning process, if the modified sigmoid activation function is used, as in the program by Palosaari and Bulsari.

APPENDIX 5 1/5 03.02.1998 Residuals derived with the selected network

0.50

0.40

0.30

0.20

0.10

0.00

-0.10

-0.20

-0.30

-0.40

-0.50 0.00

0.10

0.20

0.30

0.40

0.50

0.60

0.70

0.80

0.90

1.00

Figure 54.
0.50

Residual chart for input variable A.

0.40

0.30

0.20

0.10

0.00

-0.10

-0.20

-0.30

-0.40

-0.50 0.00

0.10

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0.30

0.40

0.50

0.60

0.70

0.80

0.90

1.00

Figure 55.

Residual chart for input variable B.

APPENDIX 5 2/5 03.02.1998 Residuals derived with the selected network

0.50

0.40

0.30

0.20

0.10

0.00

-0.10

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0.10

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0.40

0.50

0.60

0.70

0.80

0.90

1.00

Figure 56.
0.50 0.40

Residual chart for input variable C.

0.30

0.20

0.10

0.00

-0.10

-0.20

-0.30

-0.40

-0.50 0.00

0.10

0.20

0.30

0.40

0.50

0.60

0.70

0.80

0.90

1.00

Figure 57.

Residual chart for input variable D.

APPENDIX 5 3/5 03.02.1998 Residuals derived with the selected network

0.50

0.40

0.30

0.20

0.10

0.00

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1.00

Figure 58.
0.50 0.40

Residual chart for input variable E.

0.30

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0.00

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0.10

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0.50

0.60

0.70

0.80

0.90

1.00

Figure 59.

Residual chart for input variable F.

APPENDIX 5 4/5 03.02.1998 Residuals derived with the selected network

0.50

0.40

0.30

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0.10

0.00

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1.00

Figure 60.
0.50 0.40

Residual chart for input variable G.

0.30

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0.10

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0.60

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1.00

Figure 61.

Residual chart for input variable H.

APPENDIX 5 5/5 03.02.1998 Residuals derived with the selected network

0.50

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1.00

Figure 62.
0.50

Residual chart for input variable I.

0.40

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1.00

Figure 63.

Residual chart for input variable J.

APPENDIX 6 1/7 03.02.1998 Sensitivity analysis of selected network

1.0

INTRODUCTION

The Yatess algorithm can be effectively used for sensitivity analysis by calculating effects of one variable as the other variables change. Because the algorithm is based on two level test plan, a large scale analysis requires several calculation sequences. The idea in the calculation is to create a such table of variables that all combinations are tested. With 10 inputs, this requires 1024 (210) tests. The output values are then calculated with the selected neural network. The results are then processed with the Yatess algorithm to show the effects of each parameter. It is also possible to detect the cross-correlations between inputs, but in this example only the main effects of one parameter are included. TABLE 1. Calculation of data for Yatess algorithm, the lower value for each variable is 0.2 and the higher value is 0.3. Tests from 1 to 8.
B 0.3 0.3 0.2 0.2 0.3 0.3 0.2 0.2 C 0.3 0.3 0.3 0.3 0.2 0.2 0.2 0.2 D 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 E 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 F 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 G 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 H 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 I 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 J 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 Output 0.27 0.21 0.29 0.20 0.47 0.34 0.43 0.27

Test 1 2 3 4 5 6 7 8

A 0.3 0.2 0.3 0.2 0.3 0.2 0.3 0.2

TABLE 2.

Calculation of data for Yatess algorithm, the lower value for each variable is 0.2 and the higher value is 0.3. Tests from 1017 to 1024.
0.3 0.3 0.2 0.2 0.3 0.3 0.2 0.2 0.3 0.3 0.3 0.3 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.17 0.17 0.19 0.20 0.27 0.23 0.25 0.23

1017 1018 1019 1020 1021 1022 1023 1024

0.3 0.2 0.3 0.2 0.3 0.2 0.3 0.2

APPENDIX 6 2/7 03.02.1998 Sensitivity analysis of selected network

TABLE 3.
0.5 0.5 0.8 0.7 0.6 0.6 1.0 0.9 1.0 1.5 1.2 1.9 0.6 0.7 0.7 0.9

Calculation of effects with the Yatess algorithm, continued from Table 1.

2.5 3.1 1.3 1.5 2.0 2.5 1.1 1.2 5.6 2.9 4.5 2.3 8.4 4.0 7.1 3.0 8.5 6.8 12.5 10.1 8.4 6.8 12.2 9.9 15.2 22.6 15.2 22.1 11.3 16.4 11.2 15.6 37.8 37.4 27.7 26.8 48.2 47.7 35.4 33.9 75.2 129.7 294.9 54.5 165.2 -34.3 95.9 -9.3 -3.3 69.3 -24.9 -0.1 -7.0 2.4 54.2 -2.3 -5.7 -12.6 -16.5 -0.7 -11.0 -8.5 0.6 -1.1 Div. Est. 1024 0.288 512 -0.067 512 -0.006 512 0.000 512 0.106 512 -0.025 512 -0.022 512 -0.002 ID Ave. A B A B C C B C A B C A

TABLE 4.
0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0

Calculation of effects with the Yatess algorithm, continued from Table 2.

0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 512 512 512 512 512 512 512 512 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 D D D D D D D D E E E E E E E E F F F F F F F F G G G G G G G G H H H H H H H H I I I I I I I I J J J J J J J J

A B A B A C C B C A B C

The numbers in the column Est. correspond to the effect of each variable and cross-correlation are indicated by ID, for example the effect of variable A is -0.067, so the parameter tends to lower the result. The calculated effects are shown in Figures 1 to 10, the x-axis represents the value of the variable, and the lines correspond to the values of the other variables. It can be seen that the parameters C, E, and G affect the result most, while the effect of other parameters is smaller. Table 5 contains data for chart in Figure 1. Other charts have been done by using similar tables. TABLE 5. Calculation of effects with the Yatess algorithm, variable A.
Value of tested variable 0.4 0.5 0.23 0.21 0.14 0.15 0.01 0.00 0.00 -0.11 0.11 0.00 0.12 0.05 0.06 0.10 0.00 0.08 -0.04 0.03

0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9

0.1 0.00 -0.04 -0.18 -0.23 -0.21 -0.22 -0.22 -0.21 -0.19

0.2 0.04 0.00 -0.07 -0.14 -0.15 -0.16 -0.17 -0.16 -0.15

0.3 0.18 0.07 0.00 -0.01 0.00 -0.03 -0.06 -0.09 -0.10

0.6 0.22 0.16 0.03 -0.12 -0.05 0.00 0.00 0.02 0.05

0.7 0.22 0.17 0.06 -0.06 -0.10 0.00 0.00 0.00 0.00

0.8 0.21 0.16 0.09 0.00 -0.08 -0.02 0.00 0.00 0.00

0.9 0.19 0.15 0.10 0.04 -0.03 -0.05 0.00 0.00 0.00

Other variables

APPENDIX 6 2/7 03.02.1998 Sensitivity analysis of selected network

0.5 0.4 0.3 0.2 0.1 EFFECT, 0.0 -0.1 -0.2 -0.3 -0.4 -0.5 0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9

VALUE OF VARIABLE A, -

Figure 64.

Sensitivity chart for variable A, value of other variables as parameters.

0.5 0.4 0.3 0.2 0.1 EFFECT, 0.0 -0.1 -0.2 -0.3 -0.4 -0.5 0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9

VALUE OF VARIABLE B, -

Figure 65.

Sensitivity chart for variable B, value of other variables as parameters.

APPENDIX 6 4/7 03.02.1998 Sensitivity analysis of selected network

0.5 0.4 0.3 0.2 0.1 EFFECT, 0.0 -0.1 -0.2 -0.3 -0.4 -0.5 0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9

VALUE OF VARIABLE C, -

Figure 66.

Sensitivity chart for variable C, value of other variables as parameters.

0.5 0.4 0.3 0.2 0.1 EFFECT, 0.0 -0.1 -0.2 -0.3 -0.4 -0.5 0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9

VALUE OF VARIABLE D, -

Figure 67.

Sensitivity chart for variable D, value of other variables as parameters.

APPENDIX 6 5/7 03.02.1998 Sensitivity analysis of selected network

0.5 0.4 0.3 0.2 0.1 EFFECT, 0.0 -0.1 -0.2 -0.3 -0.4 -0.5 0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9

VALUE OF VARIABLE E, -

Figure 68.

Sensitivity chart for variable E, value of other variables as parameters.

0.5 0.4 0.3 0.2 0.1 EFFECT, 0.0 -0.1 -0.2 -0.3 -0.4 -0.5 0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9

VALUE OF VARIABLE F, -

Figure 69.

Sensitivity chart for variable F, value of other variables as parameters.

APPENDIX 6 6/7 03.02.1998 Sensitivity analysis of selected network

0.5 0.4 0.3 0.2 0.1 EFFECT, 0.0 -0.1 -0.2 -0.3 -0.4 -0.5 0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9

VALUE OF VARIABLE G, -

Figure 70.

Sensitivity chart for variable G, value of other variables as parameters.

0.5 0.4 0.3 0.2 0.1 EFFECT, 0.0 -0.1 -0.2 -0.3 -0.4 -0.5 0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9

VALUE OF VARIABLE H, -

Figure 71.

Sensitivity chart for variable H, value of other variables as parameters.

APPENDIX 6 7/7 03.02.1998 Sensitivity analysis of selected network

0.5 0.4 0.3 0.2 0.1 EFFECT, 0.0 -0.1 -0.2 -0.3 -0.4 -0.5 0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9

VALUE OF VARIABLE I, -

Figure 72.

Sensitivity chart for variable I, value of other variables as parameters.

0.5 0.4 0.3 0.2 0.1 EFFECT, 0.0 -0.1 -0.2 -0.3 -0.4 -0.5 0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9

VALUE OF VARIABLE J, -

Figure 73.

Sensitivity chart for variable J, value of other variables as parameters.