Model Building Methodology for Complex

Reaction Systems

A thesis submitted to the

University of Manchester Institute of Science and Technology

for the degree of

Doctor of Philosophy

By

Wenling Zhang

under the supervision of

Professor Robin Smith

Department of Process Integration Manchester, United Kingdom

April, 2004

Declaration
No portion of the work referred to in this thesis has been submitted in support of an for application another degree or qualification of this or any other university, or any institution learning. other of

Wenling Zhang

II

Abstract
The complexity of chemical reaction processes and the short market window of some With

chemical products mean that detailed model building can often not be justified.

little knowledge of chemistry, this work aims to provide a new methodology for model building of chemical reaction systems with minimum experimental measurements, for the purpose of reactor design and optimisation. Most often reactor designs are scaled from experimental measurements, especially for the manufacture of fine and speciality Yet, chemicals. without a model of the reaction system, major opportunities be can

design in When developed for the the and missed optimisation of reactor. a models are reaction system in the laboratory, they are often inappropriate for reactor design and optimisation. In the first part of this thesis, the reaction scheme that best describes the production of a given chemical optimisation. kinetic and suitable equations are obtained simultaneously using

A hybrid optimisation

is deal large to this method used with problem

fits data than the where more one model same experimental within a certain confidence level. Stochastic optimisation methods provide multiple solutions that are rival models for model discrimination. An NLP method improves model precision from the

stochastic optimisation

in the narrowed search space. A strategy for reaction scheme

from is to the reacting species and to provide generate all reactions construction used during optimisation. plausible reaction schemes simultaneously These reaction schemes are screened

kinetic fit to the most appropriate reaction scheme and with models

kinetic model from the rival models.

Optimal experiments then need to be designed to discriminate among rival models. The for design the potential exploits mixing, as well as temperature and experimental discriminate between to models through the reactor superstructure. concentration effects The oleic acid epoxidation reaction is used to demonstrate the methodology. For refinery heterogeneous catalytic reactions, due to the complex nature of catalysis, a large number of rival models pose difficulties for model building and discrimination. In kinetic developed is for building three-level thesis, the the rest of study method model

III

to reduce the model complexity by separating diffusion effects from kinetic equations. In addition, catalyst characterisation is used to assist model discrimination. There are a large number of techniques available to connect catalyst properties, catalyst activities with model performance with different capabilities and limitations. However, not all of these will be useful in a given application. A classification of those techniques specified for hydrodesulphurisation (HDS) processes provides guidance for selecting suitable techniques to yield the most information with accuracy, speed, and economy. Furthermore, plausible ways for model discrimination and model improvement for thiophene and diesel HDS are explored, including operating condition, feedstock and
catalyst effects.

IV

Acknowledgements
This thesis is by far the most significant accomplishment in my life and it would be impossible without people who supported me and believed in me.
Although I always find it difficult express my gratitude to my to express myself, I know thanks never be enough to supervisor, Prof. Robin Smith, for his guidance,

inside encouragement and support and outside academia. Whatever I gain is indebted to him, his contribution inspiration and that put me in the right direction towards

his kindness drew that accomplishing my research, and patience and always me out of wandering nowhere. Special thanks to the Department of Process Integration for giving me the opportunity and the sponsorship to study at U MIST My the to and chance meet many people.

I like for help their thanks to would and support whenever needed. all staffs, sincere go to thank Chris for his magic that brings beautiful results and thank Nan for always giving me useful tips. I am also grateful to all students in the department for creating a friendly atmosphere

friends for I in time and all supporting and which spent and worked, and making a great helping me through those uneasy and depressing times of being away from families. Naming all of them will definitely double the volume of this thesis.

I would like to send deep thanks to my parents, parents-in-law and my older brothers, for their love and support through my life without any doubt about my decision ever. Last but not least, I give unlimited thanks and love to my dearest husband, Dr. Zhiqiang Meng, for his love, encouragement and being with me over last 15 years, especially his by final in the own career. compromising year companying me

Table of Contents
Declaration Abstract ....................................................................................................................... II

...........................................................................................................................

III V

Acknowledgements Table of Contents

..........................................................................................................

VI ............................................................................................................

List of Figures X .................................................................................................................. List of Tables XIII ................................................................................................................

Chapter 1: Introduction ..................................................................................................... 1

1.1 Model building challenges for complex reaction systems 3 .................................. 1.2 Research motivation and objectives 5 .................................................................... 6 1.3 Overview of thesis ............................................................................................... Chapter 2: Literature Review
2.1 Introduction

............................................................................................

......................................................................................................... 2.2 Model building procedure: step-by-step method ..............................................

9 10

10 2.2.1 Reaction paths and schemes ..................................................................... 11 2.2.1.1 Knowledge-based methods ......................................................... 12 2.2.1.2 Logic-centred methods ................................................................ 13 2.2.2 Reaction kinetics ...................................................................................... 14 2.2.2.1 Traditional approach: white box ................................................. 15 2.2.2.2 Tendency model: grey box .......................................................... 16 2.2.2.3 Approximate methods: black box ............................................... 17 2.2.3 Model reduction ....................................................................................... 19 2.2.4 Process development and optimisation .................................................... 20 2.2.4.1 Heuristic methods ........................................................................ 22 2.2.4.2 Geometric technique (Attainable Region) ................................... 23 2.2.4.3 Mathematical methods (based on superstructure) ....................... 2.3 Model building for refinery heterogeneous catalytic reactions ......................... 24

VI

2.3.1 Current approaches 25 ................................................................................... 2.3.2 Difficulties and challenges 29 ....................................................................... 2.4 Summary 30 ........................................................................................................... Chapter 3: Construction of Reaction Schemes 32 ................................................................
3.1 Introduction ....................................................................................................... 33

3.2 Feasible reaction generation 36 .............................................................................. 3.2.1 Stoichiometric analysis 37 ............................................................................ 3.2.2 Two-stage reaction generation method 40 ....................................................
3.2.2.1 Reacting species classification .................................................... 3.2.2.2 Reaction set-up ............................................................................ 3.2.2.3 Reaction feasibility: linear programming .................................... 3.2.2.4 Stage II reaction generation ......................................................... 3.2.2.5 Simplification .............................................................................. 42 42 44 46 46

47 3.3 Reaction scheme construction ........................................................................... 49 3.3.1 Incidence matrix ....................................................................................... 52 3.3.2 Feasibility check procedure ...................................................................... 53 3.4 Illustrative example ........................................................................................... 59 3.5 Conclusions ....................................................................................................... 60 Chapter 4: Hybrid Optimisation of Rival Models ........................................................... 61 ....................................................................................................... 62 4.2 Problem Description .......................................................................................... 4.1 Introduction
4.2.1 Preliminary experimental design .............................................................. 63

................................................................................................ 65 4.2.3 Reaction system modelling ...................................................................... 69 4.3 Rival Models ..................................................................................................... 70 4.3.1 Optimisation framework .......................................................................... 71 4.3.2 Objective function .................................................................................... 72 4.3.3 Hybrid optimisation .................................................................................. 72 4.3.3.1 Simulate Annealing (SA) ............................................................ 77 4.3.3.2 Nonlinear Programming (NLP) ................................................... 4.3.4 Implementation of the optimisation ......................................................... 79

4.2.2 Data fitting

64

VII

79 ................................................ 4.3.4.2 Optimisation moves 80 ..................................................................... 4.3.4.3 Parameter precision improvement 82 ............................................... 4.4 Illustrative cases 82 ................................................................................................ 4.4.1 Base case 82 .................................................................................................. 4.4.1.1 Reaction list generation 84 ............................................................... 4.4.1.2 Parameter estimation 84 ................................................................... 4.4.1.3 Results and analysis 85 .................................................................... 4.4.2 Oleic acid epoxidation reaction system 87 ................................................ 4.4.2.1 Model building 89 ............................................................................ 4.4.3 Discussion 90 ................................................................................................ 4.5 Conclusions 91 .......................................................................................................
Chapter 5: Model Discrimination Optimal Experimental Design 92 and ............................

4.3.4.1 Simulated Annealing framework

93 ....................................................................................................... 5.2 Model discrimination criteria 96 ............................................................................

5.3 Optimal experimental design .......................................................................... 101

5.1 Introduction

5.3.1 Laboratory reactors 102 ................................................................................ 5.3.2 Operating conditions 103 .............................................................................. 104 5.3.3 Reactor superstructure ............................................................................ 106 5.3.4 Simulated Annealing (SA) optimisation ................................................ 107 5.4 Case Studies .................................................................................................... 107 5.4.1 Base case ................................................................................................
5.4.2 Oleic acid epoxidation ............................................................................ 109

5.5 Conclusions

..................................................................................................... ..............

110 111 112

Chapter 6: Model Building for Refinery Heterogeneous Catalytic Reactions 6.1 Introduction

..................................................................................................... 114 6.2 Heterogeneous catalytic reactions ................................................................... 114 6.2.1 General features ...................................................................................... 118 6.2.2 Hydrodesulphurisation (HDS) processes ............................................... 122 6.3 Model building methodology for HHDS processes........................................... 124 6.3.1 Catalyst characterisation ........................................................................

VIII

128 ..................................................................................... 6.3.3 Model discrimination 132 ............................................................................. 6.4 Case studies 133 ..................................................................................................... 6.4.1 Hydrodesulphurisation of thiophene 133 ...................................................... 6.4.2 Hydrodesulphurisation (HDS) of diesel 137 ........................... ......... 6.4.2.1 Temperature effects 141 ................................................................... 6.4.2.2 Sulphur compound addition effects 142 ........................................... 6.4.2.3 Catalyst effects 143 .......................................................................... 145 .............................................................................................. 6.5 Conclusions 146 ..................................................................................................... 147 Chapter 7: Conclusions and Future Work ..................................................................... 7.1 Conclusions 148 .....................................................................................................
152

6.3.2 Catalyst kinetics

6.4.3 Discussion

7.2 Future work .....................................................................................................

7.3 Remarks Notation

153 ...........................................................................................................

154 ......................................................................................................................... 158 ..................................................................................................................... 172 ................................................................................................................... ................................................................................................................... ................................................................................................................... ................................................................................................................... 174 176 177

References

Appendix A Appendix B Appendix C Appendix D

IX

List of Figures
Fig. 1.1 Typical chemical processes Fig. 1.2 Overall chemistry of net reaction of R4 Fig. 2.1 Conventional model building methodology Fig. 2.2 Ideal reactors Fig. 2.3 Ideal reactor combinations Fig. 2.4 Industrial reactors Fig. 2.5 Triangular representation Fig. 2.6 Illustration of the complexity of a Co-Mo/A1203 hydroprocessing catalyst Fig. 2.7 The role of microkinetic analysis Fig. 3.1 Reaction model representation Fig. 3.2 Reaction scheme of 2-methyl-6-trifluoromethyl aniline Fig. 3.3 Dimethylbenzene oxidation Fig. 3.4 Reaction generation framework Fig. 3.5 Reaction set-up Fig. 3.6 Changes of reactant and product set Fig. 3.7 Complex monomolecular reaction schemes Fig. 3.8 Reaction scheme examples Fig. 4.1 General model building framework Fig. 4.2 Simulation method framework Fig. 4.3 Optimisation method
Fig. 4.4 Data fitting curve

10 19 20 20 24 27 28 33 34 39 41 43 46 48 58 61 69 70
71

Fig. 4.5 Simulated Annealing optimisation framework Fig. 4.6 Optimisation moves in SA Fig. 4.7 Example of state-to-state moves

78 80 81

Fig. 4.8 Base case Fig. 4.9 Data graph for base case Fig. 4.10 SA and NLP optimisation results Fig. 4.11 Residual analysis Fig. 4.12 Rival models Fig. 5.1 General model building framework Fig. 5.2 Data fitting and model performance Fig. 5.3 Model discrimination framework Fig. 5.4 Optimal experimental design framework Fig. 5.5 Laboratory reactors for homogeneous reactions Fig. 5.6 Laboratory reactors for heterogeneousreactions Fig. 5.7 Homogeneous experimental reactor superstructure Fig. 5.8 Multiphase experimental reactor superstructure Fig. 5.9 Model performance
Fig. 6.1 Operating conditions change with sulphur content target

82 84 86 86 87 93 94 96 101 102 103 104 104 108

114

Fig. 6.2 Steps in a heterogeneouscatalytic reaction Fig. 6.3 Method for special distribution of active ingredients Fig. 6.4 Modem refinery Fig. 6.5 Feed and product chromatogram Fig. 6.6 Dimethyldibenzothiophene reaction scheme Fig. 6.7 Relative reaction rate of sulphur compounds Fig. 6.8 Catalyst synthesis procedure Fig. 6.9 Model building framework Fig. 6.10 Catalyst properties Fig. 6.11 Catalytic kinetic model composition

115 116 118 118 119 120 121 124 125 127

XI

Fig. 6.12 Concentration profile Fig. 6.13 Laboratory reactors for heterogeneousreactions Fig. 6.14 Parity plot for Model A Fig. 6.15 Model predictions Fig. 6.16 Optimal operation conditions for model discrimination Fig. 6.17 Pseudo-component for sulphur compounds Fig. 6.18 Boiling curve of diesel fuel
Fig. 6.19 Pseudo-component performance of different models Fig. 6.20 Model difference of each pseudo-component addition

131 132 135 136 136 137 138

142 142

Fig. 6.21 Catalyst active material distribution Fig. 6.22 Model performance changing with active material location Fig. 6.23 Model performance changing with particle size

143 144 145

XII

List of Tables
Table 4.1 Experimental data for base case Table 4.2 Comparison of optimisation results Table 4.3 A 24-1fractional factor design Table 4.4 Operating levels for variables of interest Table 4.5 Experimental data from the factorial experiments Table 6.1 Quantity of sulphur in the various distillation fractions Table 6.2 European diesel specifications Table 6.3 Typical commercial hydrotreating catalysts properties Table 6.4 Compilation of techniques for HDS catalysts Table 6.5 Factors of Eq. 6.14 Table 6.6 Diesel properties Table 6.7 Kinetic parameters for Model 1 Table 6.8 Kinetic parameters for Model 2 83 85 88 88 88 113 113 120 127 134 138 140 140

XIII

Chapter 1

Introduction

Chapter 1: Introduction
1.1 Model building challenges for complex reaction systems 1.2 Research motivation and objectives 1.3 Overview of thesis

Chapter 1

Introduction

The chemical reactor is the core of any chemical process. In a typical chemical process (Fig. 1.1), the capital and operating costs of chemical reactors may be only 10 25% of the total cost, with separation units dominating the size of cost of the process. Yet the performance of the chemical reactor usually controls the costs and modes of the operation of the separation units. Thus, improvements in the reactor may have an enormous impact on upstream and downstream separation processes. However, the performance of the chemical reactor relies on the accuracy of process models.

Recycle Raw Materials Separation Process Chemical Reactor Separatio Process Products TB mroducts

Fig. 1.1 Typical chemical processes

A wide variety encountered in

of reactions for processes

are complex fine

multi-step

processes, particularly chemicals

those

and speciality

and pharmaceutical

for fine Processes chemicals. and speciality chemicals and pharmaceutical chemicals feature life (Mills cycles often products with short product & Chaudhari, 1997) that

detailed because first development the that the a company of model unattractive, make % (Cussler & Moggridge, 2001). 70 the total to the tends get of sales markets product

This creates a disincentive to study the reaction chemistry and kinetics in any detail. In turn, this often leads to reactor designs being scaled from laboratory experiments developed, kinetics. Where is the a model chemistry or reaction without any model of there tends to be a compromise between the desire to spend a lot of time to study the Yet, desire that details to the a model without production. start early and reaction be features key missed. of the reaction system, major opportunities can reflects the Heterogeneous catalytic reactions are more complex than homogeneous reactions due to desorption, diffusion, which makes adsorption, surface reaction, and the combination of development in difficult become the task building the of a new process. most the model heterogeneous for building catalytic reactions might In general, the procedure of model last up to 5 years, with a large number of experiments carried out.

Chapter 1

Introduction

1.1 Model building challenges for complex reaction systems

The design of a chemical reactor, and its optimisation and control require a quantitative description of reaction system behaviour in the form of equations. Existing methods for reactor design and optimisation can only be used after a reaction model has been obtained from laboratory experiments. In the process of the product development, chemists and chemical engineers are working at different stages. Chemists aim to find the synthesis routine for the product, focus design while chemical engineers on process and optimisation.
The conventional approach for model building done is of reaction systems generally

step by step. First, several mechanisms or schemes are proposed according to the detailed identification of the reaction products intermediates, and together with

physicochemical

insights into the reaction mechanism and catalysts. Then, reaction rate to derive the rate law for a specific reaction by appropriate data collection Rival and analysis. models are screened

data are obtained experimental

planning,

be Finally, to simplify to needed might reduction model analysis. statistical according for engineering purposes. models

Certainly, there are drawbacks using the conventional methodology. Experiments likely the to most exploring omit are evaluation carried out without simultaneous factors Important design for information important and optimisation. reactor essential by be ignored that cover regions and may chemists that affect scale-up of processesmay be likely is The to important. a process operated under non-optimal result are not conditions. from is industry R in raw produced For example, an important product pharmaceutical 1.2. Fig. in B, A as shown and materials

Chapter 1

Introduction

HN OCH3 \S ON C' SO2NH COOCH2OCH3 CHZOCONHZ COOCHZOCH, JCHZCOCI s

a-

OH 11 1 sC H2C-N\

OCH3

CHZOCONHZ COOCHZOCH,

ABR

Fig. 1.2 Overall chemistry of net reaction of R

The actual reactions are composed of five reaction steps (Paul, 1988):

A+BHR*+HCI R*+BHR**+S, R*+HC1->S1 R**+HCIHR+B +HCI

S1 -> S2 + HCl
When the process was scaled up from a laboratory reactor to an industrial scale reactor, it was observed that no R was produced at all. From the analysis, it became clear that the side product effect was overlooked in the model based on the laboratory reactor. That is, if the concentration of by-product (HC1) is not controlled, this reaction system desired the product. will give no yield of At the early stage of model building, serious errors, such as overlooking some variables, has been incorrect the the where model region an reaction scheme, extrapolation outside design the the tested, or unjustified expansion of reactor number of variables, may cause to be inaccurate or entirely erroneous. Detailed intrinsic models are critical for the design, optimisation, and control of

Unfortunately, chemical reactors.

the use of such models is hindered by several factors, large the scale of the models. and demanding, especially when

due to stiffness of the equations, high dimensionality

The numerical solution of such models is computationally

for insight hand, On the gaining other kinetics are coupled with transport phenomena. into the reaction in features key behaviour, the system and components of system

detailed models are often disguised.

Chapter 1

Introduction

1.2 Research motivation and objectives

Accuracy and efficiency are the two requirements of the desired models for reaction From the initial stages, it is preferable to direct the experimental design to systems. extract a model suitable for scale-up using process design techniques. Hence, it is find for fast by to these the approximate necessary models complex reaction systems data, development to time to market. and effective evaluation of experimental shorten
Given all stable species involved (as opposed to unstable intermediates) in the system, information without any about reaction pathways and mechanisms, this work aims to

find suitable reaction schemes and kinetic equations for the purpose of reactor design and optimisation. The methodology to be developed here will optimally determine a set of reaction

design for kinetics to then existing reaction systems and schemes and associated information that give maximum experiments based between the on models, choice on

for is discrimination the Model earlier experiments emphasised alternative mechanisms. In this work, to estimation. parameter the of precision switches emphasis and gradually the first consideration kinetically will be restricted to homogeneous reaction systems that are

important does role. transfer an play not mass where controlled

is heterogeneous for also catalytic reactions In addition, a systematic methodology hydrodesulphurisation developed be for using this The will case methodology required. In this heterogeneous reactions. catalytic typical (HDS) processes as one of refinery including heterogeneous for building reactions catalytic thesis, the procedure of model be discrimination also, explored kinetic will model and studies catalyst characterisation, be transfer neglected. cannot where mass the to set generate used are the species participating In the model building methodology, formulation all Atom-molecule allows matrix in two-stage method. a reactions of all be to for used can and analysis system reaction be represented systematically species to by two-stage a After reactions generating all possible describe the reaction equations. feasibility the of is the test to stoichiometric linear used integer programming method, A law is scheme reaction if satisfied. the conservation mass checking through reactions

Introduction

construction algorithm is used to provide all feasible reaction schemes for the optimisation search, while reaction models are obtained through the best fitting of experimental data. Since the true mechanism is rarely known, a number of alternatives will lead to a set of so-called rival models. The experimentation needs to provide evidence in favour of one model. Further experiments for model discrimination are designed by maximising the divergence among all rival models. All kinds of operating conditions, including feeding policies, phase contacting patterns, mixing types, recycles and discharges should be searched through optimisation. Here an optimisation method is needed again to guarantee a robust and fast global solution. The objective of the present work is to develop a new method to link the work of chemists and chemical engineers to reduce the risk of direct scale-up of chemical reactors, make full use of experimental information, to save expense of laboratory and pilot experiments, and to shorten time from laboratory to market.

1.3 Overview of thesis

The next chapter generally reviews existing methods from all aspectsof model building, their advantages and disadvantages. It also includes the complexities and difficulties of model building for heterogeneous catalytic reactions, focusing on the

hydrodesulphurisation (RIDS) processes. In Chapter 3, with little knowledge of reaction chemistry, feasible reaction schemes are derived directly from the information of the inlet and outlet components of reaction is It from the guaranteed that all possible chemical engineering viewpoint. systems Here for feasible a new strategy reaction schemes are generated. reaction steps and all discussed in detail is with examples, which provide reaction scheme construction feasible reaction schemes from the raw materials to products. A feasible reaction list in is to two-stage through construct reaction schemes. a used method obtained each stage Because more than one model can fit the same experimental data set, it is essential that before further kinetics are obtained all possible combinations of reaction schemes and As integer is information available. a mixed and nonlinear programming experimental

Chapter 1

Introduction

problem, hybrid optimisation can provide a global optimal solution. Chapter 4 considers a new methodology to identify suitable reaction schemes and kinetic equations by an optimisation method simultaneously with the aid of experimental data. A stochastic method is designed to obtain a set of solutions close to the optimal region by setting up reaction scheme moves and kinetic moves to generate alternatives and monitor the random search. A base case and oleic acid epoxidation will be used to illustrate how the methodology can interpret the experimental data and be used for reactor design and optimisation.
Further experimental data are necessary for model discrimination, so optimal

experimental design is carried out by an optimisation

method. All kinds of laboratory

reactors and operating conditions are embedded in a reactor network superstructure to be optimised. The same two cases continue to function as examples in Chapter 5, to demonstrate improvement. In Chapter 6, a systematic methodology of model building and model discrimination for the whole procedure for model discrimination and model accuracy

heterogeneous catalytic reactions is explored. Due to the complex nature of catalysis, a large number of rival models pose difficulties the procedure of model building for model building and discrimination. In

for heterogeneous catalytic reactions, a three-level

kinetic study method is used in this thesis to reduce the model complexity by separating diffusion effects from kinetic equations. In addition, catalyst characterisation is used to discrimination. assist model capabilities limitations and There are a large number of techniques with different available to connect catalyst properties, catalyst activities

A be in but these application. a given useful will not all of with model performance, for here discussed suitable selecting guidance techniques those provides of classification techniques to yield the most information Because with accuracy, speed, and economy. (HDS) process in the refinery industry, for thiophene and

hydrodesulphurisation importance the the of of discrimination for model plausible ways

improvement and model

feedstock and catalyst effects are HDS diesel are explored, while operating conditions, included. limitations discusses the the and the methodology of 7 work, Chapter summarises future work. recommends

Chapter 2

Literature review

Chapter 2: Literature
2.1 Introduction

Review

2.2 Model building procedure: step-by-step method 2.2.1 Reaction paths and schemes 2.2.1.1 Knowledge-based methods 2.2.1.2 Logic-centred methods 2.2.2 Reaction kinetics 2.2.2.1 Traditional approach: white box 2.2.2.2 Tendency model: grey box 2.2.2.3 Approximate method: black box 2.2.3 Model reduction 2.2.4 Process development and optimisation 2.2.4.1 Heuristic methods 2.2.4.2 Geometric technique (Attainable Region) 2.2.4.3 Mathematical methods (based on superstructure) 2.3. Model building for refinery heterogeneouscatalytic reactions 2.3.1 2.3.2 Current approaches Difficulties and challenges

2.4. Summary

Chapter 2

Literature Review

In a chemical process, reactions and reactors are at the centre of the whole process, influencing the upstream, downstream and other units. So reactor design and optimisation is central to the field of process synthesis. This poses great pressure on the model accuracy and efficiency and requires systematic methodologies of model building. Previous work for model building is reviewed in this chapter, including conventional methods for homogeneous reaction systems. Special considerations for

refinery heterogeneous here. catalytic reactionsare also discussed 2.1 Introduction

The reactor design and optimisation can only be carried out after the reaction models, reaction schemes and kinetic expressions have been obtained by chemists from laboratory experiments.
Generally, the development chemist often has a strong background in synthetic

chemistry, but may lack skills in manipulation of kinetics and chemical thermodynamics to benefit from those techniques when needed. The gap between the work of chemists and chemical engineers becomes the weakest link of process development and scale-up. As a result, processes will run under non-optimal conditions. Since the true mechanism is rarely known, there are several mechanisms consistent with the data. Even if one mechanism remains that is in agreement with all the known facts, there is no assurance that it is unique, or that new experiments will not provide evidence to discredit it.

In order to meet the requirement of cutting costs and making profit, detailed study of the be is of experiments will not preferable since an enormous number reaction system best decision fast hand, this On the the at point model on getting a other necessary. between is for There direction trade the lead a off the always to research. wrong might model accuracy and the model efficiency. Advantages and disadvantages of conventional methods in the procedure of model heterogeneous for homogeneous be building will catalytic reactions to and reviewed for inspiration methodology. new the spark

Chapter 2

Literature Review

2.2 Model building procedure: step-by-step method

A step-by-step approach is widely used for model building of reaction systems, as shown in Fig. 2.1.

Reaction scheme or mechanism

Parameter estimation

Model reduction

Fig. 2.1 Conventional model building methodology

As the first step of model building, a reaction mechanism or scheme composes the
fundamental mechanisms structure or of the reaction model. The current in research of reaction reaction schemes focuses schemes on the

situation

which

(mechanisms) that satisfy the given specification for the transformation of available raw materials to desired products are composed through either a fixed, predetermined set of elementary encountered reactions, quite or simultaneously during generated reactions. This is a problem and

frequently

research and development

of chemical

biochemical processes.

Reaction rate data are needed to obtain the rate law for a specific reaction by proper experimental planning, data collection and analysis. From this, reaction rate parameters (i. e. reaction order, frequency factor and activation energy) are determined and modified (Froment & Bischoff, 1979). Appropriate statistical analysis is necessary for model screening. Model reduction is used to simplify complex reaction systems, such as combustion factor diesel HDS. Lumping, target analysis, sensitivity system, metabolism process and analysis and perturbation theory are commonly used methods.

2.2.1 Reaction paths and schemes

There are two approaches to the study of reaction paths and schemes: optimal design of in desired and of existing to carried out advance, analysis products paths reaction reaction systems.

10

Chapter 2

Literature Review

Reaction path design is currently used by experienced chemists and engineers. Knowledge of similar reaction paths, availability of raw materials, named organic basic reactions and reaction mechanisms are used to guide their research for new reaction paths. These researchersare remarkably adept when one considers the immense lead to a simple organic molecule. of number paths, which could The aim is to find relevant paths in this multitude that could potentially lead to flexible, and safe processes.These paths could be subjected to more detailed economic, further to analysis and experiments resolve their potential. The methods of generating reaction paths are based on structure transformation (atom, bond, electron, and functional group). Structure transformation can provide many more reaction options than the reaction pathways of the reaction mechanism.
The current approaches for generating reaction steps are commonly in organic used

(Nishida into be divided design two et al., categories reaction paths can synthesis to 1981): knowledge-based methods and logic centred methods. feasible find design to that novel, aims They are commonly used as a part of synthesis for the is the routine synthesis potential considered as and economic pathways, which by been has Significant organic chemists made desired chemical product. progress towards the systematic and automatic generation of reaction paths. 2.2.1.1 Knowledge-based methods database reaction database of possible a or reactions of For knowledge-based methods, a A of defined is number stored. and priori a types for a certain molecular structure developed this been have concept, with LHASA) using SECS, (REACT, programmes search and methods evaluation reactions, different representations of molecules and strategies. 1977,1981) Powers, & (Govind The REACT first to the effort was programme

The industry. for the petroleum paths reaction chemical of automate the generation involves a REACT searching by the programme target molecule a of generation features by driven the being structural the search database of 200 generalized reactions,

11

Chapter 2

Literature Review

of the parent structure and certain basic strategies. In REACT, a molecule is represented by a connection table (CT), containing the relevant information: connectivity, atom and band types. The changes between products and reactants are checked by a list of logical functions, if the changes are feasible, reactions occur. Knowledge-based methods have the advantage that reliable reactions are used, but have the disadvantages that a large database is required and that no new reactions can be considered. 2.2.1.2 Logic-centred methods Logic centred methods (Ugi & Gillespie, 1971; Hendrickson, 1971) focus on the transformations of atom site or bond, generating sets of intermediates that can be converted to the desired molecule. The advantage is that new reactions, forward and backward searchesare considered. The large number of possible reactions generatedout of the range of the reality is its disadvantage. Hendrickson (1971) provides a constructive representation of the chemical molecule in which molecules are represented as carbon sites and was able to classify all possible interconnect For that them. a simple molecule, acrylic might reaction sites and reactions 500 This method simply generates reaction steps. paths are generated. acid, well over So an evaluation method is an important but difficult step of chemical path synthesis to infeasible reactions. prune Another situation often encountered in refinery, combustion, and biochemical reactions: from elementary reactions, or construction of construction of reactions and mechanisms P-graph 1993,1995) (Mavrovouniotis, Al Accordingly form and reactions. pathways to feature: have They be 2002) overall and all one common theory (Fan et al., used. can defined a priori. are plausible elementary reactions P-graphs, in terms based is a of The P-graph method on the unique graph-representation inclusion In the the or methods, algorithms. of combinatorial group a and set of axioms, hinges the in the general on concern of mechanism reaction elementary exclusion of one facilitated by decisions The feasible are networks. reaction of combinatorial properties balance to constraints mass set of linear a comprising problem programming a solving

12

Chapter 2

Literature Review

determine the existence or absence of any feasible solution. The search is accelerated further by exploiting redundancy. To analyse existing reaction systems, selectivity versus conversion plots of the inferences of preceding decisions, thereby eliminating

experimental data are general and useful aids to obtain insights into a reaction scheme, but it is difficult to apply to complex reaction systems. For instance, maximum

concentration versus reaction time plots are a typical feature of consecutive reactions. On the other hand, the appearance of a maximum might indicate that, rather than the system involving consecutive reactions, or consecutive reactions as a part of a more complex reaction scheme, there might be some combinations of reversible and irreversible slow and fast reactions. In most cases, the reaction pathway or mechanism is proposed based on the chemist's expertise and experience, not from systematic methods. The approaches to automatically design reaction paths are over complicated to apply if detected in intermediates) the (as and to are system unstable opposed species only stable So it for Also, systems. reaction complex suitable not are methods plot visual measured. for feasible find to develop schemes reaction is necessary to a systematic methodology existing reaction systems without missing any options.

2.2.2 Reaction kinetics

it is to for consider necessary determine a reactor, the operational strategy In order to Anything to related dynamics and operational constraints. the reaction kinetics, reactor by determined be from theory, be must and kinetics reliably estimated cannot reaction kinetic for data studies. to So obtain out experiments are carried experiments. difficult is in problem. a systems complex kinetic The analysis of chemical reactions thermodynamics from and the complex stoichiometry The major complication results networks kinetic of reaction combinations models, possible of number and an enormous involve heterogeneous Furthermore, reactions for reaction. each kinetic equations and factors by influenced is speed, stirred as such hence the rate reaction transfer and mass diffusion coefficients, etc. interfacial area,

13

Chapter 2

Literature Review

It may also be necessary to investigate some intermediate reaction steps separately, particularly these whose response in the complete process is weak. With complex feedstocks, the investigation may start with a single component, with binary and ternary mixtures, to study interaction effects before progressively increasing the complexity (Froment, 1987). Anything related to reaction kinetics cannot be estimated reliably from theory, and must be determined by experiments. So experiments are carried out to obtain data for kinetic studies. Three main methods to perform kinetic analysis with handling the experimental data: 2.2.2.1 Traditional box white approach:

The traditional approach emphasises the development of a detailed kinetic model based in kinetics in the the schemes are reactions elementary any of which on molecular for the is This reactions simple even since not always possible, method studied. be not understood. complete mechanism might still kinetic based A mechanistic state-space representation on stoichiometric and is for balances the preferred the knowledge, and on energy and material reactor, describes that the kinetic the The effect for model modelling reactors. approach The have the reactor model rate of each reaction. on temperature and the concentrations inlet the to reaction streams, (concentrations, temperature volume) and the states relates from derived typically Mechanistic disturbances. models are terms, and possible form in information the of but laws, they qualitative contain can also physico-chemical for They process of range knowledge. a wide linguistic suited well are expert and/or operations. for difficult is task reaction complex for a also Data regression parameter estimation linear and of is the methods it conventional Generally, using out carried systems. Marquardt (also the Levenberg-Marquardt called The method nonlinear regression. leastfor become has the in nonlinear standard and practice well very works method) & Wolf 1996; (Moros (GA) Algorithms Genetic et al., In years, recent routines. squares large-scale for been have 1998) systems, Froment, & used also Park Moros, 1997;

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incorporating traditional method to increase calculation accuracy by providing good starting points. However, models are difficult and time-consuming to build for industrially relevant

reaction systems. A sensitivity analysis can help evaluate the terms in a model and retain those that are most relevant to the processing objectives. No realistic model is the purely mechanistic, as new physical parameters typically need to be estimated on the basis of process data. As with data-driven models, experimental design techniques are for building tools useful sound models from a limited amount of data. 2.2.2.2 Tendency model: grey box
This method (Filippi et al., 1986,1989; Fotopoulos et al., 1998) is based on a

phenomenological

approach and on the estimation

of a small number of kinetic

by data. does It the to parameters matching model predictions experimental not require a detailed kinetic description, but takes into account general knowledge about the process, balances. kinetic This the option scheme to a very reduces such as mass and energy kinetics, lumping and normally using chemical species with simple simple one, often in functions the stages of the scheme considered. power

The tendency models are developed by using fundamental material and energy balances, The model's stoichiometric along with an approximate overall reaction network. by least-squares kinetic regression of the parameters are estimated coefficients and in kinetics tendency Because the data. model may not closely the assumed experimental for be kinetic process simulation needed may the models several network, real represent detailed less is the than Although the accurate usually model proposed optimisation. and kinetics into insights the true important the search and guide it provide mechanism, may to a more optimal operation. identification is development the of a simple stoichiometric The first stage of model final initial includes of information compositions and Necessary experimental network. for each experiment. the significant reactants in the is the that stoichiometric of kinetic calculation unique network The resulting the Parameters, the and error allowable maximum as is such user-defined. coefficients

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number of reactions, are also selected in applying available heuristic information in the If model. an appropriate solution is unattainable, the reaction may be divided into stages with each section represented by a distinct kinetic model. Identification of the tendency model's Arrhenius constants is performed with the

factor Each temperature/concentration experimental profiles. reaction's preexponential (for and activation energy non-isothermal processes) are evaluated by minimising the deviations between the model and experimental compositions over the course of reaction. The heats of reaction are then estimated by comparing the experimental heat is kinetic final The the a product generation with values calculated using network. process model that can be used in simulation and optimisation studies. The methods applied for calculating the parameters in traditional approach and tendency The have based most utilised many variations. upon regression, and model are normally integral differential have been the the method. and method methods has it high industrial be to Although the tendency model approach appears relevance, of The in little the real engineering academic research community. attention received by here as much matching, estimates parameter reliable generating of consists challenge to in to the be the criterion step to estimated minimised as possible, the prediction error be optimised in the optimisation step. data, from the the so experimental In tendency models, reaction networks are extracted In independent most is the reactions. to of number equal number of reaction steps is true. this not assumption complex reaction systems 2.2.2.3 Approximate box black methods:

The systems. reaction actual of into properties does This account of physical not take important discovery led has of the to and study development of mathematical analysis be have to proven functions, conditions, certain under which classes of approximation These functions. less arbitrary or more other, the natural means of approximating approximation functions include polynomials, trigonometric series, orthogonal basically as viewed In are the this parameters adjustable case, functions, splines, etc. do in data considerations physical reflect not fitting principle, the and, for vehicles

16

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about the reacting system. Neural network methods have been proposed to model the dynamics of discontinuous reactors (Galvan et al., 1996; Krothapally & Palanki, 1997). In this method, the amount of available data is crucial for the accuracy of the model. Although simple and relatively easy to obtain, black-box models have certain

drawbacks: 1. Even when they exhibit good interpolative capabilities, they are inadequate for behaviour the predicting reactor outside the experimental domain in which the data were collected for model building. 2. Black-box models represent a dynamic relationship only between variables that key Unfortunately, variables usually remain are manipulated or measured. unmeasured in most reactors. In brief, for the investigation of chemical reaction kinetics, it is not necessary that the detailed mechanism of reaction is studied, and also it is not easy to find approximation functions to represent experimental data for large-scale complex reaction systems. So based law), (hyperbolic functions can results, on experimental or power mathematical be best in data the interpret must of experiments the range experimental or represent developed. have In particular, for complex reaction systems, the selected regression method should kinetic large handle parameters. the estimation of a number of the ability to

2.2.3 Model reduction

in important increasingly becoming is Detailed modelling of complex reaction systems However, design processes. reaction chemical of control development, and analysis, the because First, their by hindered is two of obstacles. models complex the use of such difficult to solve. these are time models scales, multiple of the presence and size sheer kinetic large parameters. or unknown uncertain of number a Second, the models contain difficult both is models nonlinear determine the complex of parameters Regression to be to cannot uncertainties parameter simulations the of sensitivity and and unreliable, into insight the for reaction the Furthermore, gaining of purpose easily ascertained.

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system behaviour, it is usually preferable to obtain simpler models that bring out the key features and components of the system. For those reasons, model simplification and order reduction are becoming central problems in the study of complex reaction systems. The simulation, design and control of a complex reaction system benefit from the derivation of accurate and reliable reduced models tailored to particular process modelling tasks (Okino & Mavrovouniotis, 1998). Model reduction methods used for simplifying complex reaction systems in the last two decades include lumping, sensitivity analysis, target factor analysis, perturbation theory, invariant manifold method and variable selection techniques (Edwards & Edgar, 2000). The choice of model reduction methods depends on the accuracy required for the kinetic the the task, the extent of available structure of reaction system and modelling information. Lumping (Weekman, 1979) is a widely used method for model reduction in which the lumping is known, discrete is kinetic When is transformed. a scheme reaction vector dramatically increases lumping finding in difficulty The schemes appropriate possible. for large nonlinear reaction networks. 1983; Rabitz 1981; (Tilden Model reduction through sensitivity analysis et al., et al., full its feasible is 1984) the Flamm, & and Edelson complete reaction scheme when in be the to that In known. retained need species sensitivity analysis, which solution are further Recently, desired be step the a accuracy. as well as specified, can reduced model in A (1999). time Petzold by Zhu done criterion of direction nonlocal in this and was kinetics full between the chemical of systems the reduced of and closeness of solutions but the derivatives true just of closeness a It is used. a closeness of requires not dynamics. By identifying different the time the of scales important that embody the models

is 1991) & Bastin, Breusegem (van method the perturbation singular system, reaction in to that analysis of sensitivity similar a manner simplification able to perform model 1996). & Rouchon, (Duchene kinetic full to the for model solutions the need without

18

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Target factor analysis (TFA) (Bonvin & Rippen, 1990) has been used successfully with reaction data to determine, the number of independent reactions and the corresponding stoichiometry without knowledge of reaction kinetics.
The Method of Invariant Manifold (MIM) for model reduction of dissipative systems of kinetics has been developed during last two decades (Gorban & Karlin, 1992a, reaction b, 2000,2003). The MIM is based on a formulation of the condition of invariance as an

its by Newton iterations. The systematic use of thermodynamics equation, and solution structures and of the quasi-chemical representation allows to construct approximations, in Dynamic concordance with physical restrictions. and static post-processing which are procedures give the opportunity to estimate the accuracy of obtained approximations,

improve to this accuracy significantly. and All have been techniques these applied with of but there remain some success,

unanswered problems:

is best is the smallest the one, what which reduced model

dimension of the reduced model, and what is the range of application of the reduced model?

2.2.4 Process development and optimisation

The aim of reactor design and optimisation is to find the reactor network structures and that give maximum performance. conditions operating (CSTR), (PFR) flow tank batch, see and stirred There are 3 types of ideal reactor: plug
Time
Feed

10

uct

Product

Batch

PFR
Fig. 2.2 Ideal reactors

CSTR

form in be the ideal different series, of used can reactors Fig. 2.2. Also, combinations of

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.
Series

Parallel Fig. 2.3 Ideal reactor combinations

Series Parallel -

00000 00000 00000 00000 00000 00000

Fig. 2.4 Industrial reactors

parallel or series-parallel_ of ideal reactors, as shown in Fig. 2.3. In reality, generally more complex reactors are used (Fig. 2.4). Also it is necessary to determine the operating conditions to be used. For example, it is

necessary to determine the feeding policy and temperature profiles as well as flow contacting types, or equipment sizes. Furthermore, other information such as physical properties, mass transfer, heat transfer, fluid kinetics thermodynamics, mechanics, and especially chemical are chemical design to and optimise a reactor. required Different reaction systems, homogeneous, heterogeneous or catalytic, have different different have features, but in design Accordingly, the should methods characteristics. (Attainable heuristics, into 3 divided be techniques types: graphical generally they can Region) and mathematical methods, and sometimes combinations of these. 2.2.4.1 Heuristic methods for homogeneous be (1962) the Levenspiel reactors and can also most useful rules gives It includes heterogeneous directly to systems. six general rules: applied

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Chapter 2

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Rule 1: For Single Reactions To obtain the minimum reactor volume, the concentration of a reactant whose reaction is order n>0 should be kept as high as possible, low for components where n<0. Rule 2: For Reactants In Series Consider reactions in series: A-R-S-->"""Y-Z

To maximise any intermediate, fluids that have different concentrations of the active ingredients - reactant or intermediates, must not be mixed. Rule 3: For Parallel Reactions Consider the parallel reactions with reaction orders ni : R AS T low order nl ... n2 ... intermediate high order n3 ...

To get the best product distribution: o s 0 Low CA favours the reaction of lowest order High CA favours the reaction of highest order CA intermediate intermediate then is some order If the desired reaction of distribution best the product will give 0 is distribution not affected For reactions all of the same order, the product by the concentration level. Rule 4: Complex Reactions into decomposing their by them and series simple be analysed Reaction schemes can for reactions series Therefore, and reactions parallel rules components. parallel simple

21

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Literature Review

be can applied. For example, for the following reactions, where R is the desired product, the breakdown is as follows: A+B R -B+RS B->R and BSS

ARS

The breakdown means that A and R should be in flow, plug without any recycle, while B can be introduced as desired at any concentration level, since it will not affect the product distribution. Rule 5: Continuous Versus Discontinuous Operations Any product distribution that can be obtained in continuous steady-stateflow operations can be obtained in a non-flow reactor and vice versa. Rule 6: Effect of Temperature on Product Distribution High temperature favours the reaction with higher activation energy E, while a low temperature favours the reaction with smaller E. According to the above general rules, reactors and operating conditions to achieve be determined. However, heuristic maximum performance can methods are easy to use but they often contradict each other, especially for complex reactions, so systematic methods are necessary. 2.2.4.2 Geometric technique (Attainable Region) In the early 1960's, Horn (1964) advocated the study of optimal reactor synthesis by it He to the corresponding a prescribed attainable region, called methods. geometric feed and kinetics, which means the full set of outcomes achievable by all possible designs. In the 1980s, Glasser and Hildebrant (1987,1990) idea. reviving this attainable region Of special importance are its extreme points, as these determine the region completely, for Although isothermal there. the often realised problems are the optima reactor and for interpretation the tool the graphical of synthesis elegant an provided strategy were instrumental in

22

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problem, the extension of the method to more complicated mechanisms and nonisothermal problems unavoidably goes through the proposition of a series of curves and three-dimensional graphical simulations. An implementation of the attainable region concept has been presented by Balakrishna and Biegler (1992), who proposed a targeting approach that endeavours to bypass the difficulties attainable region in high-dimensional spaces. 2.2.4.3 Mathematical methods (based on superstructure) in constructing the

Jackson (1968) postulated a reactor superstructure made up of plug flow reactors by connected side streams. Adjoint relations were used to model the effect of flow in the side steams on the concentration of species at the exit of the reactor network. Achenie and Biegler (1986,1988) allowed for component splits and postulated a series- parallel combination of axial dispersion reactors. A reactor network superstructure that includes CSTRs and PFRs with various interconnections was formulated by Kokossis and Floudas (1989,1990 & 1991). In the problem formulation, the PFRs were approximated by a series of equal-sized sub-CSTRs to eliminate the differential equations, and integer This the to approach was of reactor units. existence represent variables were used for both isothermal kinetics handling and non-isothermal situations. arbitrary capable of Mehta and Kokossis (1996) extended this method to multiphase reactor design and optimisation. The key advantage of the superstructure-based approaches is that they can determine simultaneously the objective value and the explicit optimal reactor network

limitations One the the superstructureof of conditions. operating and configuration initial is the is superstructure. as based approaches that the optimal solution only as rich does initial if ignored be the not superstructure The true optimal solution can missed include all possibility. design for different and optimisation are addressed, reactor So far three approaches kinetics are available. and schemes that reaction provided

23

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2.3 Model building for refinery heterogeneous catalytic reactions

Catalysis is used to describe the phenomenon of increasing the rate of a chemical reaction by a chemical present in the reaction medium (homogeneous catalysis), or by a solid surface on which the reaction can occur (heterogeneouscatalysis). A material that

Reaction Mechanism

Catalyst Synthesis

Catalyst Characterisation

Fig. 2.5 Triangular representationof Catalysis

can cause catalysis is a catalyst. Heterogeneous catalysis is commonly used in the because industry chemical of the easy separation of products from catalysts than homogeneous catalysis. Heterogeneous catalysis not involving solid catalysts will not be in the scope of this work. Heterogeneous catalysis is more than a subfield of chemical kinetics and includes in catalyst synthesis, catalyst characterisation and reaction mechanism, as shown Boudart's triangular representation (Boudart & Djega, 1984), Fig. 2.5. Catalyst synthesis deals with the composition, structure and texture of catalytic information Characterisation on catalyst of catalysts provides quantitative materials. the the aid of chemical and physical that with performance catalyst affect properties level, information is the The on an atomic reaction techniques. reaction mechanism likely is unknown. most which When the three aspects are combined together, quantitative and systematic methods to difficult. become them interrelationships very describe the among For this reason vast

investigation. knowledge systematic await exist and empirical of amounts

24

Chapter 2

Literature Review

Catalysis has been applied in the chemical industry for at least 150 years, whereas the experimental techniques for investigation of catalysis at the atomic level were not available until 25 years ago. Also, the computational techniques are even younger and have yet to become routine. The major processes in the chemical or petroleum refining industry are based on heterogeneous catalytic reactions, such as, hydrodesulphurisation, methanol synthesis, methanation, Fischer-Tropsch synthesis, ammonia synthesis, toluene disproportionation, benzene isomerisation etc. Every process has unique features. The model and ethyl building methodology here will be developed based on the hydrodesulphurisation (RIDS) process in order to be more specific.

2.3.1 Current approaches

Hydrodesulphurisation (HDS) processes are used to meet the requirements for high fuels, in which the sulphur content is the main concern. quality In petrochemical applications, such a complex process must be modelled if an optimum fuel be In design to petroleum refining, realized. and operating policy are plant improving become the accuracy of the model more and more strict, so specifications for building time the of new processes and catalysts model prediction and speeding up become increasingly important for cost reduction of HDS processes. Industrial reactions are usually involving complex, several simultaneous and

In leading feedstocks, to of products. a variety consecutive reactions with complex kinetic studies the actual reaction network is frequently reduced to simplify overall law is by interpreted data that only valid a power the are experimental reactions, while Hougen-Watson More type rate often conditions. operating of within a narrow range fit better imported 1947) Watson, to & of experimental a (Hougen get are equations data, due to the increased number of parameters. form in largely thiols, the in sulphides, of are present oil crude The sulphur compounds detect difficult derivatives, to to thiophene and are which and thiophenes various and increase the of with number rapidly will models The reaction of complexity measure. has (1994) Ma al. et through scheme. reaction a complex going reacting species

25

Chapter 2

Literature Review

detected more than 60 kinds of sulphur compounds in a gas oil, all exhibiting very different reactivities. If these are described by reaction equations individually, the size of the reaction model will be huge. A commonly used method is to lump the compounds into several groups. Each group is represented by one single compound (pseudocomponent) that features similar properties. Moreover, the reaction scheme between those pseudo-components is composed of several typical reactions regardless of the actual reaction mechanisms. Catalytic reactions depend on the interrelationship between chemicals and catalysts. Hence, properties of the contact area between the phases are important reaction variables, which need to be accounted for simultaneously in order to model heterogeneous catalytic reactions. More complicated approaches are built on the surface science. With the aid of chemical and physical methods for catalyst characterisation, bulk, texture and surface properties can be obtained to provide proofs for the mechanism kinetic interrelationship between in analysis and catalyst properties assumptions made (CoMo/yCobalt-molybdenum behaviour. kinetic y-alumina on oxides supported and A1203) and Nickel-molybdenum oxides supported on y-alumina (NiMo/y-A1203) are the for hydrotreatment. most generally used catalysts Catalytic activity is related to the presence of sulphides of Co, Mo and Ni elements. is Mo Ni is the Co important to However, the most while as promoters, act and of role focusing the Most the of understanding on the are efforts catalyst. precursor of Mo-based catalysts. on promoting effects of cobalt and nickel Delmon (1979) proposed the presence of two distinct phases to explain the synergetic (1986a) Froment Parijs From this, and between van molybdenum. and cobalt effect for the varying concentration of active to introduced a remote control model account linking to further is It towards reaction properties catalyst step a the catalyst. sites of from basis lacks characterisation. it catalyst but solid a still rate,

26

Chapter 2

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On the other hand, Topsoe and developed the co-researchers (1981,1986,2001) CoMoS theory standing on the discovery of a special signal in Mssbauer emission spectroscopy. The behaviour can be ascribed to a mixed CoMoS phase, in which cobalt is located on the edges of MoS2 crystallites as shown in Fig. 2.6. However, the detailed structure of the CoMoS phase is still unclear after many years of efforts.

Co9S8

MoS2-Itke domains

ri irasar-.
ra r-

Qs
" Co (Nf) 0 Ma

Co: AE203

i
Co 'Z' Co

Co

Co
Co

Fig. 2.6 Illustration of the complexity of a Co-Mo/A1203 hydroprocessing catalyst

The term microkinetic simple description of

is used to distinguish between the approach outlined from a kinetics, i. e. power-law kinetics Hougen-Watson or rate

expressions, and the surface science approach. Microkinetic analysis (Dumesic et al., 1993) is an examination of catalytic reactions in terms of elementary chemical reactions that occur on the catalyst surface and their during to the a circle, provide a catalytic surface and with other each with relation From for basis another application chemical reaction engineering. reaction mechanism for is level the very useful chemistry catalytic the of understanding of view, of point development. catalyst for has into tool turned a valuable unravelling In the last decade, microkinetic analysis kinetic for heterogeneous in of parameters evaluation and catalysis reaction mechanisms for kinetic In the the model a catalytic approach, microkinetic steps. of the elementary

27

Chapter 2

Literature Review

reaction is formulated with kinetic parameters which are physical meaningful and, as far is as possible, can be derived from theoretical calculations or from experimental results. Fig. 2.7 displays the interplay of the most important data required for microkinetic analysis (Hinrichsen, 1999).

Single crystal surfaces (UHV)

>idarly-f

Tr teAx p

eY1erirnents

Material Gap 1

irt o zat

ri-

tOicrc kineli c analysis

ktros3p CUPIC
studies

Pressure
Gap

Real catalysts (high pressure)

Fig. 2.7 The role of microkinetic analysis. In the past 10 years, a new type of laboratory reactor, now popularly called a TAP

(temporal analysis of products) reactor, has been developed that shows promise of being level. So both kinetics transient the the step elementary to at reaction able characterize for data be to provide experimental carried out operation and steady-state operation can microkinetic analysis.

Due to the non-Langmuirian behavior, a coverage-dependence included into the rate between better experimental agreement a yield the would steps elementary constant of data. and calculated have Most by been has studies numerous researchers. Hydrodesulphurisation studied in dissolved pure solvents to simulate petroleum investigated sulphur compounds Parijs 1986b; & Froment, Parijs Gates, 1991; & Girgis 1978; van van fractions (Daly, Kilanowski Froment, 1996; & Vanrysselberghe 1981; Gates, & Broderick 1986; et al., is Thiophene 1998). the studied sulphur Vanrysselberghe most al., et 1978; et al.,

28

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compound (Satterfield & Roberts, 1968; Lee & Butt, 1977; Morooka & Hamrin, 1977; Van Parijs & Froment, 1986b). 2.3.2 Difficulties and challenges

Industrial processes generally involve reactions that consist of several steps and quite frequently deal with complex feedstocks. Difficulties and challenges arise in the SIDS building model process accordingly. In a heterogeneous catalytic reaction, one or more of the reactants form intermediates intermediates These in the then the the take of catalyst. catalyst on surface part with final in the that result products and the regenerated catalyst. subsequent reactions Understanding of the reaction mechanisms has always been the most difficult task for but lacks has building. This still prominent attracted significant attention, model theories. The ability to reliably predict the structure of catalyst or catalyst intermediate is a very important aspect to the model, design and catalyst improvement. The Hougen-Watson approach is generally recommended for expressing rates of the that the terms adsorption of reacting characterise contains which catalytic reaction, for it the But law account adequately than cannot still equations. power species rather interaction of the reacting species with the catalyst. be HDS conveniently studied, Although the mechanism of with model compounds can HDS individual between interactions the they cannot be used effectively to study the between and interactions property, catalyst preparation, catalyst the reactions and feedstocks. hydroprocessing in petroleum the of real reactivity catalyst HDS detailed have real petroleum with few of analysis Unfortunately, reported studies interpretation in involved difficulty the due of to the feedstocks (e.g., light cycle oil) limited data to In was analysis the studies, real-feedstock of most experimental results. Froment 1995; (Ma (pseudo-component) et al., et removal lumped sulphur considering Moreover 1994). al., is between those pseudo-components the reaction scheme the mechanisms. reaction actual of typical regardless reactions, composed of several individual in dealt terms sulphur of removal sulphur with few these studies Very of

29

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species (Kabe et al., 1992; Ma et al., 1994,1996), while simple first-order or secondlaw order power reaction rate equations were employed. Catalytic rate-modelling forms an integral part of process development and design, as well as providing insight into the underlying reaction mechanisms. Complex catalytic chemistry needs to be explored in terms of the choice of the reaction scheme, mechanism assumptions and different mixture representations. The effects of different catalysts are usually unclear with no quantitative correlation available to examine for fitting data information Unfortunately, cannot provide accurate structure sensitivity. be large in discrimination. All to this a number of rival models of results mechanism discriminated between, without any of the assumptions being able to be validated in the for 174 For development. there rival models are example, early stages of model Dibenzothiophene HDS (Vanrysselberghe & Froment, 1996) or 15 rival models for Diesel HDS (Hidalgo, 1999) in the literature.

2.4 Summary
been have for building The current methods of model complex reaction systems in been has be It all that, made in progress although this seen can chapter. reviewed to is building there methodology systematic no still procedure, aspects of the model because detectable from of: derive reaction models species Complex multiple or multi-step reactions Process chemistry not well understood Short product market window " Lack of high reliable computation tools

below: as The shortcomings of the step-by-step method are summarised " " " be information missed Important might Might lead to inappropriate models final for the Measurements carried out under conditions not appropriate design optimised

30

Chapter 2

Literature Review

9 0 0

Chemists do not work closely with chemical engineers Might lead to process scale-up failure Detailed models for complex reaction systems are time-consuming to build

Accuracy and efficiency are the two requirements of desired models for the reaction systems. So it is important to explore all the possibilities and determine important information to avoid being disguised by minor factors with minimum experimental design design, instruct Using techniques to the to process experiment measurements. for building for in is the model scale-up, a preferable approach extract a model suitable complex reaction systems.

31

Chapter 3

Construction of Reaction Schemes

Chapter 3: Construction of Reaction Schemes

3.1 Introduction 3.2 Feasible reaction generation 3.2.1 Stoichiornetric analysis 3.2.2 Two-stage reaction generation method 3.2.2.1 3.2.2.2 3.2.2.3 3.2.2.4 3.2.2.5 Reaction species classification Reaction set-up Reaction feasibility: linear programming Stage II reaction generation Simplification

3.3 Reaction scheme construction 3.3.1 Incidence matrix 3.3.2 Feasibility check procedure 3.4 Illustrative example 3.5 Conclusions

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Chapter 3

Construction of Reaction Schemes

For the models to describe reaction systems, two aspects must be included: the reaction scheme and associated kinetic models, neither of which can be neglected as shown in Fig. 3.1. Reaction schemes are considered first, but later the reaction scheme and kinetics will be optimised simultaneously. In this chapter, a strategy to find appropriate reaction schemes to represent reaction systems is presented and discussed.

Model

Reaction scheme: Which of the reactions involved " " How many reactions involved

Reaction kinetics: " " Reaction equation type Kinetic parameters

Experimental data: Reactor type (CSTR, PER, Batch, etc. ) " Raw materials and products " Operating conditions (T, P, Feeding policy, " etc. )

Fig. 3.1 Reaction model representation

This new strategy, including

finding all plausible generating single reaction steps and

Feasible for is reaction generation complex reaction systems. suitable reaction schemes, is based on a two-stage into Once the are classified all reacting species method.

Linear in two-stage procedure. a reactants and products, all possible reactions are set up feasibility. is the to reaction check used programming

from the combinations Construction of reaction schemes provides all plausible reactions The from that two-stage the feasible algorithm procedure. reactions generated of that all plausible reaction can guarantee combinations step reaction all possible searches schemes are obtained.

3.1 Introduction
have interest a complex reaction scheme. In industrial practice, many reactions of Using involve than one more one reaction step. Complex reaction systems generally

33

Chapter 3

Construction of Reaction Schemes

reaction to describe a reaction system from raw materials to products is in most cases inadequate for reaction system analysis. For instance, 2-methyl-6-trifluoromethyl aniline is the intermediate for producing the

widely used speciality agricultural chemical, Herbide (Tremont et al., 1988). It is converted from 2-methylthiomethyl-6-trifluoromethyl aniline using hydrodesulphuriThe desired reaction is: sation.

33

F3C

JAH2SCH3

H2 i Catalyst

H3

In practice, many other side reactions occur at the same time, the whole reaction scheme
is given in Fig. 3.2.
NH F3C

3 H2 S-CH H2 FCC CH3SH H2

CH4 + H2S

H2 3C + CH3 S -CH3

Fig. 3.2 Reaction scheme of 2-methyl-6-trifluoromethyl aniline

A reaction scheme is defined to describe a multi-step reaction, containing one or more The the the relationships among covers all reacting species. reaction steps, which determination first is the the reaction scheme of step of the model building

kinetics based. Hence is are experimental effort required to methodology, on which to the the obtain scheme and coefficients of reaction reaction postulated validate kinetics. For one existing reaction system, given all stable species involved (as opposed to in the intermediates) reaction systems, without unstable information any about

34

Chapter 3

Construction of Reaction Schemes

find this to elementary reactions, reaction pathways or reaction mechanisms, work aims final That is, to products. a reaction with a set of plausible routes materials connect raw defined is is as one reaction step. composed scheme of routes, any of which The reaction steps are single stoichiometric reactions instead of elementary reactions, for example, one single reaction (Doraiswamy, 2001): CH4 +C'2-> CH3Cl + HCl following by be described the reaction mechanism: can C12-> 2C1" Cl "+CH4 --> HCl + CH3 CH3 +C12 --> CH3C1+ Cl (3.1)

(3.2)

in be the for kinetic Even though the written can reaction elementary every equation free is the law the form of power reaction coefficients, same as and the reaction order Accordingly, detected be intermediates and measured easily. cannot radicals or active by derived be the quasi-steady state or rate-determining kinetics the reaction should because the for inappropriate is it systems Furthermore, reaction complex step. by disguised be and into a complicated using important insights might systems reaction detailed kinetic model. So, in this thesis, only single stoichiometric reactions are valid (3.1) Eq. This based. kinetics means using for reaction steps on which reaction are instead of Eq. (3.2). between Certainly there is more than one reaction scheme that can provide connections the through For even a complex reaction system, the same reactants and products. steps is of reaction the combinations of feasible number small, steps reaction of number Finding large. the be appropriate most very can constituting the reaction scheme but building, the is at the describe of model aim the system to reaction reaction scheme is is determining appropriate more scheme reaction which early stage of research, information important In to further avoid order study. experimental impossible without then find first validate and schemes, reaction to potential is all it being missed, critical them.

35

Chapter 3

Construction of Reaction Schemes

First of all, the task of the model building methodology is to identify which reactions and how many reactions can be used to describe the reaction system, and what is the skeleton of the reaction scheme before kinetics are coupled Candidate reaction scheme construction is done in two stages in this thesis in order to find all plausible reaction schemes. In the first stage, all possible reaction steps in the reaction schemes should first be generated. A database of molecular structure transformations (atom, bond, electron, and functional groups) is good for the study of reaction mechanisms, but from the standpoint of chemical engineering, stoichiometric describe to the reaction system, regardless of the reactivity of the reactions are enough actual molecular structure. So stoichiometry is used to analyse the existing reaction system. In the second stage, the reaction scheme is constructed by picking up reaction steps from generated reactions. In order to guarantee that all plausible reaction schemes are searched, enumeration and combination methods are used first, then a matrix transformation procedure checks the feasibility of the reaction schemes. Oleic acid epoxidation will be used to illustrate how the strategy can find all feasible reaction schemes through matrix transformations after the two-stage reaction step generation.

3.2 Feasible reaction generation

In the first stage, the reaction steps should be generated for constructing reactions All between This chemical stable species. should cover all possible reactions schemes. including law the the is the of to conservation mass, of of conservation subject change in For involved. the a reaction any element species chemical elements making up fixed, is that is that the element amount of system, there a conservation equation stating how combined or recombined, and regardless of reaction rate or whether no matter is attained. equilibrium The conservation of atomic species is commonly expressed in the form of chemical We to the to stoichiometric chemical reactions. refer corresponding equations, is A this system as chemical reaction stoichiometry. simple way expressed constraints

36

Chapter 3

Construction of Reaction Schemes

represented by one chemical equation and a complex system by a set of chemical equations. Determining the number and a feasible set of chemical equations, for a specified list of species (reactants and products), is the role of chemical reaction stoichiometry. So the first task of the model development is the identification of simple stoichiometric reactions one-by-one.

3.2.1 Stoichiometric

analysis

When limited information is available from initial experiments on the reaction system, the best tool for analysing the species involved in the reaction system is chemical reaction stoichiometry, which can give us basic information about the system.

Knowledge of the stoichiometry ensures that all the reacting species are detected, and forms a starting point for selection of analytical methods suitable for the study of formulation initial kinetics It the the of an also enables of reaction system. reaction hypothesis about the reaction and provides important information regarding the number be In N1nd. independent to turn, this allows preliminary experiments reactions, of designed. Assume there are N reacting species (molecules) in the reaction system, M types of in R (or functional one reaction steps reaction groups) consisting of all species, atoms described for So as: a complex system are chemical equations scheme.

AX=o
A is the atom-molecule matrix, where
all a21 AM xN _ a12 a22 ... ... alN a2N

(3.3)

(3.4)

aij
aM 1 aM 2 ... aMN

jth (functional ith species. of group) is atom the of number a,j 1> 0 ith atom exists in jth species a.. = =0 otherwise

37

Chapter 3

Construction of Reaction Schemes

X is the stoichiometric coefficient matrix of one reaction scheme,

x11
X21 NxR X XN1 XN2 Jk XNR x12 x22 ... ... x1R X2R

= Lx1

X2

...

XRI

(3.5)

...

xk is the reaction stoichiometric coefficient column vector for one reaction, x is the Jk stoichiometric coefficient of jth species of kth reaction and is an integer variable. >0 X1k=<0 =0 for products for reactants not involved

For an existing reaction system with little chemical information, the number of reaction in be determined R is to any candidate steps reaction scheme and varies according to different schemes. At this moment X remains unknown. The construction of reaction becomes in X, the which the reaction scheme and construction of matrix schemes included. information are reaction stoichiometric coefficients A from The reaction system analysis starts the atom-molecule matrix and useful information is extracted from the matrix characterisation. The rank of matrix, R, is the larger number of the independent columns and the independent rows. For any reaction SVD R, the in the reliable rank of an atom-molecule matrix order to get system, (Singular Value Decomposition) method is used to calculate the rank (see Appendix A), So, be the in because matrix. the a singular might matrix atom-molecule some cases Gaussian be the through elimination obtained cannot matrix atom-molecule of rank method. is independent Thus N. M the reactions number of R must be less than or equal to or 1963): Mah, & (Aris by gained N) Njnd <_ min(M, -R

(3.6)

38

Chapter 3

Construction of Reaction Schemes

This is regarded as the statement of Gibbs's rule of stoichiometry. In the meanwhile, it provides important information for degree of system freedom. In theory Njnd reactions are enough to describe the reaction system. But in most cases,it does not mean only Nand reactions occur in the reaction system, and also cannot determine which Nind reactions
occur. In this work, mild is used as an important constraint for constructing a reaction scheme, be described in 3.3, the to represent the main skeleton of the reaction will which section system. For most complex reaction systems, it is difficult among reacting species and reactions. As mentioned before, functional be in the construction of atomcan separated groups to describe the relationship

in form, formula but isomeric Not the the phase also only molecular molecule matrix. ionic functional is the the charge of species can groups and even present, species which be used to distinguish In if this situation, the rank of the atomapplicable. a species

Nind independent be increased, the reactions number of accordingly molecule matrix will for be feasible the to It decreased. is the to used reactions of number reduce aims construction of reaction schemes.

For example in the dimethylbenzene oxidation, 1,2-dimethylbenzene

be can only

does 1,3benzoic 3-methyl benzoic 2-methyl so acid, to not acid converted into form is isomeric the atom-molecule If 3.3). (in Fig. the dimethylbenzene added be infeasible avoided. reaction reactions will matrix, the

CH3 ul CH3 -

CH3

COOH
0 Feasible reaction Infeasible reaction ....................

CH3

CH3

CH3

COOH Fig. 3.3 Dimethylbenzene oxidation

39

Chapter 3

Construction of Reaction Schemes

In a reaction system, according to linear algebra, there are infinite solutions for this linear problem, AX (see Appendix B). In order to obtain all possible solutions that =0 satisfy reaction constraints and have the smallest values of coefficients, a two-stage strategy is proposed to guarantee all solutions are explored. This algorithm is based on the pretreatment of a stoichiometric coefficient vector in order to make the mathematical equation have a practical reaction meaning. The sign of the elements in the vector is determined during the reaction set-up, positive for products, negative for reactants and zero if not involved. The smallest integer values can be obtained through linear programming if a feasible solution is available, otherwise the reaction does not exist.

3.2.2 Two-stage reaction generation method

Given all stable species involved in the system, a strategy is needed to identify single reactions step-by-step to represent the situations usually encountered in which more than one reaction step is involved. A constraint of feasible reactions is that it should have an atomic balance. For the benefit of the reaction scheme construction, a two-stage method is used in the reaction generation, including reacting species classification, reaction set-up, atomic balance and generation of reaction list for each stage. The whole framework for the procedure is shown in Fig. 3.4. From this, the two reaction lists are obtained for the construction of the reaction scheme. In any reaction system, regardless of reaction kinetics, reactions whose reactants are happen either products or combinations of raw materials and products can only only from the combinations of raw materials. For after reactions whose reactants are purely first hydrogenation in Fig. 3.2, the the requires reaction to reaction scheme example, for the reaction scheme to exist. occur In any reaction scheme, one set of reactions can be obtained whose reactants are The from the of combinations raw materials. other set of reactions obtained purely involve reactants that are either products or combinations of raw materials and products. into based these two Accordingly, reactions are classified stages on reactants.

40

Chapter 3

Construction of Reaction Schemes

Fig. 3.4 Reaction generation framework

At least one reaction from Stage I can guarantee that the reaction scheme has a feasible start. The two-stage method can also simplify the feasibility checks for the reaction
scheme.

In the construction of a reaction scheme, reactions are selected from the reaction list of identifies involving Stage I the of procedure reactions with reactants only raw each set. identifies II involving Stage the procedure reactions with of reactants materials. A in the of raw materials and products. subsequent step products, or combinations from feasible Stage I Stage II into and reaction schemes. procedure combines reactions

41

Chapter 3

Construction of Reaction Schemes

3.2.2.1 Reacting species classification The proposed two-stage method is based on the classification of the reacting species into reactants and products. A reaction system consists of N species, represented as Species Set S, which has two subsets: the Reactant Subset R and the Product Subset P. R and P are dynamic sets, changing with the stage in the procedure. Eq. (3.7) between the the set and subsets. gives relationship S=RUP Where RcS, PcS (3.7)

In any reaction, reactants must be chosen from Reactant Set R, whereas products must be chosen from Product Set P. {Sl, 11 For Stage I, the Reactant Set is Ro= S2,""", S,. which includes all the raw materials fed to the reactor. Consequently, the Product Set is 1={ ST+,, S SN15 which +2,...,

includes all the new species generated in the reactor. For Stage I: S=Ro+Po (3.8)

For Stage II, the Reactant Set is Rl =S and includes all the species. The Product Set is the same as in Stage I, Pl = Po. No reacting species that are raw materials are allowed to be produced in any reaction of this two-stage strategy. When determining the reaction be irreversible. to scheme, all reactions are assumed 3.2.2.2 Reaction set-up An algorithm for selecting reactants and products from the different sets is used to set issues There are species two whether set-up: reaction regarding are up reactions. Stage In the of the each reactants/products. number of reactants or products, and Set R Reactant from selected with products are combined selected procedure, reactants 0 Y build P Set are the sets of combinations of to and from Product reactions. reactants and products.
Vf (S2),..., ={(Sl), (Sl, `'2), (S, )S3/,... 9(S1IS2)S3)... 1 (3.9)

42

Chapter 3

Construction of Reaction Schemes

O=

{(ST+1

)' (ST+2 /, .. ''

( T+1 I

), (ST+1, ST+2

), ST+3

(ST+1' " .. '

ST+2,

)... ST+3

(3.10)

According to the combinatorial theory, for any set W (n dimensions), an unordered choice of r different elements from a set of W is called an r-combination of W. Note that an r-combination is just a subset with r dimensions.
n
r

We denote the number of r-combinations of an n-dimension set W by

n! (n-r) r!

(3.11)

So the total number of reactions through the match of combinations of reactants and
products is:
T
rr

N-T

(3.12)

is is T N total the number of reactants. the number of reaction species, and where Fig. 3.5 shows the match of reactant and product combinations.

Fig. 3.5 Reaction setup

different This I. index three is allows vector The reaction set-up carried out using an or none. product, for reactant, species: reacting statuses

43

Chapter 3

Construction of Reaction Schemes

IT

lul

u2 , +1

IN

(3.13)

in which uj _ -1 , 0

for products for reactants not involved

In one reaction, any species cannot be a reactant and a product at the same time. That is, any element in the index vector I has a unique value. For example, an index vector A IT = [-1 B -1 F G """ 1 0] """

following the represents reaction: A+B -- F 3.2.2.3 Reaction feasibility: linear programming After obtaining all combinations of reactions, the reactions must be tested to determine balance in At the same time, the smallest value they or not. stoichiometric whether are for is the every combination chosen. sum of absolute reaction coefficients of If any reaction exists in the reaction system, species vectors are linearly dependent. That is, the atom-species matrix will be singular. Stoichiometric coefficients that are any bigger than the smallest value of stoichiometric coefficients have the same physical for for The the are required each steichiometric coefficients smallest values meaning. have is the to this Any to that ability match must problem solve chosen method reaction. both be linear linear A can programming equation solver and these two requirements. but linear the balancing, for can easily solve problem programming only atom used duplicate in to avoid order solution a minimum gives and of singularity, regardless find it is linear if feasible then is A can a solution, programming only reaction reactions. by the list the given coefficients stoichiometric reaction with added to the reaction solution.

44

Chapter 3

Construction of Reaction Schemes

A reaction can be described by the following reaction equation: Ax=O v is the reaction stoichiometric coefficient vector for one reaction
vT =[ vl v2 ... VNJ

(3.14)

(3.15)

which vj is the non-negative integer variable. So the stoichiometric vector is:

x=I"v

(3.16)

If a combination of reactions is feasible, then Eq. (3.14) must be satisfied and the is: between I x and relationship xi>0, xi=0, 0, < xi ifp=1 ifuj =0 if uj = -1

The objective function for linear programming is:

N

Min Z=>, ; _l St.

v,

(3.17)

A(I "v) =0

I <_ 0 clpj vi 0 >_ v feasible If then bound exists, solution the a value. is coefficient of the upper e where the values of x=I"v become the column vector of the stoichiometric coefficient matrix list. is the to reaction 0. The feasible reaction added

45

Chapter 3

Construction of Reaction Schemes

3.2.2.4 Stage II reaction generation After the reaction list of all the feasible reactions in Stage I is complete, the Reactant Set R for Stage II is updated accordingly (shown in Fig. 3.6). The procedure of reaction

Reaction list 1

Reaction list 2

Fig. 3.6 Changesof reactant and product set

setup and feasibility check in Stage I is repeated for Stage II to complete the reaction list. Any combination of reactants in Stage II cannot be the same as reactants of any reaction in Stage I. So
NT

j>1 j=l

where j =1,2.... T,... N

(3.18)

must be satisfied. When all the feasible reactions have been obtained, reaction lists for the two stages and the stoichiometric coefficient matrix 0 are complete. 3.2.2.5 Simplification If possible, the size of the reaction lists should be reduced by deleting some reactions. There are several different situations that need to be taken into account, even though In been it is in have the step. practice, added previous already often the some constraints 3 3 Also, than the that are reactants and products very rare. reactions with greater case for is less than the coefficients reacting species usually many absolute reaction value of 10. Furthermore, specific knowledge that particular reactions cannot take place allows them to be eliminated.

46

Chapter 3

Construction of Reaction Schemes

Once any possible simplification of the reaction lists has been carried out, the two reaction lists are complete. Assuming there are U reactions generated from Stage I and V reactions from Stage II, the stoichiometric coefficient matrix 0 is aNx (U + V) matrix.
I
rl al a2
O/R = aT r2 ru : ru+1

II
ru+2 "' ru+v

OUR

aT+l aT+2 oIIP aN OIIP

3.3 Reaction scheme construction

For a complex reaction system, the number of possible routes from raw materials to is large; products potentially very and it is impossible to tell which one is more appropriate than others. So choosing a reaction scheme for a complex reaction is always difficult for task, a especially a new reaction process. The most appropriate reaction be identified when combined with kinetic equation analysis, as will be scheme can only following limited in With the carried out chapter. preliminary experimental information, the second step of the reaction scheme construction methodology is to provide all important being in to schemes missed. plausible reaction schemes order avoid potential The reactions generated in Stage I and Stage II provide useful information about but it is difficult describe be to to that systems, still reaction can used possible reactions determine which reaction and how many reactions are involved in the reaction scheme. In general, the relationship among reaction steps in one reaction scheme can be described as different types: series reaction, parallel reaction and competitive and consecutive reactions. Series reactions: {A S R -> ->

47

Chapter 3

Construction of Reaction Schemes

Parallel reactions:

1AR AS or

AR B-*S

Consecutive and competitive reactions:

A+B

R -> B+R -*S

For more complex reaction systems, the definition is not clear. As there might be no appropriate type to describe it by, for example the reaction schemes shown in Fig. 3.7. With respect to different reacting species, a parallel reaction can become a series reaction. R A"" S yT A<R)T S/ A-S TW U V

B
Fig. 3.7 Complex monomolecular reaction schemes

If the reaction is a bimolecular

reaction, or a trimolecular reaction, the reaction schemes

will be more complicated.

The most important feature of a strategy to solve this problem involves the ability to generate feasible reaction schemes to include all plausible reaction schemes, and to provide basic information A the reaction about structure of any reaction scheme.

scheme constructed through randomly choosing reaction steps provides no guarantee that the reaction scheme is feasible. Also, the total number of all possible reaction from be describe theory. existing that calculated system cannot a reaction can schemes Relationships be in simply a complex reaction system cannot among reaction steps

described as consecutive reactions or competitive reactions.

So in this work, the concept of level is introduced to represent the relationships among first level The for in of construction. scheme reaction scheme reaction one reaction steps (and between involves 1) the (Level raw materials only reactions scheme a reaction involves (Level 2) level The the I Stage of reactions next reactions). corresponds with level of reactions (Level 3) involves the The level. first third from the species generated levels, two and so on. from the previous species

48

Chapter 3

Construction of Reaction Schemes

There are two possible extreme Situations that might exist for a possible reaction scheme: all reactions occur in parallel, or all reactions occur in series. The number of parallel reactions or series reactions is restricted to the number of independent reactions Correspondingly, Ni,,, d. in a feasible reaction scheme, the number of reactions selected

from Stage I must be equal to or less than Ni,,d, and also the total levels of any reaction scheme cannot exceed Nind-

Any feasible reaction scheme is a feasible route to connect raw materials with products by selecting reaction steps generated in the two-stage strategy. So all the species involved in the reactions must be either consumed or produced in the reaction scheme. Only after reactions occur between raw materials, can the whole reaction system be initiated. The number of reactions selected from Stage I must be at least 1 to guarantee that one reaction occurs from raw materials. Whether a product of the reaction system be inside in be a reaction scheme or not, cannot some reaction steps a reactant can determined by simple observation that this product has already been produced in dependent The that two of maybe steps reaction exists possibility step. reaction another help level test So to the also to the can concept others. each other without connection the feasibility of reaction schemes. determined be from they can Reactions in the first level only start raw materials, so depend level following the in I. The on the Stage list from the reaction reactions of is the Their the level. raw of sum in set reactant the previous products of reactions is If levels. there reaction any from the previous of reactions materials set and products feasible, is not level, this scheme in this reaction included been means any that has not deleted. be it and should 3.3.1 Incidence matrix

information 0 stoichiometric provides only not The stoichiometric coefficient matrix be to but used also can between products, and reactants on the relationships feasibility scheme. reaction a the of systematically check

49

Chapter 3

Construction of Reaction Schemes

An index vector qp is used to represent a specific reaction scheme, in which elements of the vector are integer variables. If reaction k is selected in this reaction scheme, it is set to be one, otherwise zero.
[(o T = i 9a (iou CPU+i (Pu+2 ... 4Pu+v

(3.19)

So as aNx

(U + V) matrix, the reaction step space 0 is divided into four submatrices:

O, 01 OR and 0,1p, according to the classification of reacting species and different R1 1 lists. reaction
rl al r2 ru rU+l rU+2 ru+v

a2
OIR aT (D
... aT+l ... ... ... ... ... ... ... ... ...

OIIR

(3.20)

aT+2 oIIP aN oIIP

Reaction through coefficient

scheme construction the information

finds the possible routes between reacting species the two-stage strategy. The stoichiometric

obtained from

feasible 0 be the reaction schemes. used as solution space of can matrix matrix in graph theory is used to represent the incidence of labelled

An incidence

is 1, The & Aldous, 1993). (Dolan the labelled matrix element value of arcs vertices and incident Similarly, the depends toward 0, the vertices. of arcs orientation on which or -1, labelled N U+V describe be and reactions a reaction system with used to matrix can also

defined is D incidence The as a labelled species. of a reaction system matrix Nx (U + V) matrix,

1 d17_ if species i is a product in reaction j; if species i is a reactant in reaction j;

-1 0 otherwise.

50

Chapter 3

Construction of Reaction Schemes

The incidence matrix D can easily be derived from the stoichiometric coefficient matrix 0 by restricting the elements of the be to matrix no less than -1 and no greater than 1.
rl r2 ru ru+l ru+2 ru

a,
a2

+v

dIR
aT

duR

(3.21)
a T+l aT+2 d1
aN

dj1

+1 ojk >0 where d jk = oak <0 -1

ojk=0

The incidence matrix no longer represents the molar balance within the stoichiometric but between the equations, connectivity certain reactants and certain products. The incidence matrix D is divided into 4 submatrices, d. d, d,, and d1p p ,m,

according to the classification of reacting species and reaction lists. Through matrix
transformations, it aims to:

1. Calculate the sum of row elements. This should be greater than 0 for products feasible for for 0 less than a reaction scheme. raw materials and 2. Make the values of all elements in submatrix d1p greater than 0 through in level in those the to the remaining previous column addition of a reaction
reactions.

3. Classify the reactions into different levels. If any of the three cannot be satisfied, this is not a feasible reaction scheme.

51

Chapter 3

Construction of Reaction Schemes

3.3.2 Feasibility check procedure

Before the feasibility check of reaction schemes is carried out, it must be ensured that be the reverse reaction of any other reaction steps in one any reaction step cannot reaction scheme. It aims to avoid the duplication of reaction reversibility when kinetic expressions are combined. In order to test the feasibility of a reaction scheme, the basic following 7 steps: the procedures and constraints are summarised as 1. Generate the incidence matrix D from the stoichiometric coefficient matrix (D. 2. Modify the matrix D based on any specific reaction scheme. From this, D(l) is obtained: djk(l) = dJk' (Pk (3.22)

3. Start from any reaction in Stage I, whose column is not equal to 0, add to every by II in Stage one. one reaction 4. If all the elements of any addition column in sub-matrix d11 are equal to or greater belongs I. It in Stage to following listed is the 0, this reactions all than then reaction 2, Level into be this is reaction that Level 2. If there classified can no reaction is incidence Otherwise the matrix feasible is therefore stops. and not scheme level, then the D(2), the represents superscript where updated and marked as continue. 0, less d than in start still are is sub-matrix 5. If there any reaction whose elements j1P incidence 4. The the 3 Steps mark of and from any reaction in Level 2 and repeat the procedure. is continue and accordingly, changed matrix level, the but outside Nid, there reactions some still level are 6. If the total reaches delete this reaction scheme. basic 3 following Nind N< rules the Level in and 7. If all the reactions are classified , feasible. is scheme this reaction are satisfied,

52

Chapter 3

Construction of Reaction Schemes

i)

The total number of reactions selected from Stage I is less than the number of independent reactions, and more than 1.
U 1_<L cp <_ Nina j

(3.23)

;_l
ii)

Every species in the raw materials must be consumed at least in the once reaction scheme, except catalyst, solvent or diluent.
U+V

D(L) <_ Vj T =1,2,..., -1,

(3.24)

iii

Every species except raw materials must be produced by the reaction step in the reaction scheme.
U+V

D(L) >_1, Vj=T+1, j=

T+2,...,

(3.25)

Because the elements of the index vector combined with the incidence matrix can only represent one orientation of any reaction step, it is straightforward to represent irreversible reaction schemes but not for reversible reactions. In order to avoid affecting the feasibility check of reaction schemes, missing the possibility of the reaction

duplication the of representations, the reaction reversibility reversibility and causing be This later in kinetic be the through will procedure. expressions represented will discussed in the following chapter. In addition, some empirical constraints can also be used, according to the specific in instance, For reactions, or some some products cannot appear as reactants system. be The in will the procedure scheme. reaction same appear cannot reactions demonstrated using an example.

3.4 Illustrative example

between desired is the oxygen, the net reaction product of Oleic acid epoxide Through in the dissolved chemical as solvent. acetone benzaldehyde and oleic acid,

53

Chapter 3

Construction of Reaction Schemes

analysis, all the species, including by-products and intermediates involved in the reaction system are: A: benzaldehyde, C6H5CHO B: oxygen, 02 C: oleic acid, CH3(CH2)7-HC=CH-(CH2)7-COOH D: perbenzoic acid, C6H5CO3H E: benzoic acid, C6H5000H F: oleic acid epoxide, CH3(CH2)7-HC-O-CH-(CH2)7-COOH A detailed model for oleic acid epoxidation in terms of a free radical mechanism 11 developed by Kuo and Chou (1987) from consisting of elementary reactions was initial rate data. Here it will be assumed that any intrinsic mechanism and kinetic information is unavailable. Without a model, reactor design and optimisation cannot be be data interpret So that well and can can experimental carried out. a reaction model be design for and optimisation must obtained. reactor used The atom-molecule matrix for oleic acid epoxidation is:
A B C D E F 0 0 1 0 0 1 0 7 H
0

M1 M2 AC

0 0 0
2

1 0

1 3
3

3 7 7
2 3 2

6
1

3 6 6 3

in which M1 represents CH3(CH2)7 M2 represents (CH2)7. , is 3, A, the the from matrix the atom-molecule matrix rank of After the SVD calculation is NNnd independent reactions =6-3=3. so the number of for Stage I Set Product Set Reactant the are and For oleic acid epoxidation, the {D, from is the The {A, F} E, set up Po reaction B, C} and respectively. Ro = = Po. Ro and combinations of Reaction list:

54

Chapter 3

Construction of Reaction Schemes

AHD A-E A<->F Stage I: AHD +E At->E+F At->D+F

After checking the stoichiometric feasibility

of all reactions using integer linear

balanced, feasible. is The third three reaction stoichiometri cally are programming, only but is impossible in practice from knowledge of chemical thermodynamics, and is deleted. 1 2 3B+ (A+B=D 2A+B=E 2C = 2F 1 2 A+B=D 2A+B=E

In Stage II the same procedure for the reaction step-up and feasibility check is carried II from Stage list Set. The Product Set Reactant the the reaction and after updating out includes three reaction steps: 3 4 5 C+. D=E+F A+D=2E B+2E=2D

is: for this reaction system The stoichiometric coefficient matrix

rl r2 r3 r4 r5

A B C D E F

-1 -1 0 1 0 0

-2 -1 0 0 1 0

0 0 -1 -1 1 1

-1 0 0

0 -1 0 2 -2 0

-1 2 0

55

Chapter 3

Construction of Reaction Schemes

Accordingly,

the incidence matrix is generated from the stoichiometric coefficient

matrix by restricting the elements to be -1: x< <-1 : rl r2 r3 r4 r5

A B

-1 -1

-1 -1

0 0

-1 0

0 -1

C
D= ... D E

0
... 1 0

0
... 0 1 ...

-1
... -1 1

0
... -1 1

0
... 1 -1

In this system, the number of possible combinations

of reaction steps is 21. After

feasibility check of reaction schemes, only 10 reaction schemes remain feasible.

Now three reaction schemes are selected to demonstrate how they are determined to be either feasible or infeasible. The level of the reaction system is shown using matrix transformation. Finally the reaction scheme is drawn as a flowsheet.
Reaction scheme 1:
011 0]

rpT=[1

rl A B C00 ... D1 ... -1 -1

r2 00 0000

r3

r4 -1 00 ...

r5 0 I> D(2)=C ... 0

rl

r2 -1 -1 0 0

rl + r3 -1 -1

rl + r4 -2 -1 0 0

r5

A B

-1 ... ... 011 ...

00
... ... ...

-1
...

00
... ...

-1
0 0 0 1 2 1

D E F

1 0 0

0 0 0

0 1 1

0 1 0

E00110 F00100

d11P D(1) are incidence two sub-matrix of elements In the original form of the matrix , less than 0 (highlighted by circles). So add column rl to column r3 and add column rl is There d11 in no element sub-matrix Check elements the all of value to column r4. . belonging to Check species 0, the reacting any of less sum is than stop. so whose value 0 is Po belonging than to greater 0 the species less any of is sum than and R0, its value be feasible, be must reactants to all For scheme a reaction (right side of the matrix).

56

Chapter 3

Construction of Reaction Schemes

consumed, i. e. the sum must be negative, and all new products generated, i. e. the sum must be positive (from the summation on the right of matrix). So this reaction scheme is feasible and the number of levels of the reaction scheme is 2. This reaction scheme is also obtained by Rastogi (1990). Reaction scheme 2: (OT=[l
rl

011

1]

r2

r3

r4

r5

rl

r2

rl + r3

rl + r4

rs

-1 -1

0 0

0 0

-1 0

0 -1

A B

-1 -1

0 0

-1 -1

-1 -1

0 -1

0
D E F 1 0 0

0
0 0 0

-1
(9 1 1

00
01 1@ 00

C*

D(2) -C

0
00

-1

0 ...
0 1: 0

0 ... ...
1 G 0

... ----. .:....

D E F 1 0 0 01 01

rl

r2

rl + r3

rl + r4

rl +r4+r5

A B C D3 = D E F

-1 -1 00

0 0

-1 -1

-1

-1 -2 0

_4 -5 _1 2 2 1

-1 0 TILL 0 1 1 0 1 0 :

10 00 00

1 0 0

In the original form of the incidence matrix D"),

three elements of sub-matrix d11Pare

less than 0 (highlighted by circles). So add column rl to column r3 and column r4 and , d11P There is in Check the still one sub-matrix value of al elements column r5 . . into Level 2. 0, less is than and reaction r4 so put reaction r3 element whose value is less is There than Continue to add column r3 to column r5. no element whose value less its is Ro belonging that to Check value 0, so stop. the sum of any reacting species 0. The is Po belonging than to criteria greater than 0 and the sum of any reacting species levels feasible is the the of reaction of number and scheme this reaction are satisfied, so 3. is scheme

57

Chapter 3

Construction of Reaction Schemes

Reaction scheme 3:
(pT = [0 111 0]

rl A0 B0

r2 -1 -1

r3 0 000

r4 -1

r5 0

rl

r2

r3

r4

r5

A B

0 0 00

-1 -1

0 000 -1 QG

-1 00

00 Df\-C ... ... D00 E01110 F00100 ... ...

-1 ... J]

00 D(2) ... G0 ... -C D E F

_1 0 3 1

00 01110 00100

In the original form of the incidence matrix D(1) two elements of sub-matrix d11p are ,

less than 0 (highlighted by circles). So add column r2 to column r3 and column r4 .

Checking the values of the elements in sub-matrix d11 there are still two elements less ,

feasible species/reactic Reaction scheme 1 Reaction scheme 2

infeasible species/reactions """""""""""""" Reaction scheme 3

Fig. 3.8 Reaction schemeexamples

is D Because the not species reacting infeasible is scheme. reaction an than 0, so this level. following in be the it level, first then a reactant in cannot the produced

58

Chapter 3

Construction of Reaction Schemes

Finally, the reaction schemes are drawn in the form of flowsheet in Fig. 3.8 to clearly show the feasibility of reaction schemes.Dotted lines in reaction scheme 3 represent the impossible appearance of reacting species, then reactions.

3.5 Conclusions
Conventional methodologies of reactor design and optimisation for speciality chemicals applied to complex reaction systems lead to the process being operated under nonoptimal conditions. A new systematic method to combine the work of chemists and chemical engineers is necessary, to make full use of experimental information, to extract an optimal model suitable for process design and with the minimum number of laboratory to the expense of and pilot experiments. experiments reduce In this chapter, a new methodology of reaction scheme construction is proposed. After all detectable and stable species (reactants, products and reaction intermediates) are known, a matrix formulation allows all participating atomic and molecular speciesto be factor is important The the and matrix as a very rank of systematically represented. decomposition) (singular SVD the to the through obtain method value calculated for independent a specific reaction system. reactions number of Integer linear programming is used to test the stoichiometric feasibility of the reactions in the reaction set-up through products and reactants of random combinations generated list. A into is feasible the Each reaction stoichiometric reaction entered reaction step. is list, to from built is provide the two-stage used which reaction matrix coefficient for generating all possible reaction schemes. guidance is from derived used the reaction stoichiometric coefficient matrix An incidence matrix 7-step following by procedure. a to test the feasibility of combination of reaction steps The levels whole strategy can obtained. At the same time, the of reaction scheme are feasible generated. are schemes reaction all guarantee

59

Chapter 4

Hybrid Optimisation of Rival Models

Chapter 4: Hybrid Optimisation of Rival Models

4.1 Introduction 4.2 Problem description 4.2.1 Preliminary experimental design 4.2.2 Data fitting 4.2.3 Reaction system modelling 4.3 Rival models 4.3.1 Optimisation framework

4.3.2 Objective function 4.3.3 Hybrid optimisation 4.3.3.1 4.3.3.2 Simulated Annealing (SA) Nonlinear Programming (NLP)

4.3.4 Implementation of the optimisation 4.3.4.1 4.3.4.2 4.3.4.3 Simulated Annealing framework Optimisation moves Parameter precision improvement

4.4 Illustrative cases 4.4.1 Base case 4.4.1.1 Reaction list generation 4.4.1.2 Parameter estimation 4.4.1.3 Results and analysis 4.4.2 Oleic acid epoxidation reaction system 4.4.2.1 Model building 4.4.3 Discussion

4.5 Conclusions

60

Chapter 4

Hybrid Optimisation of Rival Models

In this chapter, a new approach is discussed hybrid a using optimisation method to obtain a set of reaction schemes and kinetic expressions as rival models for model discrimination. This will efficiently make use of experimental information.

4.1 Introduction
As a complete model for describing the reaction system, it includes two aspects: the reaction scheme and associated kinetic expressions. In chapter 3, the strategy for the reaction scheme construction was discussed in detail. In this chapter, rival models for the same reaction system will be derived as a part of the model building procedure.

Stoichiometric analysis

Model Derivation

Preliminary experiments

Reaction scheme and kinetic rival models Further experimental design

Model Discrimination

Model discrimination and improvement of model accuracy

Fig. 4.1 General model building framework

For a complex reaction system, the number of possible reaction schemes is very large. Also it is impossible to tell which one is a better representation than another without any information from experimental data and kinetics. The experimental measurements must 1978) & Pasek, (Horak building to hand hand in the make use of model with go for target the information to minimum experiments. efficiently and reach experimental is information that 4.1, to Fig. in As shown provide preliminary experiments are derivation. for rival model essential dynamics describe the to kinetics of reaction Chemical consists of a set of equations industrially fitting. For from data most estimated are parameters systems, whose

61

Hybrid Optimisation of Rival Models

relevant reactions, the kinetic parameters cannot be estimated reliably from theory and be determined by experiments. must In practice, the kinetic description is still amongst the most difficult tasks in the model building procedure. In particular, detailed models for complex reaction systems confront the following difficulties: the reaction mechanism remains unknown or too many assumptions; a large number of reacting species and possible reaction steps are involved; there is a large number of possible reaction schemes; a large number of model parameters need to be estimated. If the reaction system involves heterogeneous catalytic reactions, there are also a large number of variables available to represent the external and internal diffusion effects. Because of the complexity of chemical reaction processes and the short market window of chemical products, there is always a compromise between the desire to spend a lot of time to study the detailed mechanism of complex reactions and the requirement that an approximate model should have ability to represent the key features of the reaction system to avoid major opportunities being missed. Hence, it is necessary to find approximate models for these complex reaction systems by the fast and effective evaluation of experimental data, to shorten development time to market. With limited preliminary experimental data, there are many applications in which an experiment can conform to more than two models within a certain confidence level. So no reaction model can be determined without further experimental validation. At the early stage of reaction model building, a premature decision on which reaction is the best model might lead to the wrong research direction and process scale-up failure. In it is to the appropriate to explore all potential order obtain most reliable reaction model, data. have It is that essential that good agreement with preliminary experimental models the method selected for data fitting has the ability to provide multiple solutions as rival kinetic including expressions. reaction scheme and models,

4.2 Problem Description

fitting from data directly. be It information Kinetic obtained experimental will also can help For information to to schemes. some screen rival reaction reaction useful provide

62

Chapter 4

Hybrid Optimisation of Rival Models

schemes, their kinetic models might not be in good agreement with experimental data within the range of feasible kinetic parameters and thermodynamic constraints.

4.2.1 Preliminary

experimental design

The primary objective of the preliminary experiments is to collect enough data to begin the model identification and parameter estimation procedure. It is also desired to

determine which variables have a significant effect on the response of the system, and what are the ranges of these variables that will give the most desirable value of from The this stage of experimentation are expected to provide a response. results insight behaviour. into For example results from the initial the qualitative system help in deciding experimentation may upon an appropriate optimisation variable, or may kinetics information the of the system. on provide valuable Many techniques are available for the design of preliminary experiments, e.g. the classical one-variable-at-a-time factorial approach, design and nonlinear/optimal

discussion detailed design. A of the methodology and relative advantages or sequential disadvantages of the various approaches can be found in the many books (Box et al., 1978; Cochran & Cox, 1957; Montgomery, 2000) on the design of experiments. The knowledge 1992) & Donev, (Atkinson design techniques require nonlinear and optimal the to and approximate the variables, operating the response relating model of knowledge of the model parameters. Since at the stage of the preliminary experiments, is the kinetics used knowledge thermodynamics commonly available, and of no clear for is It the best is design studying efficient the factorial more choice. usually method of factors than experiments. one-variable-at-a-time two more or effects of be data forces design to the orthogonal and allows The method of factorial experimental determined be thus input to and importance variable determine each of the to relative us Factorial efficient represent also experiments to develop a parsimonious model. time, than at a one rather All simultaneously, the changed are variables experimentation. Because the is property orthogonality of reduced. needed experiments the of number so be lower than have obtained can variance a design, estimates factorial coefficient the of 1978). (Box design al., et experimental with a nonorthogonal

63

Chapter 4

Hybrid Optimisation of Rival Models

From a practical standpoint, the decision on which input variables be should studied will determine the number of tests that must be carried out. In a standard factorial design, 2 tests are required, where n is the number of input variables to be studied. The determination of the region of experimentation requires process knowledge. The experimental range should be chosen so that the resulting measurements of the response do not involve errors in the sensors that are greater than the typical noise level. After the experimental design method is chosen, variables expected to influence the response (yield, selectivity, conversion) must be analysed carefully. For a reaction system, temperature, initial concentrations, pressure, catalyst concentration etc. all can be factors.

4.2.2 Data fitting

Once the experimental data are available, extracting as much information as possible from the limited data for the reaction scheme and reaction kinetics is the main aim for data regression. Finding the model that closely matches the experimental data becomes an optimisation problem. In order to measure or evaluate the agreement between the data and the model with a designed be in to which small chosen or particular set of parameters, an estimator needs The to then the adjusted model are of parameters agreement. values represent close The best-fit in the adjustment parameters. estimator, yielding achieve a minimum dimensions. in in is thus many minimisation a problem process The most commonly used estimator is the least square, which is based on the principle independent likelihood, the and are errors measurement the assuming maximum of deviation. distributed with constant standard normally There in be interpreted data are some kinetic ways. several In general, can experimental from kinetic for kinetic the model coefficients estimating of conventional methods differential integration (or the of set of data: numerical) analytical experimental Both directly. data to straightforward are the differentiation empirical of or equations, apply to a single reaction system.

64

Chapter 4

Hybrid Optimisation of Rival Models

For a complex reaction system, the reaction model most likely depends nonlinearly on model parameters, while the number of parameters to be estimated increases very rapidly with the complexity of the physico-chemical model. The application of iterative non-linear least-squares regression techniques is necessary. The Levenberg-Marquardt (also method called the Marquardt method) works very well in practice and has become the standard for nonlinear least-squares routines. The nature of the problem of obtaining a set of reaction schemesfrom a large number of feasible reaction schemes and rival kinetic models is aM NLP problem. The approach have to this the ability to cope with the selection of the solve used problem should kinetic For reaction scheme and expressions simultaneously. a complex reaction system, the problem size will be increased, thus the approach should be able to solve a large for large initial MINLP Furthermore, a guesses number of parameters will also. scale difficulties In to the optimisation. addition, multiple solutions are required to present data fit the that than the same experimental one model can more phenomenon represent due level, to experimental errors. confidence certain a within The drawback with deterministic methods is that they are only able to find the solution for initial depends The in the neighbourhood of starting point. value on good solution better If local in be is the it trapped starting a optimum. very easy to starting point, so be the be more accurate. result will obtained using other methods, point can It MINLP handling in difficulties have problem. Deterministic methods such a complex is necessary to use a robust estimation method, allowing the whole parameter space to be explored in order to determine multiple solutions to the problem, and not merely a is the hybrid search allows In which chosen, this optimisation work, a single solution. including the is This rate of to correlation large converge able through parameter spaces. parameters and provides multiple solutions.

4.2.3 Reaction system modelling

balances all reaction of mass on concentration, the In order to obtain model prediction formation disappearance The be of or of rate out. carried in the system should species In when depends general, temperature composition. and on A, rA or rA component -

65

Chapter 4

Hybrid Optimisation of Rival Models

one species in a specific reaction is selected, its concentration is monitored as a function of time or flowrate, depending on whether the reactor is batch or continuous.

Commonly, two kinds of kinetic equations are used: power and hyperbolic equations. For instance, the reaction rate of the following reaction: A -> products be linear function may a of the species concentration, kCA - rA = form a or general of the algebraic equation, such as:
kACaCB.... - rA = -k' CSCT.... (4.2)

(4.1)

The second general form is hyperbolic: kACACB.... -r=A 1+kACCB.... (4.3)

k from is determined termed as the reaction rate experimental observation. which are both be irreversible kinetic These to and used represent expressions can constant. by determined term. the the of reversible appearance reactions, reversible The temperature effect is accounted for within k, k=A exp(Ea RT ) (4.4)

is T R is factor, Ea the frequency is A the constant, and gas the activation energy, where is the temperature. Thus to that a It is often necessary to convert the rate of reaction of a species of another. stoichiometric between the all rates of reaction relationship provide can reaction

Considering the general reaction: species. VAA+VBB--4VCC+VDD it can be easily written:

-RA
VA

Y=

RB VB

=Rc

Vc

=RD

(4.5)

VD

66

Chapter 4

Hybrid Optimisation of Rival Models

where r is the extent of this reaction. In complex chemical reaction systems, typically multiple reactions will occur, some desired and some undesired. The net rate formation of of each species is required for the mass balance. If R reactions are taking place Reaction 1: Reaction 2: Reaction 3: A+B k' > 3C+D > 3E 4F

A+ 2C k2 k3 2B + 3E

Reaction R:

A+ 1/2B -

kR )G

Then the net rates of reaction of all species are

RA =( -rl )+( -r2 )+ (-r3 )

RB =(-rl

)+(-2r3

)+(-1/2rR )

Rc =(3r1)+(-2r2

General chemical equations for a complex reaction system are given by:
xkAi =0

k=1,2,..., R

(4.6)

The net rate of reaction for speciesAi is the sum of all rates of reaction in which species Al appears, that is:
R RA; = xik rk

(4.7)

k=1

All reaction systems, batch or continuous, should satisfy the mass conservation law. A following in instant At the for time, balance t, equation: yields species at any mole In - Out + Generation = Accumulation That is, for a homogeneous reaction system:
Fa, 'in-F.. + f dV_dN4 RA; dt

(4.8)

67

Chapter 4

Hybrid Optimisation of Rival Models

For batch reactor FAQ FA 0, = so the general mole balance equation becomes: =
RA,dV = dNA, dt (4.9)

dN` For a CSTR operated at steady A. state =0, dt FA - FA' RAi

RA. dV = VRA, it becomes: ` (4.10)

Similarly, for PFR the mole balance equation is:

dFA, dV RAj (4.11)

When the mole balance equations are combined with reaction rate equations, a set of ordinary differential equations (ODEs) is obtained. Also, mass transfer and heat transfer equations are coupled, leading to an ODE/algebraic, initial value problem (IVP). There are several methods for solving ODE problems. The fourth-order Runge-Kutta method is most often used. Before any method is used, system analysis must be done. For a fixed reaction scheme and associatedkinetic equations, the ODEs present either a stiff problem, or a non-stiff problem. When a stiff problem is integrated in some interval, such as [0, b], the stepsize needed to maintain stability is much smaller than that needed to meet the accuracy requirements. This is a criterion to test if the problem is stiff or not. So the integration method should be chosen accordingly. In this research work, the reaction scheme and kinetic equations are moved randomly during the optimisation, so sometimes the ODEs are non-stiff, at other times they are ODEs. Also, it is the the the with construction of possible stiff, and method must switch that in some situations, the ODEs are ill posed, which should be deleted to avoid inaccurate physical meaning. The method initially assumes the system of ODEs to be for does integration. If Runge-Kutta fourth-order this the not method non-stiff and uses be integration to then the to switches accuracy achieved a the numerical required allow difference The in backward for this method. case a stiff systems, method suitable in Fig. 4.2. described is calculation procedure

68

Chapter 4

Hybrid Optimisation of Rival Models

Fig. 4.2 Simulation method framework

4.3 Rival Models

There are many applications in which an experiment can conform to more than two

known probability models, all within the same sample space.

For instance, maxima on concentration versus reaction time plots are a typical feature of indicate In the only a maximum might not appearance of reverse, consecutive reactions. that (Horak & Pasek, 1978) the system of reactions taking place involves consecutive but reactions, or consecutive reactions as a part of a more complex reaction scheme, fast irreversible, reactions. slow and also some combinations of reversible and

features, fit have 4.3 Fig. in the and The two reaction schemes shown same further information, it Without level. data well within a certain confidence experimental is impossible to select one reaction model to describe the reaction system. larger is than the balance, the reactions possible all Through an atomic number of Selection to scheme a reaction construct independent of reactions reactions. number of

69

ter 4

Hybrid 0

n of Rival Models

Model 1
A+ B---> C A+ C----> D
a2 (i = k, C C 73 Z = k2`"f+1 C

Model 2
{A+ A+ B<-4 C B- D
ri = k1Cq'Cgz
r2 = Y, k2CA

CC3 -k k

)/ 2 CC

80 j-60 ' :

"

Exp. Data -Model 1 Modelt

0246

Time

Fig. 4.3 Data fitting curve

be done in two ways, sequentially or simultaneously. can

For example, in a 6-species

reaction system, the number of possible reactions is 7, but the number of reaction schemes exceeds 20, and every scheme includes more than 3 single reaction steps. Then data fitting can be used for the parameter estimation to obtain kinetics for all reaction schemes, so the model space is too big for the next step of model discrimination. The new approach uses an optimisation method for reaction scheme construction and

kinetic selecting a expression, while obtaining a set of suitable schemes and kinetics as rival The stochastic method enables consideration models. of complex non-linear

formulations,

decisions addressed as closed or sequential simulation models, with many

is is first The that obtained near the a group of solutions advantage stochastic variables. optimal region.

4.3.1 Optimisation

framework

After the reaction system is formulated as an MJNLP problem, hybrid optimisation is 4.4, in Fig. in to in order obtain a two-stage scheme, shown optimisation a carried out set of rival reaction models.

70

Chapter 4

Hybrid Optimisation of Rival Models

Problem Statement

MINLP Problem

Stochastic Optimisation

NLP Optimisation

Fig. 4.4 Optimisation method

The initial

stage uses stochastic optimisation techniques in the form of simulated

final the the annealing, which guarantees solution within a optimum performance of level. certain confidence The second stage makes use of mathematical programming techniques to fine tune the by from varying the continuous variables. stochastic optimisation solution obtained

4.3.2 Objective function

In order to fit the model to experimental data, a non-linear multi-parameter estimation factors, frequency (i. Thus followed. is energies, activation e. all parameters approach to reacting species) are evaluated simultaneously. respect with orders reaction fitting data the to function evaluate needs For a reaction system, the objective of different for the species. difference between measured and predicted concentrations Yet low they high be somehow must different concentrations. These or at might species be combined to give a single objective function. i=1,2, data N have Suppose we points yi, parameters ai ,i=1,2, N, to a model that has M adjustable ...

between the functional M. The model predicts a relationship ...

dependent variables: independent variables and

(xi; a2,... at yj yi = ,

aN)

(4.12)

71

Chapter 4

Hybrid Optimisation of Rival Models

The data have a different precision due to the different analysis methods. This would normally be quantified by an objective function of the type of general least squares (GLS) : Min a2 = jjjk,
i=1 j=1 k=1

j, k(eXPtl)-Yi, j, k(calc)p

(4.13)

or Min y,,fi k (exp tl) - yi jk (calc) 62 = (exp ) tl yi, i=i j=i k=1 j, k 2 (4.14)

indices k i, j, the where relate to experimental runs, samples and reacting species, and kth is the the concentration of sample of jth experiment in ith experimental yt.j_k condition. However, the number of reaction steps in one reaction scheme used to describe a factor for building. is important More model reaction specific reaction system another be difficulties in the simulation and to solved and pose steps mean more equations need control of the system. A new objective function is proposed to account in these factors:
EE [Yi, ) Y)-yi, l, k(calc i, k(exptl

Min

F= N`=''='k=l

_1

(4.15)

in the is N model. the used equations stoichiometric of number where between difference the measured and function the Thus, the new objective minimises the the time, model. the of complexity reduces same at and, predicted concentrations

4.3.3 Hybrid

optimisation

4.3.3.1 Simulate Annealing (SA) is (1983) by Kirkpatrick introduced and a generalisation et al. Simulated annealing was in between the a metal which way that Carlo an analogy exploits Monte method of a into structure. crystalline energy freezes minimum cools and

72

Chapter 4

Hybrid Optimisation of Rival Models

In an annealing process, a melt, initially at high temperature and disordered, is slowly cooled so that the system at any time is approximate in thermodynamic equilibrium. As cooling proceeds, the system becomes more ordered and approaches a "frozen" ground state at T=0. Hence the process can be thought of as an adiabatic approach to the

lowest energy state. If the initial temperature of the system is too low or cooling is done insufficiently slowly the system may become quenched, forming defects or freezing out in metastable states (i. e. trapped in a local minimum energy state). By analogy the generalisation of this Monte Carlo approach to combinatorial problems is straightforward (Kirkpatrick et al., 1983; Cerny, 1985). The current state of the

thermodynamic system is analogous to the current solution to the combinatorial for is The the thermodynamic system analogous to the energy equation problem. is function, the state analogous to the global minimum. and ground objective The direct precursor to the SA algorithm was the Metropolis algorithm (Metropolis et ) (with E! from Metropolis to The 1953). energy point an arbitrary moves algorithm al., ) (Ej E; finds E1) (with the at the next state equilibrium energy change and energy depends be the in Whether to on or rejected accepted that state. state space are moves by Metropolis the algorithm. probability criterion provided If immediately. is the change is in If the change energy negative the new state accepted in energy is positive, it is accepted with a probability: E. -E. `) 1, (T) exp(pi,; = min kT (4.16)

is E the Boltzmann k is energy the constant, the is T temperature system, the of where index j respectively. i, states, the new and old of are value, and development, for background the The Markov chain theory provides the essential is Process Markov A based Carlo a Monte algorithms. behaviour and convergence of the state given a of the outcome of probability where states, of sequence stochastic depends only on the outcome of the previous state.

73

Chapter 4

Hybrid Optimisation of Rival Models

Simulated Annealing is a Monte Carlo be that method can modelled mathematically using the theory of finite Markov chains. In the case of SA, a state corresponds to a move, and the set of outcomes is given by a finite set of neighbouring states.Each move depends only on the outcome of the previous attempt, so the concept Markov of chains Since the number of the states does not affect the probabilities, this feature will applies. help to remove the effects of initial guesses. This process is then repeated sufficient times to give good sampling statistics for the current temperature, and then the temperature is decreasedfollowing a cooling schedule until the final temperature is reached. To govern the convergence of the algorithm, a set of parameters, known as a cooling schedule, are specified by: " "a "a "a initial an value of the control parameter (i. e. temperature) finite length of each homogeneous Markov chain final value of the control parameter or a termination criterion decrement function for lowering the value of the control parameter.

Determining these parameters is a challenge for implementing Simulated Annealing. There has been much research on the topic, dealing mostly with heuristic schedules. There are two main categories of heuristic schedules: static and dynamic. In a static during fixed be the execution the and cannot changed parameters are cooling schedule, dynamic With the cooling schedule, the parameters are adaptively a of algorithm. during the execution. changed A suitable initial temperature is one that can make the average acceptance probability depend initial the temperature 0. Thus, the on specific problem. the will of value about The Markov chain length Lk is a very important parameter for stochastic optimisation implementation. if it is too large, the optimisation is very slow, as many simulations it is If level. too the temperature system small, be annealing at each to performed need be "quenched" obtained. and no reliable results will will be

74

Chapter 4

Hybrid Optimisation of Rival Models

In some implementations of the SA algorithm, the final temperature is determined by no improvement (i. e. no new best solution) being found at this temperature or the acceptance ratio falling below a given small value. There are two widely used cooling schedules: 1. The simplest and most common temperature decrement rule is: tk+, = a' tk k =0,1,2.... (4.17)

where a is a constant close to, but smaller than 1. This exponential cooling scheme (ECS) was first proposed by Kirkpatrick et al. (1983), a=0.95. 2. Another cooling schedule is the Linear Cooling Scheme (LCS) in which tk is in reduced every trial (while avoiding negative temperatures): tk = tk - AT k=0,1,2,... (4.18)

Randelman & Grest (1986) found the reductions achieved using the two schedules to be comparable, and also noted that the objective function was, in general, improved with Finally, they the expense of greater computational effort. slower cooling rates at depended than the the that the on rate on cooling more algorithm performance observed individual values of control parameter and Markov chain length. Some general guidelines exist when choosing an annealing schedule. For instance, there is a trade-off between choosing small decrements of the control parameter (tk) and

decrements (Lk ). Usually lengths the Markov long control of small chain choosing long Apparently, long (tk) when a sufficiently chains. are chosen to avoid parameter improvement iterative the optimal as is replaces annealing simulated used, schedule schedule. is (1985) temperature the updated annealing Aarts and van Laarhoven suggested that according to:
tk+l tk (1 +) '

ln(1 + y)tk

(4.19)

3(tk)
75

Chapter 4

Hybrid Optimisation of Rival Models

where a is the standard deviation of the objective function, and y is a parameter that controls the speed of cooling and stands as a measure of the proximity to equilibrium. However, the standard deviation might be very small for an annealing temperature and the system will be quenched. To prevent this, Mehta (1998) suggested the use of an additional constraint:
to

6(ta) k

10,

(4.20)

/2 Lk so either moves are accepted or a maximum of Lk moves are attempted, first. whichever occurs Researchers have proposed more elaborate, mostly adaptive, annealing schedules, using statistical measures to modify the control parameters. Unexpectedly, non-monotonic have been in observed as optimal schedules some situations. In stochastic optimisation the search proceeds in a stepwise manner to generate a based in the space, on a set of probabilities. solution random path Start with an initial guess " Propose a random modification to the system " Apply criteria to accept or reject the modification Iterate " until termination criteria are met Simulated Annealing (SA) has advantages and disadvantages compared with other tabu search, and neural techniques, algorithms, as genetic such global optimisation implementation the its Among the ability and of ease relative are advantages networks. Though for a many combinatorial problems. to provide reasonably good solutions for deal for time include drawbacks its the of computer great a need technique, robust tunable parameters. chosen many runs and carefully discrete for is (SA) Annealing variables. problems with suitable Generally, Simulated discrete and continuous variables, continuous to When it is applied a problem with

76

Chapter 4

Hybrid Optimisation of Rival Models

variables are unlikely to reach the exact optimal points, due to the discrete nature of the moves. Optimisation tools start from an initial guess, search through the solution space, and converge to an "OPTIMAL" state. Unlike deterministic methods, where gradient information is used to evolve the search, in stochastic optimisation the moves are In random. process synthesis, each stochastic move outputs a new design instance, which is assessed to guide the evolution of the search. The assessment calls for simulation of the design and calculation of the overall performance. The search generates a chain of design instances, thus the programming effort is minimised to a series of simulation tasks. The stochastic evolution enables the consideration of: " " Complex non-linear formulations Closed or sequential simulation models

decisions Many " addressedas stochastic variables "A set of solutions close to targets

The convergence properties of the stochastic search depend on the strategies adopted to guide the evolution of the process. One extreme is to accept every design generated through the search, which leads to a completely random process of no use for The is iterative improvement, other optimisation. extreme where only moves that Stochastic based benefits immediate to the accepted. algorithms, objective are present Carlo Monte simulation, assume a probabilistic acceptance scheme that allows on deterioration of the system as well as improvement, starting from the completely improvement. iterative to random mode and smoothly switching The choice of SA allows flexibility in the way that the solution space is represented and large for is parameter spaces. complex reaction systems with searched that suitable 4.3.3.2 Nonlinear Programming (NLP) NLP deterministic method is used in the parameter precision improvement, after Discrete that represent reaction variables are obtained. solutions multiple near-optimal Continuous from fixed be variables optimisation. stochastic can scheme composition

77

Chapter 4

Hybrid Optimisation of Rival Models

that represent kinetic parameters need to be further optimised. In this work, a successive quadratic programming NLP methods. SQP (SQP) algorithm (NAG subroutine) is adopt from the available uses an implementation of Powell's successive quadratic

programming algorithm and is aimed specifically solves the quadratic programming

It large, sparse at nonlinear programs. reduced

by subproblems using a sparsity-exploiting

gradient method. Sparse data structures are used for the constraint Jacobian, and there is an option to represent the approximate Hessian as a small set of vectors using a limited memory-updating scheme.

Even though SQP is likely to be trapped in the local optimum in the neighbourhood of

framework Annealing Simulate 4.5 Fig. optimisation

78

Chapter 4

Hybrid Optimisation of Rival Models

the starting point like other NLP optimisation methods, with good initialisation based on results of SA optimisation method, it can guarantee that optimum points can be reached and multiple solutions obtained as rival models for model discrimination.

4.3.4 Implementation

of the optimisation

This specific reaction scheme and kinetic model optimisation involves problem combinations with a large number of continuous variables and discrete variables. Which is reaction selected, which type of rate equation is used, and which species affect the reaction rate, etc. are all addressed as discrete variables. Reaction order, activation energy and frequency factor are described as continuous variables, moving between lower bounds and upper bounds assigned by the user. 4.3.4.1 Simulated Annealing framework During SA optimisation, starting from an initial state and annealing temperature, a new is its state generated and objective is evaluated, as shown in Fig. 4.5. When the different the acceptance criterion stipulates rejection of new state, a state is generated. The acceptance criterion is controlled by move probabilities. When the new state is Markov long for As be basis it the the the the of as end next modification. accepted, will is Markov deviation is the the the chain of elements of standard chain not yet reached or too low, the Markov loop will be continued. If no acceptable standard deviation can be found, the optimisation ends abnormally. Otherwise the cooling schedule is applied at the end of the Markov loop to generate a new annealing temperature. The stochastic following termination the criteria are satisfied. of any when optimisation ends indicating bound, lower beneath that the falls 1. The annealing temperature a Simulated Annealing terminates properly indicating Markov that for steps, 2. No transitions are accepted a certain number of frozen is the system Markov for 4.19 Eq. does a certain number of not satisfy 3. The standard deviation frozen is the that indicating system steps,

79

Chapter 4

Hybrid Optimisation of Rival Models

4. A maximum number of Markov chains are evaluated, indicating that the Simulated Annealing did not reach a stable solution with minimum energy yet.
In order to obtain reliable results, annealing parameters should be adjusted to fast obtain convergence based on specific problems. It is also suggested that multiple runs can be used to analyse the average value of the objective function, avoiding the result of one run beyond a certain confidence objective value. level according to the normal distribution of the

4.3.4.2 Optimisation
Modifications

moves
include two kinds of moves: reaction scheme moves

in SA optimisation

kinetic and model moves as shown in Fig. 4.6. Reaction scheme moves are discrete moves, including: " 9
"

Add reaction Delete reaction

Change reaction

Reaction scheme moves are subject to the construction strategy of reaction schemes. form discrete be both the kinetic to hand, On the other moves modify model moves can

Optimisation Moves

Kinetic model changes

Reaction scheme changes

Change equation

Frequency factor

Reaction order

Activation energy

Number of reactions

Reaction involved

Fig. 4.6 Optimisation moves in SA

80

Chapter 4

Hybrid Optimisation of Rival Models

of the equation and continuous moves to modify the reaction parameters, including: " 9 9
"

Change of the form of kinetic equation Activation energy modification Frequency factor modification
Reaction order modification expression for any reaction step in a certain reaction scheme is in the

If the kinetic

reversible form, the feasibility of the reaction scheme will not be affected.
Moreover, kinetic parameters as continuous variables have constraints to satisfy the

For instance, frequency factor should be lower than the collision the physical meaning. frequency of the molecules in the gas phase, and normally ranges from 10-6 to 1016.The 50 be 5 kcal/mol, lower than than activation energy must a positive number greater and kcal/mol, the order of magnitude breaking for bond the the chemical of energy

(Santacesaria, 1999). The reaction order for individual species is between -2 and 2. In Fig. 4.7, three reaction models are used to show how the variables move from state to

discrete and continuous moves. state using

A+ B-> D A+D-2E C+D-> E+F

A+ B--> D A+D->2E C+ D-> E+F

A+ B---> D C+D ---* E+F +2E---> 2

CACB r, =k,
r2=k2CACo r3=k3CCCD

ME*

r, = k, CACB
r2 = k/$ '0

=I*

r, =k, CACB r2=k2CCCo

r3 = k3 CBCE

r3 = k3CCCD
Fig. 4.7 Example of state-to-state moves

These by driven is modifications. random the search During the stochastic optimisation, which moves, into perturbation called are from state a new state old an modifications These kinetic probabilities parameters. and by structural of probabilities are controlled towards to during preferences reflect fixed optimisation be modified or can either kinetic parameters. and certain reaction schemes

81

Chapter 4

Hybrid Optimisation of Rival Models

In practice, the sum of move probabilities is normalised to 1. The value is distributed among all the moves, the bigger the probability is, and the more important the decision
is.

4.3.4.3 Parameter precision improvement In order to searclafor local optima near SA optimisation results, the search regions are narrowed. In this work, 10% is allowed while still in the range of kinetic parameter constraints.
In order to obtain the multiple solutions, multiple runs of optimisation should be carried out. In each run, simulated annealing and NLP are running sequentially.

4.4 Illustrative

cases

In this chapter, a base case and catalytic epoxidation of oleic reaction are used as examples to elucidate the method of model building. First, the hybrid optimisation was tested on a case for parameter estimation, to see if this method is suitable for continuous he is fixed. In this method, the reaction order, ': reaction scheme variable problems when frequency factor known through optimisation moves. are activation energy and

4.4.1 Base case

Time A, D
A: R1R2 B: RIRZR3 C: RIR2(R3)2 D: R3 E: (R3)2 R1,R2,R3: Functional b oups

A, B, C, D, E
Fig. 4.8 Base case

A, 2001), (Coker, materials raw In this homogeneous constant-volume reaction system C, A, B, in C, E B, components which batch then observed, are fed into D are reactor, a The kinetic for the study. method analytical D are measured using a suitable in 4.8, Fig. in listed order assumed are which are species these reacting of compositions R3. R2, R1, functional groups using feasible steps reaction to generate
82

Chapter 4

Hybrid Optimisation of Rival Models

Reaction conditions are: Experimental reactor: batch reactor Reaction temperature: 25 C Reaction time: 10 hours Experimental data are listed in Table 4.1 and Fig. 4.9.
Table 4.1 Experimental data for base case
Time(hr. ) CA(moUm3) CB(moUm3) Cc(mol/m3) CD(mol/m3)

0 0.5
1 1.5

0.2 0.185
0.1717 0.1599

0 0.0147
0.0272 0.0378

0 0.0003
0.0011 0.0022

0.4 0.3809
0.3634 0.3473

2 2.5 3 3.5
4

0.1494 0.14 0.1315 0.1239

0.1169

0.0469 0.0547 0.0613 0.067

0.072

0.0037 0.0053 0.0071 0.0091

0.0111

0.3324 0.3187 0.306 0.2942

0.2831

4.5 5 5.5 6 6.5 7 7.5 8 8.5 9 9.5 [-l 0

0.1106 0.1048 0.0996 0.0947 0.0902 0.0861 0.0823 0.0788 0.0755 0.0724 0.0696 0.0669

0.0762 0.0799 0.0831 0.0858 0.0882 0.0902 0.092 0.0935 0.0948 0.0959 0.0968 0.0975

0.0131 0.0152 0.0173 0.0195 0.0216 0.0236 0.0257 0.0277 0.0297 0.0317 0.0336 0.0355

0.2728 0.2631 0.2541 0.2456 0.2375 0.2300 0.2228 0.2160 0.2096 0.2035 0.1977 0.1922

83

Optimisation of Rival Models

0.45 0.4 XX 0.35 0.3 0.25 0.2 0.15 0.1 0.05 0 02 4Time
AAAAAAAA;

Experimental

Data

fA B

xxX XXxD
XX

AC Xxxx XxX

( 1!

ffxxx

"ff

(hr6)

10

Fig. 4.9 Data graph for base case

4.4.1.1 Reaction list generation Feasible reaction list for Stage I is 11) 2D --> E 21) A+D-->B 31) A+2D-->C for Stage II is 411) 2C --> 2B +E 511) A+C 2B -->

611) 2A +E 2B --> 711) A+E 811) B+D C --> C -->

911) 2B +E --> 2C 4.4.1.2 Parameter estimation

First of all, hybrid optimisation was tested on the base case for parameter estimation, to for is if this suitable continuous variable problems, when the reaction see method frequency factor In fixed. is this method, reaction activation energy and order, scheme described The is known through moves. method above simulation optimisation used are to calculate reaction rate and concentration corresponding to experimental conditions. operating

84

Chapter 4

Hybrid Optimisation of Rival Models

dC1 dt =V1rj, for i=1... 5, j=1... 3

dT _0 dt Cl(t=O)
=C fJ

(4.21)

T(t=o) = To t= [1,10]

Generally, experimental data available are concentration values, then the objective function becomes:
N2

Min

2= 07

[Ci (exp tl)

Ci (talc )] -

(4.22)

Reaction scheme is chosen from the model, which is developed, by Coker (2001). Accordingly initial guessesfor kinetic equations are obtained randomly, as follows: Reaction 1 Reaction 2 Reaction 8 1I) 2D --> E 21) A+D --> B 8II) B+D C --> rl = 0.0003 * CD r2 = 0.0003 * CA*CD 0.0003 * CB*CD r3 =

4.4.1.3 Results and analysis The optimisation results for the kinetic models are shown in Table 4.2. Fig. 4.10 shows that different model performances compared with experimental data.
Table 4.2 Comparison of optimisation results
SA optimisation
Objective value: 0.000048 Kinetic equation:

NLP optimisation
Objective value: 0.0 Kinetic equation:

Reaction 1(I): Reaction 2(I):

0.0263CD2 r, = 0.392CACD r2 =

Reaction 1(I): Reaction 2(I): Reaction 8(II):

0.0250CD2 r, = 0.4000ACD r2 = r3 = 0.2000BCE

Reaction 8(11): r3 = 0.198CBCE

Note: least square used as objective function hr k is m3/kmol. unit of

85

Chapter 4

Hybrid Optimisation of Rival Models

04

SA
D_4 o ob

NLP
X B(ExP) 2(EXP) C
C(EXP - D(ExP)
0 25 c 0.1

0.35 0

,J 0

E S

D. 3

0.25 0,2

E v

015
a

0.15

0,1 0.05 0.0 D. 0

E
U

o.

0 05 D. D -

1.0

20704D5D6.0 Time [hr]

7.0

8.0

90

10D

D. 0

1, D

2.0

3.0

4.0 5, D Tlme [hr]

6.0

7,0

6.0

9.0

1D.0

Fig. 4.10 SA and NLP optimisation results

Fig. 4.11 is the result of residual analysis after NLP optimisation.

2. E-04

A
1. E-04

fC

XD

0. E+00

15 x x x xx

"

E-04 -1.

E-04 -2.

Fig. 4.11 Residual analysis

From the results, it was observed that the model gives good agreement with the data using SA to provide a good initialisation for the NLP. So the SA/NLP hybrid method is

suitable for problems with continuous variables and can access the global minimum,

Also, the reaction simulation though the even ranges of parameters are extremely wide. So hybrid both this equations. stiff and non-stiff reaction rate method can cope with in is to which the reaction scheme and more complex problems method now extended kinetics are to be obtained simultaneously.
Finally, three rival models are generated from the preliminary data fitting experimental

frequent from They the most model if reaction scheme moves are allowed. are screened in the multiple optimisation appeared fit Results the that rival models all show results.

86

Chapter 4

Hybrid Optimisation of Rival Models

the experimental data well in Fig. 4.12. Discrimination between them be left to the will next chapter.

Model 1
a. 4 o 35

Model 2
x_ (EXP) C(ExP) --- C(EXP) D D(EXP)
D. 4 0.35 D. l
E

0 a

.3

D 25 c

0 25 0 ,2
Y

c
D. 2

CL E
a U

0,15
0.1

0 15 a

-*
D0D5 L

D.

0,05 .0

D. 0

. [hfl Time

....

D. D D, 0

1.0

Z. 0

3, D

4. D 5, D Ttme [hr]

6, D

7.0

0.0

9, D

10.0

Model 3
D. 4 (EXP) 0.33 (EXP) D. 3 0 E 0.25
c

(EX P}. (EXP)

0.2 0 15
E O V

n
D. 1

0 05
0.0 =---s--v 71

D.0

1.0

2.0

3.0

4.0 5.0 6.0 rime [ter]

7.0

0.0

9.0

10,0

Fig. 4.12 Rival models

4.4.2 Oleic acid epoxidation reaction system

The net reaction is between oxygen and oleic acid, both dissolved in acetone. The
desired product is oleic acid epoxide. In Chapter 3, from information of species

involved in the reaction system, two reaction lists are obtained as follows:

D4 1 A+B F-->
2 2A+BHE

3 1C+D t- E+F A+D H 2E 5 B+2EH2D

be screened by the

During

the optimisation

of rival models, reaction schemes will

last in described the chapter. strategy

for data (Rastogi 1990,1992) the oleic design Experimental et al., and experimental in Table 4.3,4.4 4.5. listed and are reaction acid epoxide

87

Chapter 4

Hybrid Optimisation of Rival Models

Table 4.3 A 24-1 fractional factorial design

Factor Order of Run

1
+

2
-

3
-

4
+

runs
4 1

ID
RF4 RF1

+
+

+ +
-

+ +

+ + -

8 3
2 7

RF8 RF3
RF2 RF7

+ +

+ +

5 6

RF5 RF6

Table 4.4 Operating levels for variables of interest

Factor Variables Lo-level(-) Hi-level(+)

1
2 3 4

Temperature
Catalyst concentration Initial oleic acid concentration Initial benzaldehyde concentration

25C
1x10-5 M 0.24M 2.5M

35C
4x10"5 M 0.48M 3.5M

Table 4.5 Experimental data from the factorial experiments

Run ID Time (min. ) [A] (M) [D] (M) [C] (M) [E] (M) [F] (M)

RF1

0
40

3.5663
3.4603

0.0042
0.5961

0.2346
0.1799

0.0198
0.0708

0.0000
0.0487

80 RF2 0 40 80 0 40 80 0 40 80 0 40 80 0 40 80

3.2676 3.4290 3.4082 3.4042 2.4753 2.3697 2.1452 2.4635 2.4470 2.4416 2.6492 2.6233 2.5969 3.5106 3.4089 3.2683

0.0876 0.0047 0.0168 0.0188 0.0057 0.0479 0.0911 0.0057 0.0136 0.0155 0.0059 0.0156 0.0243 0.0049 0.0183 0.0664

0.0845 0.4800 0.4706 0.4669 0.2427 0.1741 0.0616 0.2366 0.2309 0.2247 0.4781 0.4719 0.4632 0.5019 0.4080 0.3066

0.2349 0.0236 0.0322 0.0343 0.0331 0.0966 0.2779 0.0210 0.0296 0.0331 0.0010 0.0184 0.0340 0.0373 0.1255 0.2181

0.1308 0.0000 0.0087 0.0117 0.0000 0.0623 0.1595 0.0000 0.0074 0.0111 0.0000 0.0077 0.0139 0.0000 0.0765 0.1721

RF3

RF4

RF5

RF6

88

Chapter 4

Hybrid Optimisation of Rival Models

RF7

0 40 80 0 40 80

2.5543 2.5353 2.5144 3.5043 3.4442 3.3305

0.0046 0.0096 0.0145 0.0037 0.0160 0.0414

0.4810 0.4649 0.4541 0.2412 0.2139 0.1832

0.0263 0.0403 0.0563 0.0432 0.0837 0.1329

0.0000 0.0131 0.0278 0.0000 0.0261 0.0569

RF8

Without a reaction model, reactor design and optimisation will be based on factorial from laboratory. from From Table 4.5, if is the the the experiments goal maximum yield level be: high then the chosen conditions would reactor or maximum reactor conversion, low level initial (35C) (4x10-5M) temperature of and catalyst concentration of with indicate (0.24M) benzaldehyde (2.5M). This a would oleic acid and concentration 65.69% for the reaction of and a maximum yield of maximum conversion of oleic acid from Scale-up initial benzaldehyde 6.44% to the concentration. with respect epoxide of the laboratory data could then lead to the first reactor design. Clearly, further design in factorial be a narrowed experimental carried out using experiments could search space to gradually refine the optimum conditions. However, this creates greater risk that the potential optimum conditions will be never Instead, In development delays that thesis, this the can a model program. and reached interpret experimental data well and can be used for reactor design and optimisation will be derived by the proposed methodology. 4.4.2.1 Model building Before the data were processed, assumptions were made to simplify the reaction system. It was assumed that there was no evaporation of the liquid phase, reaction occurs only in flow Thus by liquid no mass rate. gas the phase, and reaction rate was not affected in Also, the in the the of gas concentration saturated transfer resistance exists phase. gas liquid phase was assumed at the gas flow rates used to obtain the experimental data. After optimisation, three rival models, Model 1, Model 2 and Model 3, whose 0.364191,0.36161 objectives were from 0.374843, the multiple obtained were and

functions. the relative minimum objective optimisation results with

89

Chapter 4

Hybrid Optimisation of Rival Models

Model 1 Reaction steps Reaction 1(I) A+B ->D Kinetic equations

Ea1 )CACcat rl = Al exp(RT

Kinetic parameters Al = 78.6867 Eat 909.392

Reaction 3(II) C+D->E+F Reaction 5(II) B+2E-> 2D

A2 exp(r2 =

Eat RT

)CDCl

A2 = 0.0148583 Eat 60.8269

Ea3 A3 CECat exp(r3 = RT

A3 = 0.100000E-05 Ea3 2000.00

Model 2 Reaction steps Reaction 1(I) A+B -D Reaction 3(11) C+D ->E+F Reaction 4(II)
33 r=A

Kinetic equations Ea1 )CACar Al exp(rl = RT Ea2)CDC1

RT

Kinetic parameters Al = 19.2384 Eat= 56.6036 A2 = 0.285781 Ea2 2000.0

A2 exp(r2 =

A+D

2E ->

Ea3 C exp(- RT )C AD

A3= 0.00708276 Ea3 673.469

Model 3 Reaction steps Reaction 1(I) A+BD Reaction 3(II) C+D --> E +F Reaction 4(11) A+D 2E ->
A2 exp(r2 =

Kinetic equations
rl = Al exp(Eal RT 1 )Ca C

Kinetic parameters Al = 166.795

t oa

Eat = 50.4892 A2 = 0.134936 Eat= 1665.0 A3 = 0.0585312 Ea3= 2000.00

Ea2)CDC1 RT

Ea3 )CACD A3 exp(r3 = RT

90

Chapter 4

Hybrid Optimisation of Rival Models

These three models all fit experimental data reasonably well, but have different reaction kinetic and schemes expressions.

4.4.3 Discussion
From the results of two cases, the rival models which fit the same experimental data have similar values of objective functions, but give different reaction models that satisfy the statistical screen. Hybrid optimisation can easily deal with the large scale MINLP far So be further validated rival models cannot problem and provide robust solutions. data. with currently available experimental

4.5 Conclusions
The experimental data can be used to identify which reaction network is most derive kinetic for to the reactions within the networks parameters appropriate and by designed A is to obtain a an optimisation method. stochastic method simultaneously by in the the of optimum setting up reaction network moves and region set of solutions kinetic moves to generate alternatives and monitor the random search. The SA deletion the through risk of model mismatch avoiding premature algorithm can reduce for SA initialisation NLP. Also, in the provides a good of a model preliminary stage. Conclusively, SA optimisation combined with NLP provides good solutions for the MINLP problem and a set of rival models is determined for model discrimination and design. optimal experimental

91

Chapter 5

Model Discrimination and Optimal Experimental Design

Chapter 5: Model Discrimination Experimental

5.1 Introduction 5.2 Model discrimination criteria 5.3 Optimal experimental design 5.3.1. Laboratory reactors 5.3.2. Experimental conditions 5.3.3. Reactor superstructure

Optimal and

Design

5.3.4. Simulated Annealing (SA) optimisation 5.4 Case studies 5.4.1. Base case 5.4.2. Oleic acid epoxidation 5.5 Conclusions

92

Chapter 5

(D, irs r,at , i .

--1

Design . r _ ._1_-rimental

A set of rival models can be obtained within a certain confidence level to fit the same
set of experimental data. However, they cannot be discriminated without further

data find to the best model. In this chapter, a methodology that can obtain experimental optimal experimental design for rival model discrimination to reach the minimum

experimental measurement target is proposed and validated by two case studies, whose rival models are derived in the previous chapter through hybrid optimisation.

5.1 Introduction
............................. ti

Stoichiometric analysis
Model Derivation
....................................... I.......... ti

..;

Preliminary

experiments """"""""""""

Reaction scheme and kinetic rival models

,...

....................................................
Model Discrimination

Further experimental design

Model discrimination and improvement of model accuracy

Fig. 5.1 General model building framework

There are many applications in which one set of experiment data can conform to more than two models, all within the same sample space, as discussed in the previous chapter. In the first step of the model building methodology, model derivation aims at providing multiple solutions to avoid any premature decision. On the other hand, a set of

further for design screening can only cause chaos process competing models without and optimisation. As shown in Fig. 5.1, the remaining building the work of model

procedure is model discrimination.

There is a probability that at other operating conditions these rival models have different decide discriminate How be to the to used among rival models. performance, which can for For instance, is discrimination. task the a critical model next experimental point following two reaction models fit experimental data very well from experimental time

93

Chapter 5

Model Discrimination and Optimal Experimental Design

in Fig. 5.2. If further experiments are carried out within the same to t, as shown zero time range, no extra information be provided except parameter precision can

improvement. So accurate model fitting is not enough for model discrimination. Consider again the example in Fig. 5.2, if the experimental time is extended, the two different Alternatively, if to experiments performance. models start exhibit significance different different in types the two produce of reactors, models might are carried out be distinguish distributions. This to among rival models. concept can also used product

70 60 50 CIO 40 0 30 20 10 0

13579 Exp. Time

11

13

Fig. 5.2 Data fitting and model performance

The objective of model discrimination models (i. e. polynomial

is that, given that several different

kinds of

how should experimental points vs. exponential) are available,

be chosen to distinguish between them? In other words, some experimental data have been used to derive rival models, where should the next experimental point be located to learn the most about which is the right model? It is desirable to build the relationship between model discrimination and experimental design.

The concept of optimum experimental design was first presented by Kiefer in 1959 at the Royal Statistical Society. Optimal experimental design can provide the

in for information the tools order to reach wellproducing most relevant mathematical high The aim of optimal efficiency and at minimum cost. predefined objectives with for for discrimination. is design parameter estimation, or either model experimental

94

Chapter 5

Model Discrimination and Optimal Experimental Design

There are two general groups of optimal experimental design: simultaneous (statistical) or sequential. Optimal experimental design has received a considerable amount of attention in the literature, for example Anderson (1962), Hunter and Reiner (1965), Box and Hill (1967), Hunter and Mezaki (1967), Pazman and Fedorov (1968), Froment and Mezaki (1970), Meeter et al., (1970), Atkinson (1972), Atkinson and Cox (1974), Atkinson and Fedorov (1975a, b), Hill (1978), Atkinson (1981), Spruill (1990), Dette (1994,1995), Dette and Ro der (1997), Dette and Haller (1998), and Pukelsheim (1993). Commonly, design optimal experimental methods are also based on statistics, such as factorial design, fractional factorial design, orthogonal design and uniform design. Experimental design theory for precise estimation of the model parameters has been developed in For well recent years. example, D-optimum, T-optimum and other designs have been in alphabetic optimum successfully applied many subjects, which belong to the first group (Atkinson & Donev, 1992; Pukelsheim, 1993; Fedorov & Hackl, 1997). However, the design problem for discrimination between models has received much less for has been developed attention and simple models only. Various criteria were by (1967), Atkinson (1975a, b), Box Hill Fedorov Burke considered and and et al. (1994,1995), Stewart et al. (1998), Ponce de Leon and Atkinson (1991), Mller and Ponce de Leon (1996), Felsenstein (1992), Fedorov and Khabarov (1986). The best design for discriminating among several rival models may be quite different from the design that is optimal for estimating all the parameters in the unknown true design, design A-optimum D-optimum If an method, such as a model. an optimum design or an E-optimum design (Pukelsheim, 1993), is chosen, efficient estimation of for discrimination, design is But the resulting model may model parameters guaranteed. design for Furthermore, be these models. many optimal criteria some of even singular for model discrimination depend on the specific ordering of competing models and b). is (Atkinson 1975a, & Fedorov, the true the one models which one of

95

Chapter 5

Model Discrimination and Optimal Experimental Design

In this work optimal experimental design will be considered that simultaneously achieve two objectives: generation of optimal design points so as to discriminate among rival improve to models and estimation of all the parameters in that model.

5.2 Model discrimination

criteria

To identify which is the best model to describe the reaction system, further experimental data are needed. The basis of experimental design is that, at other operating conditions than those at which rival models are derived, rival models might have different have The biggest difference, the point where rival models performance. provides the for the experimental design. In other words, it provides the optimal operating conditions

Preliminary experimental data

Rival models

Further Experimental design

Model precision improvement

Model discrimination

One model
Yes Final model

Fig. 5.3 Model discrimination framework

96

Chapter 5

Model Discrimination and Optimal Experimental Design

best opportunity to determine which model is the best model, if further experiments are carried out at the optimal operating conditions. In principle, it is necessary to avoid a routine approach by making extensive measurementswithout simultaneous evaluation. The basic problem is to select the set of experimental points that will provide the best discrimination amongst the models. The whole procedure of model discrimination used in this chapter is shown in Fig. 5.3. Further experimental design is determined according to the predictions of existing rival models to provide maximum discrimination, at the same time aiming to improve the fitting adequacy of with additional experimental data. Several alternative models are often proposed to explain the same data, and objective criteria are needed to choose amongst models. The choice of objective criteria can affect the method of data evaluation. The rival models may be nested or non-nested based on their origins. Nested models are a series of models that allow a simpler model to be obtained from a more complex by model eliminating one or more parameters from the more complex model. Thus determining is to the appropriateness of the additional choosing among models reduced Non-nested parameters. models are not related in this way, and any model is valid under a certain hypothesis. In this thesis, the rival models have the feature of non-nested models. Accordingly, the discrimination criteria are different from those for nested models. There is a large number of possible optimality criteria, depending on the particular task at hand, named by letters of mnemonic value: maximizing the determinant is Doptimality, minimising the variance of predictions is G-optimum. There are A-, c-, C-, DA-, D, beta-, D's-, E-, L-, T- and V-optimum also, and there are equivalence

theorems connecting many of these. Sequential design of experiments (Hunter & Reiner, 1965; Box & Hill, 1967) is the in kinetic Experiments for discrimination. method are most widely used studies and direction in improvement a of successively performed until the optimum is reached. The is is design carried method out while an optimisation method applied. sequential

97

Chapter 5

Model Discrimination and Optimal Experimental Design

Suppose there are m rival model after fitting to N experiments. , Model H1: 17,, f, (e1, ) = Model H2: i7 = f2(82, 2 )

Mode H:

m) fm(0m, 17 = .

u =1,2,...N

(5.1)

hypothesised is the i where model response; 0= (0 , 02,"""9p) is the vector of p model (t1, ;= J2 parameters; Jk) is the vector of k dependent vari ables. ,"""

The observed response y should be: y=11e (5.2)

where the error e is normally and independently distributed with constant variance 62 . It is desired to find the best setting of tN+1 for N+1 experiments that will best discriminate between rival models. According to Hunter and Reiner (1965), the best experimental condition for model discrimination is the one that maximises the divergence among the responses of the models. It has been applied to the system with two rival models (m = 2). Assume that either model H1 or H2 is correct (not both will hold), the design criteria is either:
N+1

Si =
u=1

(YU- f2U)2
N+l

(5.3)
N+1

where
or

YN+1

_1

le1N+1'

1N+1 l'

f2 (eN+l'1

N+1

s2=
U=1

(Yu-fiu)2

(5.4)

98

Chapter 5

Model Discrimination and Optimal Experimental Design

where

yN+l

=f

N+1

fa (e2

+1

+1)

fN+i

fi (8N1 +1

J,

Box and Hill (1967) showed that the design procedure should take experimental errors into prediction and model variances account in order to improve the performance of the discrimination procedure. They extended the method to general problems (m >_ 2). A multiple hypothesis test is a generalisation of a binary hypothesis test. Suppose m Ho, HI, from Hm_ data are rival models: obtained preliminary experimental and j .... is best based Hi that the a certain model assume model on the performance of further experiments.
Then the problem arises: how to identify which model is the best model that closely data? This is the experimental an optimisation matches problem again. Choice of the

function, i. e. the choice of the quantities to be compared, is a problem for the objective for kinetic design. be is It the responsible measurements and reactor engineer who must description to achieve an accurate selected so as important. of data in those regions that are

Experiments are selected on the basis of an entropy criterion suggested by Box and Hill (1967) that measures the information increment provided by each of the experiments. The concept of entropy commonly used in the thermodynamics is adopted in the information theory (Shannon, 1948), to measure the amount of information contained in from information it is in Therefore, the the to maximum system order obtain a message. desirable to have a maximum change in entropy between input and output. As a discrimination criterion, entropy has also been used in the work of Reilly (1970) de (1987) Kleer Williams in (1972) in Fedorov the and and work of statistics and and Struss (1994) in model-based diagnosis.
D=II ][I i=1j=i+l JPi In p` dyN JP; In p' dYN + jN-1 A P; (5.5)

N-ill

where i, j N A

index of models, i, j=1,2, index of experiments

m ....

i function density the of n-th experiment under model probability

99

Chapter 5

Model Discrimination and Optimal Experimental Design

YN

expenment

11N-1 prior probability II N posterior probability total distance measurement of information

This criterion D is called Kullback's

(Kullback, 1959) when discriminating between hypotheses Hi and Hj. It was derived from statistical theory when experimental errors are considered. The minimum mutual information is corresponding to the maximum function D, representing the maximum difference of two hypotheses. This concept is now applied to the discrimination among m models where it is desired to informative from to a more situation. a non-informative situation go The predicted value at the next operating conditions is determined from the probability level. within a certain confidence
(YN Pt -1
6c2 -t- 6l2

exp -1 2(62

62

- YN

(5.6)

is form first N known is the the the 62 variance experiments; variance where 62 -1 i i. N-th model under experiment yN of predicted value of The objective function for model discrimination among the m rival models is to maximise
mm22

(cTi
-6'l

I2

D= 1I 2

Y, HEN-1fl jN-1

(2+22+2)

j=i+1

6i

`'11 + yN -ya

225.7 2+ 6 -I- 6i -I- 6i

()

It can be simplified according to the specific problem. Normally it is an unconstrained optimisation problem.

100

Chapter 5

Model Discrimination and Optimal Experimental Design

5.3 Optimal experimental

design

A model generally includes a set of independent variables , and a single scalar dependent variable, called the single response model. Or a model with a vector of dependent variables is called multiresponse model. 17u =f(0 ,) (5.8)

0 is the vector of estimated model parameters. where

The purposes of experimental design are, either estimating parameters of the model, or discriminating distribution among models. An experimental design is, for these purposes, a variables, at which the

(discrete or continuous)

over the independent

response is measured. Based on the concept that either within different reactor types or at different operating describe the that the same reaction system can of conditions, predictions rival models have different independent configurations performances, variables which is preferred of discrete for model discrimination. to represent conditions, The reactor such as

are composed

variables

and continuous

variables to represent operation

temperature, pressure, and so on.

Rival models Model 1

Model 2 ,,,,,, Model m-

.--.

Model 1 Model 2 =Modeli

4
Reactor superstructure Operating conditions + Experimental reactors Optimise J

160

120 j80 " 40

C a

'-

0246

Fig. 5.4 Optimal experimental design framework

101

Chapter 5

Model L)i; Lrimination and Optimal Experimental Design

In order to achieve the maximum objective, an optimisation approach is required to provide a robust solution, while handling both discrete and continuous variables. Here Simulated Annealing (SA) optimisation is applied. A reactor superstructure is necessary for effective optimisation, in which all possible combinations of reactor configurations and operating conditions are embedded (as shown in Fig. 5.4).

5.3.1 Laboratory

reactors

The type of reactor to be used in laboratory experiments to obtain data for process evaluation or kinetic modelling depends on the nature of the reaction. Laboratory

be in for data in two a chemist's can generally used ways: reactors gathering reactors laboratory with the objective of developing a feasible synthetic routine for a chemical, kinetic data isothermal to obtain precise under conditions, which also and reactors used take into account the mass and heat transfer features of the reactions. Alternatively, Laboratory reactors can be divided into two categories: reactors for

homogeneous reactions and reactors for heterogeneous reactions. Choosing the type of laboratory reactor for evaluating process kinetics may be the most crucial step in an industrial in Not development choice result only would a wrong program. process

data be but delays, may obtained which would scale-up erroneously, also expensive leading to a disastrous commercial design.

The most common reactor types used in the laboratory are shown in Fig. 5.5 and Fig. 5.6.

Time Feed Feed

Time

Batch

Product

Semi-batch Feed

Product

Feed PFR

Product Product Stirred tank

Fig. 5.5 Laboratory reactors for homogeneousreactions

102

Chapter 5

Model Discrimination and Optimal Experimental Design

Fluid-Solid Reaction Feed

Feed

le-O

Feed R

Produ t

Product Stirred tank

Product
Stirred basket tank loop reactor

Fluid-Fluid Reaction

Fluid-Fluid-Solid Reaction

Feed Fee Pro uct

Prnrinrt

Feed

"P

"Q"G( O: O

Feed

Product

Product

Feed 2 Stirred tank Fig. 5.6 Laboratory Tower reactor Stirred slurry reactor Stirred basket reactor

for heterogeneous reactors reactions

5.3.2 Operating conditions

It is obvious that the inclusion of operating conditions is dependent on the specific
reaction system and reactor chosen. The following operating conditions cannot usually

be ignored:
9 " " Temperature Pressure Reaction/residence time

"
" "

Phase contacting type

Mixing type Feeding policy

" "

Recycle or bypass Etc.

Operating variables can be addressed as continuous variables, optimised within divergence. bounds to achieve maximum reasonable

103

Chapter 5

i( del 1i: i irninetil; ti and

L.-yperimental Design

5.3.3 Reactor superstructure

The optimal experimental design requires the evaluation of the most promising

............................................................................................................................................... FEED `r

Fig. 5.7 Homogeneous experimental reactor superstructure

If a new experimental point seems to be promising, it should experimental conditions. be investigated and compared to previous conditions. Completely different reactor

be included, but that should also so arrangements novel promising missed. Therefore accommodate optimisation. the superstructure for the optimal reactor configurations

solutions are not design should during

experimental

different

and operating

conditions

Fig. 5.7 is the reactor superstructure for homogeneous reactions with one feed and one be in Also, the this extended to multiwork. reactor superstructure can product used phase reactions. Two-phase be described systems can by one pair of reactor

5.8). (Fig. compartments

> ....................................

...................................

.......................................................

"

FEED
"`"R ....... .........................:.......:......................

L.

............}...................................................................................................

j r.......

..........................

....

..........................

......

j...............................................

FEED
r

PRO] .....................................
.........................................

y................................
............................................................................

Fig. 5.8 Multiphase experimental reactor superstructure

104

Chapter 5

Model Discrimination and Optimal Experimental Design

The superstructure representation is based on reactor units and splitter/mixer units. The follows the concepts developed by Mehta (1998) for multiphase reactor representation By different using networks. simulation models, the same generic representation can be for different scopes and applications. The models applied by Mehta (1998) for used multiphase reaction systems can be modified to address the issues required in design. experimental The presentation of reactor units is based on ideal reactors: CSTR or PFR. Isothermal and steady state is assumedwithin the unit of superstructure The superstructure accommodates each phases independently. The two phases are by mass transport within a reactor unit. For each reactor unit, the options for coupled mass transfer, reaction, number of compartments, flow direction can be controlled, so that each unit either represents a well-mixed reactor (CSTR), a cascade of CSTRs, a (PFR), in plug-flow reactor co- or counter-current mode. In the reactor superstructure, the splitter unit can facilitate connections between the reactor compartments of a given phase as feed condition, bypass or recycle. The mixer unit can function as feed condition controller. The models associated with the various detail described in included in the this options superstructure of as work are more follows: 0 Reactor configuration

All commonly used reactor configurations in the laboratory can be represented in the reactor superstructure, but the reactor configurations for a specific reaction system are for fluid-solid For the the to groups. example, reactor configurations restricted certain reaction system are not suitable for fluid-fluid reaction systems. In order to reduce the incremental to the and avoid modifications to the superstructure size of superstructure between function, little the the numbers one objective range of valid unit with effect on discretised (e. ). is into 1,2,3. In and a maximum value a series of valid numbers g. different than three reactors are used to study one reaction practice, generally no more system 0 Mass transfer

105

Chapter 5

Model Discrimination and Optimal Experimental Design

Mass transfer is reflected by mass transfer coefficients. Reactions only occur in one phase and no phase-transfer happens between any two phases. 0 Feeding policy/recycle/bypass

By specifying flow fractions for each splitter or mixer and other operational variables like mass transfer coefficient, flow direction of a compartment, etc., a unique reactor will be generated. " Flow direction

The flow direction can be varied for a unit, so that both the counter-current and coflows current are included in the superstructure. 0 Phase contacting type

For multiphase reactors, which type of the phase contacting pattern, plug flow/plug flow, or plug flow/mixed flow or mixed flow/mixed flow is applied depends on whether CSTR or PFR is chosen as the ideal unit.
0 Continuous parameters

All continuous parameters such as temperature, pressure, reaction/residence time, feed flow rate and initial concentrations, can be varied also.

5.3.4 Simulated Annealing (SA) optimisation

During the optimisation step, the superstructure is reduced to a final structure with a near-optimal performance. Because of the severe non-linearity of the equation system discrete decision deterministic large the variables, and number of optimisation

be in Instead to successful. a stochastic optimisation scheme the approachesare unlikely form of Simulated Annealing is applied. When variables of experimental reactor superstructure are optimised, all possible experimental reactors and operating conditions are generated to achieve maximum divergence for model discrimination.

106

Chapter5

Model Discrimination and Optimal Experimental Design

5.4 Case Studies

In Chapter 4, two examples were used to illustrate the first step of the model building Three rival models were generated for each example. In this Chapter, the methodology. for discrimination be model procedure will applied to these two cases.

5.4.1 Base case

Three rival models were generated from the preliminary experimental data fitting in Chapter 4. Model 1 1) 2D --> E 2) A+C-->2B 3) A+E --> C Model 2 1)A+2D-->C 2) 2C --> 2B +E 3) 2B +E --> 2C Model 3 1) 2D --> E 2) A+C --> 2B 3) 2A +E --> 2B 4) 2B +E --> 2C 0.1177 CD2 rl = 1.854CACc r2 = 7.5032x106CACE r3 = 1.3552x106CBCE r4 = rl = 0.0311 CACD 1.2435x105CC r2= 5.5563x105CBCE r3 = 0.0385CD2 r1= r2 =3.0168CACC r3 = 13.356CACE

In this case, there are two feeds, each comprising one of the pure raw materials (A and D). Only the feed composition can be optimised in order to design a new experiment to discriminate between the three candidate models. So during the optimisation, the feed feeds is the modified as the optimisation parameter. charge size of one of The initial guess for the feed of component A is 0.2 kmol; 0.4 kmol for component D. After optimisation, the optimal charge size for component A is 0.107 kmol, while the feed of component D is fixed. The performances of the different model are shown in Fig.

107

Chapter 5

Model Discrimination and Optimal Experimental Design

5.9 under optimal operating conditions. It is concluded that the predicted responses of the models to the new input conditions are easily distinguished from each other based D in different the of prediction on models.
0.05 Model 1 -1 -- Model 2 Model 3

E 0.04
0.03 ' 0.02 0.01

2468 Reaction

10 time (hr. )

--t0.15

Model 1

Model 2

Model 3

B 0.12
0.09 0.06 0.03 0 02468 Reaction time (hr. ) 10

-f0.05

Model 1 ---

Model 2

Model 3

-0.5

Model 1

Model 2

Model 3

C 0.04
0.03 0 U
0

0.4 0.3 0.2

0.02 0.01 cz 0 U 02468 10

0.1 0
0

Reaction

time (hr. )

2468 Reaction time (hr. )

10

Fig. 5.9 Model performance

By creating new experimental data at the optimal conditions sequentially, this will allow to be selected the best model. In the design of new experiments, only the effect of the initial composition was considered. In principle, other network parameters (reactor ) be could etc. also considered. volume, number of reactors,

108

Chapter 5

Model Discrimination and Optimal Experimental Design

5.4.2 Oleic acid epoxidation

Again, oleic acid epoxidation is used as an example to demonstrate how the optimal design is obtained using optimisation. Saturated concentration of gas in experimental the liquid phase will be assumed for the three rival models. In this case, the reactor type fixed, but be the are operating and size mode can changed from batch to semi-batch. Optimisation parameters are temperature, reaction time, and feeding rate. Maximum is 48 C (5C less temperature than the flash point of the acetone operating allowable solvent). After optimisation, the optimal experimental design for model discrimination is: Reactor type: Batch time: Temperature: Feeding rate/time: batch 83.177 min. 48C
0.25 litre/min

Unfortunately experimental data are not available at these conditions, and so the methodology cannot be pursued further. However, the performance of the different be models can still compared. Assume that all three models are used to design the reactor for maximum oleic acid conversion (which is corresponding to maximum epoxide yield). The change of oxygen partial pressure has no effect on the forming of epoxide product, low Model 1 irrational. Model 2 favours initial the reaction scheme of which makes high benzaldehyde initial for best design, the and oleic acid concentration concentration initial is 5 lower is 15 that to times consistent with oleic acid concentration which benzaldehyde in data. Model initial 3 with the to concentration compared experimental the same reaction scheme cannot give the same design. So Model 2 is assumedto be the best model, which is consistent with the model developed by Rastogi (1992). Reactor design and optimisation are carried out using Model 2. The highest conversion following %, OA is 92.38 the operating conditions: at of Batch cycle time: Temperature: 32.17 mins 48C

109

Chapter 5

Model Discrimination and Optimal Experimental Design

Feeding rate (OA):

0.497 litre/h.

Now check the performances of the other models at these conditions. The conversion of 57.9% is The Model Model 2 1, 37% lower than the using prediction. around oleic acid 2 is Model 0.36% 3, 99% lower Model the than conversion of oleic acid around using prediction. So if the model is not chosen and tested carefully, a reactor designed on the basis of an inappropriate model cannot operate under optimal conditions.

5.5 Conclusions
The methodology for reaction model building is completed in this Chapter through the design is discrimination described. Further carried out procedure experimental model from the rival model optimisation method. All kinds of laboratory reactor and operating for SA in the the optimisation reactor network superstructure. conditions are embedded MINLP problem and the most appropriate reactor configuration, along with operating for design, determined for discrimination and experimental are model conditions design. optimal experimental

110

Chapter 6

Model Building for Refinery Heterogeneous Catalytic Reactions

Chapter 6: Model Building for Refinery Heterogeneous Catalytic Reactions

6.1 Introduction 6.2 Heterogeneous catalytic reactions 6.2.1 General features 6.2.2 Hydrodesulphurisation (RIDS) 6.3 Model building methodology for HDS processes 6.3.1 Catalyst characterisation 6.3.2 Catalyst kinetics 6.3.3 Model discrimination 6.4 Case studies 6.4.1 Hydrodesulphurisation of thiophene 6.4.2 Hydrodesulphurisation (HDS) of diesel 6.4.2.1 Temperature effects 6.4.2.2 Sulphur compound addition effects 6.4.2.3 Catalyst effects 6.4.3 Discussion 6.5 Conclusions

111

Chapter 6

Model Building for Refinery HeterogeneousCatalytic Reactions

The model building methodology discussed so far has been restricted to homogeneous Heterogeneous reactions. reactions other than those involving solid catalysts will not be in the scope of this study. Heterogeneous catalytic reactions are much more complex than homogeneous reactions, so the general procedure of model building is more for heterogeneous complex catalytic reactions. In this chapter, the model building is heterogeneous to to extended apply methodology catalytic reactions in accordance features. This its with special work aims at exploring general model building procedures from aspects of catalyst characterisation, kinetic studies and model discrimination with minimum experimental effort.

6.1 Introduction
Heterogeneous catalytic reactions generally involve a solid catalyst and a fluid phase (gas and/or liquid) that supplies reactants to the site of catalysis, the fluid-solid interface (Carberry, 1976). As mentioned in Chapter 2, catalytic reaction depends on the interrelationship between chemicals and catalysts, from the nature of catalytic reactions, as well as on other operating factors (temperature, pressure, concentration, etc.). Hence, properties of the contact area between the phases are important reaction heterogeneous implicit in Diffusional components systems, since variables. steps are be from transported their phase to another one or more reactants and/or products must for Factors the that govern interphase phase, where, reactants reaction actually occurs. heat and mass transport therefore become important reaction parameters, which need to be accounted for simultaneously in order to model heterogeneous catalytic reactions. Typical heterogeneous catalytic reaction systems in the chemical industry include hydrodesulphurisation, methanol synthesis, methanation and Fischer-Tropsch synthesis, disproportionation, benzene isomerisation, etc. To toluene ammonia synthesis, and ethyl illustrate the model building methodology for heterogeneous catalytic reactions, the hydrodesulphurisation (HDS) process from petroleum refining is selected because of its importance in the refinery industry. Sulphur reduction in motor fuel has been prompted by several factors. First, air pollution control standards require removal of up to 80% or more of the sulphur that

112

Chapter6

Model Building for Refinery HeterogeneousCatalytic Reactions

be in present would various fuels. Second, many catalysts in down stream units are sensitive to the amount of sulphur in the feed. Third, the reduction of sulphur reduces the amount of corrosion in the refining process, improves the odor of the product, and reduces the amount of sulphur that can poison the catalytic converter in a motorcar.
Table 6.1 Quantity of sulphur in the various distillation fractions
Fraction Boiling Point Percentage sulphur (wt %)

Light gas oil Naphtha Kerosene

Diesel

0-70 70- 140 140 - 250

250 - 350

0.001-0.02 0.002-0.02 0.01-0.2

0.1-1.4

Residue

> 350

0.3-4.1

Sulphur compounds are present in all distillation fractions of crude oil. Crude oil itself, depending on type and origin, contains 0.1- 2.5 wt% sulphur. After distillation, the boiling increases different fractions, the the the average sulphur with quality of point of in distillation fractions in in the amount of sulphur content various of crude oil shown Table 6.1. In recent years, the supply of heavy types of crude oil on the world market has increased have for liquid fuel become At the time, the specifications significantly. same products more and more strict.
Table 6.2 European diesel specifications*
Unit Year: 2000 Year: 2005 Year: 2010

Sulphur
Cetane number

ppm (max)
min

350
51

50
51

10
51

T95 PNA Density

C %wt (max) Kg/m3 (max)

360 11 845

360 11 845

360 11 845

* Directive of the European Parliament and of the Council 98/70/EC

113

Chapter 6

Reactions Catalytic Heterogeneous Model BuilJinL fier R. A'inery

Sulphur content is the main concern of the diesel quality. Take the EU market as an 6.2). (Table The 50 fuels be diesel to sulphur ppm example content of should reduced by 2005, further to 10 ppm by 1st January 2011, to finally achieve a zero-sulphur target. More strict markets with low-emission fuels, such as UK, Germany, and Norway have 50 S diesel the target already. ppm reached
If reducing the sulphur level from 500 to 50 ppm by conventional HDS processes, the beds have be increased 3.2 times, compared with the current to will volume of catalyst SIDS catalyst bed, or the temperature of reaction will have to be increased by 38C (Knudsen et al., 1999), as shown in Fig. 6.1. Furthermore, a 200% increase in catalyst be if is 10 the to reduced required sulphur content ppm. volume will
f 40 30 EM 20 a) 10 0 Relative activity Delta T 500 400 300 200 100 0

500

100 40Q 300 200 Sulphur content (ppm)

Fig. 6.1 Operating conditions change with sulphur content target

These options result in accelerating catalyst deactivation with no additional profit to the is Choosing a more active catalyst, or process revamping required to meet the process. profit target. Accordingly, improving the accuracy of the model prediction and speeding

for becomes for building increasingly the time and catalysts new processes model up important for process profitability.

6.2 Heterogeneous catalytic reactions

6.2.1 General features
Generally, heterogeneous catalytic reactions comprise of adsorption, surface reaction in heterogeneous (Fogler, 7 1992): desorption. There catalytic reaction are steps a and inside bulk diffusion in the the the the transfer of reactant phase, reactant mass of

114

Chapter 6

IVI, dd Buildin

Reactions Catalytic Heterogeneous Refinery ur

catalyst, adsorption of reactant onto the catalytic surface, reaction on the surface of the from desorption from diffusion the the the the of products of catalyst, products surface, interior of the pellet to the external surface, and mass transfer of the products from the bulk fluid, 6.2. in Fig. to the surface as shown external pellet

nFl
----_E lJ ---

11

Eitetnal diffusion

----------

--

AB EiI 6 Internal diffusiun

-------------------

-----w----

--------

Gc iR1yfiC

5urfDI6

Fig. 6.2 Steps in a heterogeneous catalytic reaction

Understanding of the reaction mechanism has always been the most difficult building. model This has attracted significant

task for

but lack is there attention, still a of

The theories. ability to reliably predict the structure of catalyst or catalyst prominent intermediate is a very important aspect to the model, design and catalyst improvement (Cundari et al., 1998). Studies show that through a reaction mechanism in a stabilized catalyst, better activity depends on the ability of the transition metal components of formation of the active site is important, the the as it affects the accessibility of on effect of geometry surface, and active sites. This information can be obtained directly from a variety of diffraction ray, neutron, and electron being the most common) experiments (Xfrom

be inferred or can

EXAFS, (NMR, spectroscopy two aspects, firstly,

infrared, etc. ). Spectroscopic techniques are valuable in potential catalytic intermediates, and secondly about catalytic intermediates.

to confirm/exclude

information tool to reveal chemical as a

115

Chapter 6

Model Budding fur Refinery Heterogeneous Catalytic Reactions

Molecules could be adsorbed on the crystal surfaces, and their structures and bonding be low-energy For the techniques. studied with available could electron example, diffraction (LEED), Auger electron spectroscopy (AES), X-ray photoelectron

high-resolution (XPS), electron energy loss spectroscopy (HREELS), spectroscopy could be used. Recent progress in developing and improving these techniques for examining surface
bulk However, it is of properties solid catalysts and provides encouragement. unlikely that a universal theory can be applied to a wide variety of reactions.

A wide range of catalysts has been used in industry applications. Commonly they are into two categories: metal and metal oxide. Hytrotreating catalysts belong to classified
metal oxide catalysts. Catalysts ingredient, precipitation, are generally and promoter. composed of three main constituents: supporter, active

There are three methods for preparation

of catalysts:

deposition or impregnation, depending on how the active ingredients are

deposited to the support surface.

Fig. 6.3 Method for special distribution of active ingredients

For hydrotreating catalysts, impregnation is the most widely used method. This method is faster, and allows the final property and configuration to be controllable. It is,

116

Chapter 6

Model Building for Refinery HeterogeneousCatalytic Reactions

however, more difficult to prepare high concentration catalyst and to obtain an even dispersion of catalyst components on the surface. Special techniques (in Fig. 6.3) are developed to deposit the catalyst on the surface skin of the pore structure (egg shell) or inner (egg by the to structure pore on yolk) a competitive chemisorption of special formic HCI. The eggshell arrangement of catalyst e. g., citric acid, acid or adsorbate, desirable is in diffusion-controlled a components reaction. The egg yolk arrangement allows the smaller reactant molecules to contact with the active component of the This is in impurity the the sometimes used catalyst. case where reactant stream contains high Both of molecular weight substances. arrangements enable the saving of precious metal. Catalytic reaction-rate expressions can be derived for ideal surfaces by the LangmuirHinshelwood-Hougen-Watson (LHHW) approach. This approach derives rate equations in terms of surface concentration of adsorbed species and free sites and then expresses these concentrations in terms of Langmuir isotherms. The formulation of LHHW equations involves the postulation of steps 3,4 and 5 of the 7-steps and their corresponding rate equations. First, the rate-determining step (RDS) assumption should be made to simplify the reaction expression for subsequent steps. If one of the steps is significantly slower than the others, then this determines the overall known it is rate of reaction and as the rate-controlling step or rate-determining step (RDS). In the derivation of LHHW models, the RDS is often specified prior to kinetic data. regression of It is also usually assumed that the conditions on the surface are stationary. The balance the the combination of rate equations, on the catalytic sites and equality of the by indicated the steady-state assumption allows the elimination of all surface rates dependent terms. Every reaction system has its own distinguishing features. To be more specific, hydrodesulphurisation (HDS) processes will be discussed.

117

Chapter 6

Mt, dei

Heterogeneou" I'atalvtic Reactions f', r 11_cfinery

6.2.2 Hydrodesulphurisation

(HDS) processes

A refinery is a complex network of interdependent processes, reflecting the result of advanced chemistry, engineering, and metallurgy. Hydrodesulphurisation processes are
in important in 6.4. Fig. the units modem refinery shown very

Primary Separation
I

Conversion

Impurities removal

Light ends upgrading

Isomerisation

Product LPG

Propane/Butane
Light Gasoline

Naphtha

Hydro-

NAPHTHA GASOLINE JET FUEL

High Vacuum
Distillation

Vacuum Distillates

DIESEL

LUBE OIL

Vacuum

FUEL OIL ASPHALT

Fig. 6.4 Modern refinery

The hydrodesulphurisation process involves net reactions on the catalyst surface to

Feed: +/- 5000 ppm Sulfur
Counts

250000 200000 150000 100000 50000 0

10

15

20

25

Fig. 6.5 Feed and product chromatogram

30 min

118

Chapter 6

Model Building for Refinery Heterogeneous Catalytic Reactions

by hydrogen the to sulphur various compounds sulphide reactions with convert hydrogen. The sulphur compounds in crude oil are present largely in the form of thiols, derivatives, difficult thiophenes thiophene and various are and which sulphides, to

detect and to measure. For example, the number of different sulphur compounds that are detected in the chromatogram shown in Fig. 6.5 is enormous. Each single species goes through a complex reaction scheme in hydrodesulphurisation (HDS), mainly composed of hydrogenolysis and hydrogenation. Fig. 6.6 gives the for dimethyldibenzothiophene. scheme reaction

H3C

CH3

Hydrogenation

Hydrogenolysis H3C

ss CH3 H3C CH3

S H3C CH3 H3C CH3 H3C CH3

Fig. 6.6 Dimethyldibenzothiophene

HDS reaction scheme

The general approaches to characterise the fuel mixture

are to classify

sulphur

lumping have into groups, which compounds similar structure and reactive behaviour. Every group is represented by a typical component, in the form of pseudo-component. Fig. 6.7 shows the relative reaction rate of six typical pseudo-components.

119

Chapter 6

Model Building for Refinery Heterugeneu s

100

80 a
cz c 0
U

60

a cz T

40

20

Fig. 6.7 Relative reaction rate of sulphur compounds

The properties of two commercial HDS catalysts are listed in Table 6.3. Ni-Mo/y-A1203 has higher activity for hydrogenation, which is typically used for hydrodenitrogenation (HDN). The ratio of molybdenum to cobalt is always considerably greater than 1.
Table 6.3 Typical commercial hydrotreating catalysts properties
Chemical content and properties Chemicals (wt % dry basis) MoO3 CoO 15.0 3.2 18.5 A B

NiO
Physical properties Surface area (m /g) Pore volume(cm3/g) Diameter (in. ) Average length (in. ) 310 0.80 0.125 0.23

3.3

180 0.53 0.062 0.18

Compactedbulk density
Average crush strength

36
4.2

52
3.1

Fig. 6.8 shows the procedure of catalyst synthesis for hydrodesulphurisation (HDS) desired in This the specification, size and shape; catalysts. method starts with a support the precursor of the catalyst is then coated or impregnated onto the surface of the incipient by wetting with a minimum amount of saturated solution of the support an be in This times order to reach a repeated several process may precursor mixture. desirable level of catalyst concentration on the support if all the component salts cannot

120

Chapter6

Model Building for Refinery HeterogeneousCatalytic Reactions

dissolve at one time. The procedure for the promoter is similar. Once the catalyst is impregnated onto the support, it is then dried, calcinated or reduced as required. During the whole procedure, the volume of solution should be controlled to be about equal to the pore volume of support to ensure total absorption of the solution into the pore

Fig. 6.8 Catalyst synthesisprocedure

structure of support and to avoid waste of the active ingredients and avoid causing an dissolving differ from Optimum in the pH of solution may one salt to error composition. the other. For example, Co-salt prefers low pH whereas Mo-salt prefers high pH. The catalytic activity and selectivity of hydrotreating catalysts may be very sensitive to even small changes in the preparation procedures employed. The major factors are: (pH, loading (concentration, impregnation time, order of metal ratio), procedure metal The temperature. calcination effect of preparation method on the addition of metals) and interaction in Co-Mo/Al203 be by can studied structure, stability and metal/support different methods (Sie, 1993; Khorashen et al., 1998; Adachi, 1996; Leliveld et al., 1998; Farag, 2002). Industrial HDS is generally carried out between 573 K and 698 K and pressure from 10 to 200 atm, depending on the feedstock and process requirements. HDS processes are

121

Chapter6

Model Building for Refinery HeterogeneousCatalytic Reactions

highly exothermic. Hydrogenation is favoured only at low temperature and at high pressure.

6.3 Model building methodology for HDS processes

Any factor in each of the three aspects of chemistry, catalyst and the process cannot be ignored in model building for heterogeneous catalytic reactions. Accordingly,

difficulties and challenges arise in the HDS model building process. For example, further exploration on the choice of the reaction complex catalytic chemistry needs different Effects of assumptions or mechanism mixture representations. scheme, different catalysts are unclear, and no quantitative correlation is available for structure sensitivity. Accurate data fitting and changing different type of reactor or reactor size (batch, continuous fixed bed reactor, CSTR) cannot provide future information for discrimination. mechanism Hytrotreating catalysts are presently going through a major development program. The for for development is this the that catalysts presently used primary reason hydroprocessing are quite satisfactory when employed for the lighter crude petroleum, but the United States and much of Europe may find the lighter petroleum crudes to be less available, either because the supplies are exhausted, or because of geographic or develop As the to political problems. a consequence, need processesthat are satisfactory for heavier crudes, coal-derived liquids, and shale and tar sands oil is evident. In

for heterogeneous have building duration the catalytic reactions will of general, model being 5 large to a number of experiments carried out. up years, with Hydrodesulphurisation has been studied by numerous researchers. However, most following have the or more of methods or assumptions to simplify the studies used one building: model 1. Sulphur model compounds are dissolved in pure solvents to simulate fractions petroleum 2. The reaction schemes are simplified as parallel reactions: hydrogenation and hydrogenolysis (Studies have indicated that the hydrogenolysis and

hydrogenation reactions occur on separatesites).

122

Chapter 6

Model Building for Refinery HeterogeneousCatalytic Reactions

3. 4.

Surface reaction is assumed as the rate-determining step Sulphur compounds are lumped as groups

However, there are some unanswered questions: which kind of adsorption of hydrogen, dissociative kind and which of surface reaction, single site or dual site or molecular or Eley-Rideal? Should catalyst active site concentration be constant or variable? Also, how be the the catalyst geometric properties affect reaction cannot exactly rate still determined easily. A large number of rival models from the combinations of all possible for heterogeneous inevitable catalytic reactions. assumptions are For instance. there are 174 rival models for Dibenzothiophene HDS (Vabrysselberghe, 1996) or 15 rival models for Diesel HDS (Hidalgo, 1999) in the literature. It is difficult to carry out mechanism discrimination without information from catalyst

characterisation. HDS kinetics of a mixture of sulphur compounds in an industrial feedstock is far more However, for than that complicated of a pure substance. although process engineers these power rate equations are simple and can easy predict the effect of the reactor operating changes on performance, they fail to predict interactions between reactants, products and the catalyst. The LHHW approach for expressing the reaction rate is used. In this work, reaction model building will be divided into three levels, in order to kinetic separate from diffusion Catalyst effects. characterisation and optimal

design in level help discriminate to are used each experimental among rival models. Model discrimination in the early stages can help to save experimental effort in the later stages. Practical operating conditions are preferred. Thus, the best model will be obtained to provide reliable parameters for process development. The whole procedure 6.9 discussed in Fig. be in detail in following the shown will sections.

123

Chapter 6

Model Building for Refinery Heterogeneous Catalytic Reactions

Low External diffusion Extrinsic level

Optimal
Discrimination
iscri

experimental design

>1 ,40
0 o,

Internal diffusion
U

Apparent level

Catalyst characterisation
Discrimination

No diffusio

Intrinsic

High

effect

level

Fig. 6.9 Model building framework

6.3.1 Catalyst characterisation

Heterogeneous catalytic reaction occurs on the surface of catalysts. Therefore, the

for is the performance of catalysts. status crucial surface

There are three main properties related to the catalyst that need to be characterised: bulk 6.10. in Fig. texture properties, and surface properties, as shown properties, Bulk properties include:

1) Composition and constituents of a catalyst 2) Pellet size and shape

3) Mechanical strength

4) Bulk density
Texture properties include:

1) Surface area 2) Pore volume 3) Pore size and distribution Surface properties include:

124

Chapter 6

Model Building for Refinery Heterogeneous

1_. tions

1) Adsorptive properties
2) Dispersion 3) Chemical activity

4) Bonding and oxidation states of active components 5) Atomic and crystal structure of active components

Texte re
Bed density Void volume Bulk Pellet shape Pellet size

Surface area
Pore size distribution Active material distribution Pore volume 1, :', x. Morphology Structure Dispersion Acidity/

Fig. 6.10 Catalyst properties

In order to have a comprehensive understanding reaction mechanism including

of catalyst properties to study a

the function of active components on the surface, to

best design to the the guide and synthesis of catalysts and choose performance catalyst for a certain feedstock, it is desirable to obtain a complete description of both the can also

structures and active sites where the catalysis takes place. Such information known the serve catalyst and providing purposes of reproducing a future reference or for a business transaction.

a specification for

For the purpose of obtaining a clear knowledge of the catalyst properties related to the kinetic study, characterisation of the catalyst is necessary at every stage of the

development. Characterisation

link between the can provide catalyst properties and

kinetic models through catalytic activity to validate the mechanism assumptions by:

1. Reducing assumptions relating to the mechanism 2. Helping to determine kinetic parameters for single reaction steps.

125

Chapter6

Model Building for Refinery HeterogeneousCatalytic Reactions

With the aid of chemical and physical methods for catalyst characterisation, bulk, texture and surface properties can be obtained, but not all are necessary for a specific determine bulk The the the the surface properties nature of catalysts, while application. and texture properties affect the catalyst performance through mass transfer. For kinetic studies, information that can clarify the reaction mechanism and accurately determine the heat of adsorption and reaction intermediates is useful. Recently, more have been introduced identify techniques to or accurately measure and more new be incorporated in kinetic These framework the should of the catalyst properties. heterogeneouscatalysis. There are a large number of techniques available to characterise catalyst properties and measure activities. These include spectroscopic methods, diffraction methods,

isotherm adsorption methods, temperature programmed methods, methods, porosimetry be discriminating The experimentalist must and select the technique that yields the etc. information most with accuracy, speed, and economy. To achieve this, it is necessaryto know precisely the objectives of the investigation, the limitations of each technique, and the expected value of the results. capabilities and General rules for selecting characterisation techniques are: " " " " " Applicability: real catalysts Easy access:common equipment Low cost: normal working conditions Informative: multipurpose techniques Versatile: many different systems

For the purpose of kinetic studies and model discrimination of the HDS process, there are three useful properties. These are the sulphided state of the metal, which is related to the active sites of the surface reactions, metal-sulphur binding energy that also plays a desorption, in the role adsorption and and identification of intermediates that can help to describe the reaction mechanism.

126

Chapter 6

Model Building for Refinery Heterogeneous Catilytic

Reactions

The widely used characterisation techniques that can provide the above information compiled in Table 6.4 for

are

For being, building the time process catalysts. -IDS

between correlations activity and catalytic characteristics still needs further quantitative be for These design could used and optimisation research. feedstock in the future. for of catalysts a certain

Intrinsic level

No diffusion effect

Apparent

level

Internal diffusion control

d(W
Extrinsic level External diffusion control

Fo

-Vi

l7i ' 77e ' rw

Kinetic model

Fig. 6.11 Catalytic kinetic model composition

Table 6.4 Compilation of techniques for HDS catalysts

Information T ech n i ques Surface composition XPS TPD Calorimetry EXAFS* IR Mossbauer* Intermediates Adsorption heat

127

Chapter6

Model Building for Refinery HeterogeneousCatalytic Reactions

6.3.2 Catalyst kinetics

Anything related to reaction kinetics cannot be estimated from theory, and must be determined by experiments. Experimental data is essential for model derivation of heterogeneouscatalytic reactions, as is the case for homogeneous reaction systems. In comparison with homogeneous reaction systems, catalysts play a very important role in the model building for heterogeneous catalytic reactions. So in catalytic kinetic studies, catalyst effects are reflected by internal and external diffusion for a preselected catalyst. The kinetic studies can be carried out under different sets of experimental conditions, depending on whether the kinetic data is obtained in the presence or absence of internal limitations. be Therefore, transfer experiments can conducted in three or external mass levels, intrinsic level, apparent level and extrinsic level, to represent the different mass transfer effects. Accordingly, reaction models are developed level-by-level, while the kinetic expression is written in the form of separateterms that represent different levels (shown in Fig. 6.11). The Weisz-Prater (1954) and Carberry criteria are used to test if the experimental data kinetically internal diffusion in the are controlled regime, controlled or external

diffusion controlled regimes. Thus, different experimental data are responsible for the parameter estimation in different terms of the kinetic expression. (i) In the intrinsic level of kinetic studies, both internal and external mass transfer limitations should be eliminated. Generally, experiments are carried out using crushed fine catalyst particles and under appropriate conditions to achieve the target when the Weisz-Prater criterion is satisfied. The Weisz-Prater criterion for internal diffusion control is: rv "L n+1 (D _ 17102 = De Cb 2 f"
2

)<O.

15

(6.1)

factor is internal where i7 effectiveness is Thiele modulus

128

Chapter 6

Model Building for Refinery Heterogeneous Catalytic Reactions

Deff is diffusion coefficient is n reaction order Cb is bulk concentration is rv reaction rate per unit particle volume L is pore length Concentration profiles inside and outside the catalyst particle are shown in Fig. 6.12. (ii) Experiments that are conducted using commercial size catalyst, but eliminating only the external mass transfer resistances provide the experimental data for apparent kinetic study. In this level, the Carberry criterion for external diffusion control is used. Conditions are for the experiments such that: chosen C a =Cb-CS Gb < 0.05
Inj

(6.2)

Ca is Carberry where number CS is catalyst surface concentration Cb is bulk concentration is n reaction order When this criterion is satisfied, experimental data are obtained for the parameter estimation in apparent kinetic term. (iii) In the third level, experiments are carried out in such a way that neither internal diffusion resistancesnor the external mass transfer limitations are eliminated. This gives the extrinsic kinetic model of a reaction where neither the Weisz-Prater criterion nor the Carberry criterion are satisfied. Diffusion effects are accounted for using effectiveness factors. observed rate rate at catalyst surface conditions (6.3) r? 77i = e" rate at catalyst surface conditions rate at bulk conditions

129

Chapter 6

Model Building for Refinery Heterogeneous Catalytic Reactions

internal is the i7i effectiveness factor, representing the internal diffusion effect; where factor, is diffusion the the rye external effectiveness representing external effect. In the internal diffusion control regime and external diffusion control regime,

factors are calculated separately: effectiveness

tp rv 1i (C)dV

(6.4)
rv(Cs) -VP

). Vp rv((7 rte = (Cb)'Vp r

(6.5)

Therefore the complete expression of the catalytic reaction rate is: dX d(tip/Fo) 77177e rW -V`

(6.6)

where X is conversion W is catalyst weight FO is flow rate vi is stoichiometric coefficient is intrinsic the reaction rate. r,, So experiments are carried out to obtain data for kinetic studies. Finding the model that closely matches the experimental data is an optimisation problem. The method used for heterogeneous catalytic reactions is the same as those for homogeneous reactions. Hybrid optimisation is good for the resulting large-scale MINLP problem after being tested on complex homogeneous reaction systems.

130

Chapter 6

Model Building for Refinery Heterogeneous Catalytic Reactions

CS

CS

Fig. 6.12 Concentration profile

During the model

derivation

for heterogeneous catalytic

reactions, some physico-

be satisfied. chemical constraints must

Accepting that the rate coefficient should obey Arrhenius' law, Boudart et al. (1967) derived constraints on the adsorption enthalpies and entropies, which are too often also
Since is AH the adsorption adsorption exothermic, standard enthalpy must overlooked. inequality: the satisfy

>0 -AH

(6.7)

between difference in the standard entropy an adsorbed component at while -4S , in 0.5 the same component the gas phase, must satisfy: surface coverage and 0<-AS <AS (6.8)

As a rule, the following limits for the adsorption entropy should be observed 41.8<-AS0 <51.04+1.4x10-3(-AH (6.9)

AH is J AS is J K-1; the the mol-1. mol"1 unit of where unit of -

131

Chapter6

Mclui1 i,k- It_, _ineryHeteP, iu

Fig. 6.13 Laboratory reactors for heterogeneous reactions

6.3.3 Model discrimination

As discussed earlier, catalyst characterisation can provide information to discriminate

mechanisms at the early stage of model building to reduce the number of rival models. After a set of rival models is obtained, further experimental data are needed for model discrimination. It should follow the same procedure as for homogeneous reaction

difference the to systems achieve maximum among model performance. Optimal experimental design for model discrimination is obtained through combinations

The laboratory types of reactor and operating conditions. operation modes of reactors for heterogeneous listed in 6.13. Fig. The used reaction systems are classified and same hybrid reactor superstructure and optimisation reaction systems. for homogeneous approach are used as

In conclusion, to deal with complex heterogeneous catalytic reactions, kinetic studies and model discrimination are carried out in three levels, to separate kinetics from the diffusion effects. Combining the information from catalyst characterisation, the number for be in The the of rival models can early stage. reduced priority model discrimination in the three levels is in the order from the intrinsic level, apparent level, to the extrinsic

132

Chapter 6

Model Building for Refinery HeterogeneousCatalytic Reactions

level, in order to save experimental effort. To be more specific, the model building is interpreted by hydrodesulphurisation (HDS) processes. procedure

6.4 Case studies

In this section, two HDS processes will be used to illustrate the model building for heterogeneous These catalytic reactions. are -IDS processes of typical methodology single sulphur compounds and a mixture of sulphur compounds.

6.4.1 Hydrodesulphurisation

of thiophene

Firstly, a single compound thiophene HDS is used to illustrate the methodology. The hydrodesulphurisation of thiophene is a well-studied reaction, and a large amount of data have is Different tried to reveal the reaction available. researchers experimental have built different thiophene and models to represent the reaction mechanism of system. The experimental data (Satterfield, 1968; Lee, 1977) used in this case study to develop model are listed in Fig. D-1 and D-2 of Appendix D. A small proportion of from building be be held data in the procedure and will model will reserve experimental later discrimination in the stage. used model Model 1,2,3,4 (Eq. 6-10,11,12,13) have been developed by Satterfield & Roberts

(1968), Lee & Butt (1977), Morooka & Hamrin (1977), and Van Parijs & Froment (1986b) respectively. Kinetic parameters for Model 1 to Model 4 are listed in Table D-1 to D-4 of Appendix D. PT ' PH2 +K
PH2S H2S S

Y1=k' (1+KTpT

(6.10)

PT pH'r2 =V (l+KTpT
k"pT

(6.11)

+K

pH2S HZS

r=2 (i+

"pH2

(6.12)

KTPT +KH2SPH2s

133

Chapter 6

Model Building for Refinery Heterogeneous Catalytic Reactions

r=

k'KT'KH2 (1+(KH2

*PT'PH2

P.s KH KT + + PH2 PH PT PH S S/

(6.13)

Ea) k k= where "exp( RT ) KT = KT "exp( RT

HZS 0T

KHZS =KpHZS "exp( KHZ =K

0H,

RT
H2

"exp(

RT

The thiophene (T) BIDS reaction scheme is described as:

J C4H8 + H2 ->C4Hlo
1. 2. 3. 4.

C4H4S + 3H2 -

C4H8 + H2S

The following assumptions are possible: Surface reaction is the rate determining step Hydrogen adsorption type: either molecular or dissociative Hydrogen and sulphur compounds adsorption: either in the same site or not Adsorption of thiophene: either one point or two points

Eight models are obtained through combinations of the above mechanism assumptions, Model A to H (Eq. 6.14). Values of the model parameters, m, n, a, b, are listed in Table 6.5. k'KT''H2'PT'PH2 ra-H = (1+(KH2 )" Kx2s KT + + pT PH2s " PH2 (6.14) "1+(KH2 "PH2)b

Table 6.5 Factors of Eq. 6.14

ode A M 2 n 1 a 0 b 1

134

Chapter 6

Model BuiIdiri, for Refinery Heterogeneous Catalytic Reactions

C
D

3
2

0
0

1
1

0
0

E F G H

2 1 3 2

1 1 0 0

0 0 0.5 0.5

0.5 0.5 0 0

The kinetic parameters of each model obtained from data fitting are listed in Table D-5

6.14. has Model A is in Fig. Model A D. The Appendix a good shown parity plot of of
data, do the the other models. experimental as agreement with

Model A
500

400

"f / ff

300

200

100

100

y
200 300

400

500

Fig. 6.14 Parity plot for Model A

Discrimination of Model A to H needs further experimental data. However, extra following data the conditions: available at are only experimental
" 0 0 Temperature: 623K Total pressure: 780 mmHg Thiophene partial pressure range: 6 mmHg to 18 mmHg

It is further assumed that experiments will be carried out under the above conditions in a differential reactor. Therefore, the reaction rate (units: mol "min-1 " gear-' ) can be

135

`hapter 6

Reactions Heterogeneous Catalytic for Refinery MO.: l LIJ adding

directly compared and obtained

instead of conversion.

From Fig. 6.15, it can be

have H, 1 4 Model A Model 12 to to that the model predictions of and models, observed different quite The performances. maximum difference point of is at the highest

thiophene partial pressure of 18 mmHg.

When compared with actual experimental data

6.16 be ignored. In Fig. the optimal experimental point, measurement error cannot at five rival models (circled) can be eliminated because their predictions are far from the actual performance.
A E Satterfiled 1000 900 800 700 + 600 500 400 300 200 100 0 579 11 13 P(T) mmHg 15 17 19 B F Morook ^ ^ C G Van Parijs D H Lee

Fig. 6.15 Model predictions

-----f 1000 900 800 700 + 600 500 400 300 200 100 0 5 10 P(T) mmHg 15 20 ABCD EFG Satterfiled data

Morook

--

-Van

Parijs

-H

Lee

. .

Fig. 6.16 Optimal operation conditions for model discrimination

136

Chapter 6

M( dc 1B,

L,

The other models, whose model parameters are updated with the new data, can be further discriminated by using the data from the next optimal operating conditions.

6.4.2 Hydrodesulphurisation

(HDS) of diesel

In the second case study, diesel HDS is chosen because of its importance in the refinery industry. The sulphur compounds in diesel are represented here by four pseudoin building the model components of the diesel hydrodesulphurisation (DBT), Methyldibenzo-thiophene processes: (MDBT),

Benzothiophene (BT), Dibenzothiophene Dimethyldibenzo-thiophene (DMDBT).

Their molecular structures are shown in Fig.

6.17. The reason for choosing these four pseudo-components is to make use of current literature, because data in data for the the the single either experimental experimental data for diesel based four is the this on pseudo-component components are available, or assumption.

\ ss

\ IS
CH3

H3Ci

CH3

Fig. 6.17 Pseudo-component of sulphur compounds

In order

to

maintain

consistency,

the

feedstock same

is

during used

model

discrimination,

and other compounds, except sulphur compounds, remain unchanged.

The boiling curve and properties of diesel used in this case are listed in Fig. 6.18 and Table 6.6.

137

Chapter 6

Model Building for Refinery Heterogeneous Catalytic Reactions

Boiling Curve
400 380 360 340
a 320

300

280 as 260 240 220 200 0 10 20 30 40 % 50 60 70 80 90 100

Fig. 6.18 Boiling curve of diesel fuel

Table 6.6 Diesel properties

Total sulphur, wt% Density at 15C, kg/m3 Pour point, C ASTM boiling range, C Aromatics Composition, vol. % Olefins Saturates 0.706 840 -10 240-380 17 5 78

In HDS processes, the sulphur compound reaction scheme is simplified hydrogenolysis. hydrogenation and reactions,

to be parallel

Each reaction takes place on a different

for hydrogenation, denoted for hydrogenolysis the and i which site of 6 catalyst surface,

is agreed by most researchers (Delmon, 1979; Broderick & Gates, 1981; Vrinat, 1983; 1986) Parijs 1986b; Van Parijs & Froment, al., et van The options for the reaction mechanism are: 1. a -site: hydrogenolysis Hydrogen adsorption: molecular or dissociative Sulphur compound/ H2 adsorption: non-competitive or competitive

138

Chapter6

Model Building for Refinery HeterogeneousCatalytic Reactions

Sulphur compound adsorption: two adjacent or a or one -sites -site Rate-determining step: surface reaction and is irreversible 2. r -site: hydrogenation Hydrogen adsorption: molecular or dissociative Sulphur compound/ H2 adsorption: non-competitive or competitive Rate-determining step: surface reaction and is irreversible If all plausible reaction mechanisms had been considered, the number of models formulated would have been of the order of 102. Furthermore, the number of kinetic is large difficult is their task. parameters and estimation a So, only two models for the HDS process are developed to illustrate the nature of the kinetic The problem. models are used to fit the experimental data of conversion against time reported by Kabe et al. (1992), Bartsch & Tanielian (1974), Singhal et al. (1981), Ledoux et al. (1990), Kabe et al. (1994,1997), Ishihara & Kabe (1993). In Model 1, the combination of assumption options is that on o sites, hydrogen adsorption is molecular; sulphur compound adsorption is non-competitive with H2 adsorption, two sulphur compounds are adsorbed on one o' site. On z sites, hydrogen adsorption is assumed to be molecular; sulphur compound adsorption is assumed noncompetitive with H2 adsorption. Eq. 6.15 and Eq. 6.16 are the kinetic models for the two sites. The kinetic parameters 6.7. listed in Table are
r= k1 42

Kl 1+
i=1

PH2 6PKH2 O. H2,07 H2

(6.15)

(1 KH2SPH2S " + Ki + aP

Kl

rz=k

rFKH2, rPH2

. (1+

(6.16)

Ki,

zP

+ KAPA

139

Chapter 6

Model Building for Refinery Heterogeneous Catalytic Reactions

Table 6.7 Kinetic parametersfor Model 1

U -site Z -site

k BT DBT MDBT DMDBT H2 H2S Aromatic

E Ea a (kJ/mol) 47000.1 165000. 6 188000.

AH (kJ/mol) -104.50 -166.30 -190.60 -217.70 -145.07 -92.46 -

a (kJ/mol) 89000.2 140000.

AH (kJ/mol) -102.50 -97.60 -158.00 -204.80 -223.36 -120.56

-0.14; -0.2; -2.0; -3.3; -

-10.7 -10.81 -10.50

-4.7 -5.5

-7.94 -7.36

136000. -5.8 222000. -11.64 -7.5 -7.59 -5.8 -7.93 -7.79 -10.06 -7.28

201000. 0 -

In Model 2, the combination of assumption options is that on or sites, hydrogen H2 is is with non-competitive adsorption molecular; sulphur compound adsorption On two two 6 z sites. adjacent sulphur compounds are adsorbed on adsorption, and be hydrogen is to adsorption assumed molecular; and sulphur compound sites, H2 is adsorption. adsorption assumed non-competitive with Eq. 6.17 and Eq. 6.18 are the kinetic models for the two sites. The kinetic parameters 6.8. listed in Table are P x2, H2 (1 KH2, Ki,, P + K; + " 12SPH2S PH2 K PK (6.17)

r=k", 1+

Ki
i. =ki,. 4

rFKH2 rPH2 zP +KAPA

(6.18)

1+KZ, =i

Table 6.8 Kinetic parametersfor Model 2

U -site T -site

Ea (kJ/mol)

AH (kJ/mol)

Ea (kJ/mol) 0l)

AH (kJ/mol)

140

Chapter 6

N1o; di: i B uilding for Refinery Heterogeneous Catalytic Reactions

BT
DBT MDBT DMDBT H2 H2S Aromatic

-0.15
-0.19 -1.9 -3.5 -

77000
165000 198000 201000

-10.5
-10.8 -10.50 -11.64 -7.5 -7.59 -

-104.50
-146.30 -190.60 -217.70 -140.07 -102.46 -

-2.0
-5.0 -5.8 -6.9 -

89000
140000 186000 222000

-7.44
-7.36 -7.28 -8.03 -7.79 -10.06

-100.50
-120.60 -158.00 -204.80 -223.36 -220.56

In general, optimal experimental design is to optimise all parameters together, such as distribution, H2, H2S temperature, partial pressure, reactor type and size, content sulphur Unfortunately, etc. for such complex reaction systems, the data points cannot be easily

it is impossible to compare two model predictions at the randomly obtained, so

discussed here Single to clearly show the parameter effects are calculated optimal point. Firstly, temperature and sulphur compound content effects are considered methodology. without diffusional effects.

6.4.2.1 Temperature effects The only available experimental data for diesel IDS is from Ma (1994). This tested the
in change conversion Two temperature. rival models are used to calculate the with with the change of

behaviour of four pseudo-components (BT, DBT, MIDBT, DMDBT)

temperature. The objective function is to calculate four pseudo-component prediction differences of the two models separately.
f data --Modell ---A---Mode 12 f data a Model l--A2 - -Model

1
F-

o.8
w

Q
0

0.8
0.6

0.6 0 0.4 U 0.2 n

Cl) 0.4
a)

0.2
41

0
650 600 550 Temp erature(K) 700 750 500 650 600 550 Temp erature(K) 700 750

500

141

Chapter 6

Model Building for Refinery Heterogeneous Catalytic Reactions

"

data

--

-"F-----

Model 1--"A--

-Model 2"

data

---*-Model

1---A---

Model 2

E, 0.8 o O.6 70.4 ,, 0.2 0 U0 r 500 550 600 650 Temperature(K) 700 750

1 0.8 0.6

0 0.4 0.2 0 500

" ""i

VAL550 600 650 Temperature(K) 700 750

Fig. 6.19 Pseudo-componentperformance of different models

It is observed that temperature effects for the two models on four pseudo-components
Model similar. prediction are has the biggest difference on the BT conversion (Fig.

6.19) 6.4.2.2 Sulphur compound addition effects

Ideally, it is preferable to know the effect on model prediction if the sulphur compound distribution profile is changed. Because changing the content of four sulphur

laboratory, is impractical in the compounds simultaneously optimization

of the sulphur

is based be on single sulphur compound addition, which can easily compound content difference in laboratory. The is two the the of calculated when the carried out models content of four sulphur compounds is changing individually. It is shown in Fig. 6.20

that the difference of BT between model predictions is more sensitive than the other compounds. Thus, if change of the sulphur compound discrimination, BT addition is the best choice.
0 BT DBT MDBT DMDBT

content is used for model

0.45 0.4 0.35 0.3 0.25 Q 0.2 0.15 0.1 0.05 0

420% 260% 140% 180% Sulphur Compound Addition

Fig. 6.20 Model difference of each pseudo-component addition

142

Chapter 6

Model Building for Refinery Heterogeneous Catalytic Reactions

6.4.2.3 Catalyst effects

Catalyst effects on kinetic model building are reflected in the diffusional terms of the

If rival models cannot be discriminated from the operating conditions rate expression. (T, P, sulphur content distribution, etc. ), catalyst effects should be considered for further discrimination. model distribution size Catalyst pellet size, shape, active material density, location, pore In this thesis, only active

can all be used for model discrimination.

location inside the pellet and pellet size will be discussed. material 1. Active material location There are several different methods to model active material location, step function, 6dirac function, distribution and active material profiles. Here distribution of active

by function, inside is 6.21. in Fig. The idea is the pellet represented a step material as based on the different diffusion characteristics of the four pseudo-components inside the catalyst pellet.

Pellet dimension x1

Fig. 6.21 Catalyst active material distribution profile

Diffusivity

by be the DMDBT that MDBT, DBT, BT, assuming calculated will of

diffusion of sulphur compounds in the catalyst is purely Knudson diffusion. rw Deff = 9700rp
where rp is pore radius

(6.19)

T is the temperature K M is the molecular weight of diffusing species

143

Chapter 6

Model Building for Refinery Heterogeneous Catalytic Reactions

The relative diffusivity can be obtained easily through: D1_ D2 M2 M1

Model 1
"

(6.20)

1 0.96
9.1

Model 2
BT DBT MDBT 0.99 DMDBT

0.995

---K-

0.92 r'0.88 U

0.985
f--BT DBT MDBT DMDBT

0.98 0.975 0.97

0.84

0.8
0 0.2 0.4 0.6 0.8 Active material location 100.2

0.4 0.6 0.8 Active material location

Fig. 6.22 Model performance changing with active material location

From Fig. 6.22, it is observed that the change of active material location from the has less to the the surface core of catalyst pellet, effect on the compounds with higher diffusivity because the compounds with the higher diffusivity can easily reach the centre

So discrimination of pellet. model

be done by can comparing refractory compounds,

have different a performance. which quite

2.

Catalyst pellet size

While catalyst size is decreased to reduce the internal diffusion effects, Model 1 shows the changing point of conversion in the experimental range, but Model 2 shows no such determine been in 6.23). has (Fig. It the change of to the experiments used point diffusion-controlled discrimination for be This model used point can also regime.

through changing the catalyst size.

144

Chapter 6

.I_

Heteroen, 11-Iery

--()w

i( 1eactir

Model 1 0.998 0.997 0.996 . O. 995 0.994 00.993 0.992 0.991 0.99 0 10 20 30 -f--+-BT DBT MDBT DMDBT 0.982 0.981 0.98 .20.979 0.978 0.977 0.976 0.975 0.974 0

Model 2

Partical size (mm) Fig. 6.23 Model performance

20 Partical size (mm)

10

30

changing with particle size

In brief, through the above calculation results, experimental conditions for diesel model discrimination can be recommended as: "
0 0 0

Temperature: 633 - 673 K

BT addition: more than 40% of original content Catalyst active material location: centre to surface Catalyst size: 0.1 mm to 5 min

At the above operating conditions, rival models stand the biggest chance to be
discriminated.

6.4.3 Discussion
Two hydrodesulphurisation illustrate been have the to model used reaction systems

diesel HDS. thiophene heterogeneous for and building methodology catalytic reactions: From no diffusional between rival diffusion internal to effects have been explored discriminate different to ways effects, the basic view for model

models

to provide

discrimination of HDS models. In the future, the relationship between catalyst characterisation and catalyst properties discriminate them. develop amongst be included and models to effectively should

145

Chapter 6

Model Building for Refinery Heterogeneous Catalytic Reactions

6.5 Conclusions
In this Chapter, a systematic methodology for model building and discrimination for heterogeneous catalytic reactions has been explored. Due to the complex nature of large difficulties for model building and a number catalysis, of rival models pose discrimination. A three-level kinetic study method has been introduced to reduce the by diffusion from kinetic equations. In addition, complexity separating model effects has been characterisation catalyst suggested to assist model discrimination. A

discussed here provides guidance for selecting those techniques classification of techniques to characterise HDS catalysts with accuracy, speed, and economy. Because hydrodesulphurisation importance (HDS) processes in the refinery industry, the of of for discrimination model and model improvement for thiophene and plausible ways diesel HDS have been explored, including operating conditions, feedstock and catalyst effects.

146

Chapter 7

Conclusions and Future Work

Chapter 7: Conclusions and Future Work

7.1 Conclusions 7.2 Future work 7.3 Remarks

147

Chapter 7

Conclusions and Future Work

Reaction models for complex reaction systems involving

detailed chemistry and

mechanisms are crucial for the purpose of reactor design and optimisation. However, for fine reaction systems, such as processes complex and speciality chemicals and feature high value and short market window, which leads to pharmaceutical chemicals, the development of detailed models being unattractive. Processes involving

heterogeneous catalytic reactions also need a systematic approach to quickly and behaviour, design for the to and optimise a certain processes accurately predict feedstock to meet the product specifications. To date, generic model building methodologies applied to complex reaction systems have mostly been based on empirical rules, where the key features of reaction systems being lead This be to the operated under non-optimal process can missed. might in development limitation due the time the to procedure of and of costs conditions, building. model In this work, the research objective focuses on providing a new approach to model building from the chemical engineer's point of view, to avoid important information being missed and reduce the risk of process scale-up failure. is engineers A new systematic method to combine the work of chemists and chemical information, the full extract in to use of experimental make proposed this thesis, aiming to design, the for experiments minimum and arrange process optimal model suitable laboratory and pilot experiments. save expense of limitations the discuss the of This chapter will summarise the proposed methodology, to closely future areas extension potential and work methodology and recommend linked to this project.

7.1 Conclusions
derived feasible are schemes reaction With little knowledge of reaction chemistry, and systems inlet reaction of directly from information of the and outlet species to used The are data. species participating screened with preliminary experimental An matrix in atom-molecule two-stage method. a reactions the set of all generate for system reaction be represented to systematically formulation allows all species

148

Chapter 7

Conclusions and Future Work

be and analysis can used to describe reactions in the form of reaction equations. In addition, the rank of the matrix is an important constraint, which is calculated through a SVD (singular value decomposition) method. After generating all possible reactions by a two-stage method, integer linear

is programming used to test the stoichiometric feasibility of the reactions identified satisfy the mass conservation law. It is guaranteedthat all possible reaction steps and all feasible reaction schemes are generated. Feasible reaction lists in each stage through two-stage method are used to construct reaction schemes. Construction of reaction schemes provides reaction schemes from the combinations of feasible reactions generated from the two-stage procedure. The strategy that searchesall possible combinations of reaction steps can guarantee that all plausible reaction schemes are obtained, and has been discussed in detail with an example. The experimental data can be used to identify which reaction schemes are of more interest, and derive kinetic by simultaneously optimisation. Because more than one model can fit the same experimental data set, it is essential that all reaction models are obtained before further experiment information is available. Extracting reaction models from experimental data, including reactions schemes and kinetic expressions, is a mixed integer nonlinear programming problem (MINLP). Appropriate optimisation methods should be chosen to guarantee the global optimal solution. A hybrid optimisation approach is proposed to identify suitable reaction schemes and kinetic equations with the aid of experimental data. This approach combines a stochastic deterministic (SA) Annealing Simulated optimisation method a algorithm with method (SQP). The former provides potential candidates as rival models, and the latter is used to fine-tune model parameters. Stochastic optimisation is designed to get a set of solutions close to the optimal region by setting up reaction scheme moves and kinetic moves to generate alternatives and SA The the mismatch of model risk can reduce algorithm the search. monitor random parameters for the reactions within the schemes

149

Chapter 7

Conclusions and Future Work

through avoiding model elimination in the preliminary stage. Through the test of two SA cases, optimisation combined with NLP has been shown to provide good solutions for the MINLP problem. Further experimental data is required for model discrimination among rival models. Optimal experimental design should be applied to achieve the target of minimum experimental effort. Based on the phenomena that reaction models might have different performances in different types of reactors and under different operating conditions, an experimental reactor superstructure is used, in which all kinds of laboratory reactor and operating conditions are embedded. Therefore, all kinds of operating conditions, including feeding policies, phase contacting patterns, mixing types, recycles and discharges can be generated within the experimental reactor superstructure during the differences. In this work, the stochastic optimisation method is maximisation of model used again to guarantee robust and fast global solutions. This approach has been applied to two reaction systems. A small set of models are for discrimination readily obtained model and optimal experimental design. Because of the lack of experimental data, further validation of models is restricted in the available data. experimental A model building methodology for heterogeneous catalytic reactions is much more in due to the which mass transfer effects cannot complex, complex nature of catalysis, be ignored. A large number of models exist from the combination of mechanism for in decomposition the of complex reaction steps catalytic reactions assumptions, so in discrimination is Model building is the early stages, along carried out model used. further building to experimental effort. with model reduce Firstly, characterisation of catalyst property effects on reaction models provides good insights for discrimination of mechanism assumptions on diffusion, adsorption and desorption. However, there are a large number of techniques with different capabilities and limitations available to connect catalyst properties, catalyst activities with model A be in but classification of these useful a given application. will performance, not all of for techniques to here discussed suitable selecting those techniques guidance provides information with accuracy, speed, and economy. the yield most

150

Chapter 7

Conclusions and Future Work

Secondly, a three-level kinetic study method has been combined into the model building methodology to reduce the model complexity by separating diffusion effects from kinetic equations. Three levels in kinetic studies serve the same purpose of simplifying the procedure of reaction model development. Hydrodesulphurisation (HDS) is an important process in the refinery industry.

Thiophene HDS and diesel HDS have been used as illustrative examples. Plausible for discrimination improvement for diesel HDS thiophene model and model ways and have been explored, including operating conditions, feedstock, and catalyst effects. Nevertheless, there are some limitations when the methodology is applied. The main limitation of the methodology is that all the reacting species involved are assumedto be detectable. However, it is not always true in some cases, in which either species are for be known but It to existing undetectable. will add uncertainties missing or species for be building, crucial system scale-up and control. which might reaction model Another limitation involved in the new approach is that thermodynamic feasibility of Only the is are obtained. steps reaction as constrains while applied reaction systems not kinetic limitations the parameters are are applied, when wide ranges of general let it important is feasibility Thermodynamic us as would of a reaction very optimized. know in the preliminary stage if further evaluation of the reaction should be carried out or not. basis derived is the for of the chemical equilibrium The feasibility and condition on feasibility ) (OG Energy the Free Gibbs The and predicts energy, enthalpy and entropy. Energy Free Gibbs Hence the of temperature. constant equilibrium condition at formation is very important in the analysis of chemical reactions. If the change in the Gibbs Free Energy of the reaction is Negative, the thermodynamics is Energy Free the Gibbs in reaction of for the reaction is favourable. If the change the favourable. is for the Highly Positive, the thermodynamics reaction not determine the to (reactants Values of individual species and products) are required for However, reaction complex of Energy most the Free Gibbs reaction. of change in the biologic lacking are systems when especially are systems thermodynamics properties

151

Chapter 7

Conclusions and Future Work

To considered. overcome this limitation, methods such as a group contribution method for the estimation of the thermodynamic properties of reacting species should be implemented. Also, it is need to be aware that well-studied reaction steps and kinetics in the reaction help to reduce the searching space and improve model accuracy. can systems

7.2 Future work

There is still a considerable amount of work that needs to be done in order to find the best model for reactor design and optimisation. Some aspectsneed to be considered in the future are: a) The methodology has been applied to homogeneous reaction systems and heterogeneous catalytic reaction systems. It would be possible to refine the for includes that mass transfer effects. multiphase reaction systems method b) Factor sensitivity analysis should be carried out during the optimisation of rival in information This the order to wiser optimisation can provide reaction models. large the search space. reduce c) The hybrid optimisation approach can be applied to model reduction of complex is to the the able construction scheme of reaction strategy reaction systems, where feasibility the check of the reduced reaction schemes. provide d) For HDS processes, the models proposed here are based on simple pseudothe In lumping. of quantification and most work, analysis, evaluation component from been have feedstocks characterisation. catalyst out separately carried real fundamental devoted been has to Even through much effort establishing the between the reactivity, the and catalyst of structure relationships the

future, In from the far of real the is characterisation mature. still correlation feed 1992), the Shih 1998; Looij such as feedstocks (Ho, 2003; van et al., et al., distribution, boiling point density, nitrogen compounds and aromatics contents and

152

Chapter7

Conclusions and Future Work

together with catalyst characterisation, should also be included in the model building. e) Catalyst preparation and complex profiles (egg shell, egg yolk, non-uniform, etc) for the active material location inside a catalyst should also be used for model discrimination.

7.3 Remarks
The methodology proposed in this thesis has been successfully applied to homogeneous heterogeneous systems and refinery catalytic reaction systems. The most reaction is that of using chemical engineering approaches to provide concept significant develop for design for to the chemists reaction models purpose of reactor and guidelines hybrid Furthermore, optimisation methods can meet the requirement that optimisation. data fit the than and can avoid the same set of experimental one model can with more fact that decisions made early might lead to missing the best options for model building. Finally, organic synthesis chemists can also find the importance of the strategy of from in existing automated reaction scheme generation reaction scheme construction elementary reactions.

153

Notation
A X D N S R P I v U V Nlnd D d, d1 &, ,dp p1 d and jp atom-molecule matrix; frequency factor stoichiometric coefficient matrix incidence matrix number of reacting species Species Set Reactant Subset; gas constant Product Subset index vector reaction stoichiometric coefficient vector number of reactions generated from Stage I from Stage II number of reactions generated independent reactions number of Incidence matrix submatrices function density of the n-th experiment under probability i model y IIn_1 IIn experiment; observed response prior probability posterior probability

154

i, j, k r Rj Ci (p If O 0

integer indices for ith reaction reaction rate net reaction rate forjth species concentration forjth species index vector sets of combinations of reactants sets of combinations of products stoichiometric coefficient matrix element of the stoichiometric coefficient matrix hypothesised model response

u1 , 77 (01,02, 0= '' *OP)

vector of model parameters

(i'2''

k dependent variables. vector of upper bound of the coefficient value; error

62 Ea

covariance

activation energy

Fj

flow rate molar

k tk

Boltzman constant annealing temperature Marko v chain length

Lk

155

control parameter internal effectiveness factor external effectiveness factor Thiele modulus diffusion coefficient

ri

17e 0

Deff

n Cb

reaction order bulk concentration

r,, L CS

reaction rate per unit particle volume length pore catalyst surface concentration Carberry number

Ca

n X W FO

reaction order conversion catalyst weight flow rate is stoichiometr coefficient intrinsic reaction rate.

Vi

rw

AH -

standard adsorption enthalpy

156

-AS
6

difference in standard entropy hydrogenolysis site hydrogenation site

157

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171

Appendix A
Calculation of rank of matrix using Singular Value Decomposition (SVD)
For any matrix A, the column rank is the number of linearly independent columns. The is linearly independent the of number rows. The row rank and column rank of row rank Hence, A is its the are equal. rank of a matrix matrix row rank or column rank. a There are a number of ways to compute the rank of a matrix, Gaussian elimination and LU decomposition, but when the matrix that is either singular or else numerically very decomposition, SVD, is known the the technique, to or as singular value close singular, SVD is Even time-consuming. though sometimes most reliable. The SVD method is based on the following theorem of linear algebra. Any MxN its is M to A than of columns number equal or greater of rows number whose matrix U, MxN and N, can be written as the product of an column-orthogonal matrix diagonal NxN NxN transpose the W of an and elements, zero or positive with matrix

V. orthogonal matrix

A = U W J L J VJ

1
orthonormal, M
1=

1 L

their that are in columns the sense V The matrices U and are each orthogonal

UikUin
UikV jn

Skn

1<k<N 1<n_<N 1<k<N

=Skn1n<N

i=1

W. of is W values the singular The element wj in matrix

Wl>W2>.

WN>O

172

The rank of matrix A, rank(A), is the number of non-zero elements of matrix W. The SVD decomposition can also be carried out when M<N. Min(M, N) is always true. If rank(A) = Min(M, N), Under any condition, rank(A) <_ the matrix is a full-rank matrix, otherwise it is a rank-deficient, singular matrix.

173

Appendix B
Linear system solutions
A system of linear equations al, x, +a12x2 +... +alNxN= b, a21x,+a22x2 +"""+a2NxN=
aM1xl + aM2x2 +... +aMNxN=

b2
bN

be in form can written matrix as Ax=b A is aMXN where

al
a21 AM xN _

matrix of coefficients ,
a1.,
a22

...
"".

aIN
a2N

aj
aM 1 am 2 ... aMN

N is of unknowns a column vector and x

x1 x2 X xN

b is the right-hand side written as a column vector, bl b =. b2 bM The augmented matrix of A is (Alb):

174

r
(A I b) Mx(N+1) _ =I

all

a12 a22

... ...

a1N a2N

I I

bl b2

a21

aij

LaMl

aM2

...

aMN

bM

Solution exists if and only if the rank of matrix A is equal to the rank of matrix (Alb). For reaction systems, b=0 according to mass conservation law. So the linear system becomes a homogeneous system. ( (A) (A b) rank = rank There are always solutions for this linear system. For any reaction system, if M>N least and at one reaction exists (a set of the columns the system has an

dependent), linearly is A so the rank of matrix: rank(A) <N, of infinite number of solutions. If M<N, solutions under any circumstance.

the linear system also has an infinite number of

175

Appendix C
The incidence matrix of a digraph*
A digraph G= (X, U) consists of a set of elements, called vertices, and a list of ordered pairs of these elements, called arcs. The set of vertices X= (xl, x2 ,...xn) is called the vertex-set of G, and the list of arcs U= (ul, u2,...u, is the called arc-list of n) G.

The incidence matrix of a digraph D(G) involves the incidence of vertices and arcs. It is defined as anxm I d13 _ -1 0 matrix in which the entry in row i and column j is j arc is incident from vertex i arc j is incident to vertex i otherwise

Analogously, the reaction scheme for reaction systems is also a digraph with reacting species set and reaction lists. The incidence matrix is obtained from the stoichiometric 1 coefficient matrix where dtv _ -1 0 v>0 vl <0. vii =0

The incidence matrix and stoichiometric matrix all can be used to describe the latter the between one provides quantitative relationship reactants and products, while information. *Dolan, A., & AIdous, J. (1993). Networks and algorithms: an introductory approach. John Wiley &sons, London

176

Appendix D
Experimental data for hydrodesulphurisation of thiophene
1. Thiophene BIDS model and experimental data from Satterfield & Roberts (1968)* Operating Conditions: Reactor: differential recycle flow reactor Total pressure: 780 840 mmHg Temperature range: 235 265 C Catalyst: CoO-Mo03/A1203 Experimental data:

f 235
70 60
'0 50 40 30 20 l0 n v ff ;u.

251

265 :

10

20

30

40

50

60

Thiophene Partial Pressure,mmHg

N. (1968) C. Satterfield, Model for data of Fig. D-1 Experimental

Kinetic model:
k'pT'PH2 r 12 (1+KTpT+KH2SPH2S)

k=k" where

E) E exp(

177

KT = K7 " exp(

RTT

KH`S = KHs " exp(

-AHHS

RT

Kinetic parameters
Table D-1 Kinetic parametersfor Model of Satterfield, C. N. (1968) Temperature k KT KH2S Ea
kcaUmol

AHT kcal/mol

AHHZS kcaUmol

C) (O
235 251 265

mol
2 (mmHg) goat." min
0.156E-08 0.164E-08 0.180E-08

(mmHg )-1 (mmH g )-1

0.056 0.031 0.033

0.042 0.018 0.0074 3.7 24 19

* Satterfield, C. N., Roberts, G. W. (1968). Kinetics of thiophene hydrogenolysis on a 14(1), 159-168. AIChE, J., cobalt molybdate catalyst, 2. Thiophene HDS model and experimental data from Lee & Butt (1977)** Operating Conditions: Reactor: internal recycle reactor Catalyst: COO-Mo03/A1203 Temperature range: 250-313 C Partial pressure of thiophene: 20-160 Torr Partial pressure of H2: 550-750 Torr Experimental data:

178

f 313
7

Ilt 300

275

>( 249 ,

6 5
00

. .
.

0 0 20 40 60 80 P(T) torr 100 120 140

(I
160

Fig. D-2 Experimental data for Model of Lee, H. C (1977)

Kinetic model:
k'pT'PH2 r=

1+ KT pT + KH2spH2s 2 E RT )

where k=k"

exp(-

-RTOHT KT = K7 " exp( )

KH= ZS

Ko HZs exp(

-OHH? s RT

Kinetic parameters
Table D-2 Kinetic parametersfor Model of Lee, H. C (1977)
%C0

VO "T
(Torr)-1

KH2S 0

Ea

AH

H2S

mol
cat. " min-

(Torr)2

(Torr)-1

kcal/mol

kcal/mol

kcal/mol

3.40E-05

4.91E-08

3.93E-11

11.9

12.2

20.6

** Lee, H. C., Butt, J. B. (1977). Kinetics of the desulfurization of thiophene: reactions 49,320-331. Catalysis, Journal butene, of thiophene and of

179

3. Thiophene HDS model from Morooka & Hamrin (1977)*** Kinetic model:
k'PT'PH2 r= (l+KTpT

+ KHZS'PH2S

Kinetic parameters
Table D-3 Kinetic parametersfor Model of Morooka, A. (1977)
Temperature

k
kmol

KT
(kN/m2 )-1

KH2s
(kN/m2 )-1

(C)

kgcat.'s" (kN/ m2)2

250-350 1.43E-08

0.0713

0.0272

***Morooka,

A., Hamrin, C. E. Jr. (1977). Desulfurization of model coal sulfur

I. Thiophene. Cobalt Molybdate by catalyst compounds coal mineral matter and a Chem.Eng. Sci., 32,125-133 4. Thiophene HDS model from Van Parijs & Froment (1986b)**** Kinetic model:
k"KT r=
(1+ (KH2 \\ 'PH2 P. 5

'KH2
+KTPT

PT 'PH2
+KH2SICH2S /PH2

k= k where " exp(

E) E -

-OH ) KT = KT " exp( RTT

Kinetic parameters
(1986) A. I. Parijs Van Model for of Kinetic Table D-4 parameters

ko

KT

KH

Ea

KH2

180

kmol
kgcat. 'h" (bar)2
5.22E+07

(bar)-1

(bar)-1

kJ/mol

kJ/mol

kJ/mol

0.00056

91.2

29.9

10.7

0.536

Parijs, I. A., Froment, G. F. (1986). Kinetics of Hydrosesulfurization on a CoMo/y-A1203 catalyst. 1. Kinetics of Hydrogenolysis of thiophene. Ind. Eng. Chem. Prod. Res. Dev., 25(3), 431-436. 5. Kinetic parameters for Model A to Model H
Table D-5 kinetic parameters
Model A Model B Model C Model D Model E Model F Model G Model H

****Van

k
mol 4.075e+04 2.144e+02 1.016e+03 1.378e+03 9.989e+05 2.142e+02 2.516e+03 3.204e+05

(mmH& min goat."

KO T 9.396e-09 8.880e-03 1.00le-03 4.895e-05 9.801e-07 1.000e-04 9.108e-01 1.00le-03

(mmHg)-' K

1.000e-03 1

1.000e-02 9.468e-05 8.264e-08 4.995e-05 1.000e-05 2.966e-03 4.826e-08

(mmHg)-1 K0 H,s

4.167e-10

2.850e-05 6.057e-06 2.536e-10 4.294e-08 3.205e-07 9.717e-05 3.087e-09

(mmHg)-1
Ea

2.212e+04 1.835e+04 1.000e+04 1.877e+04 3.345e+04 1.835e+04 1.884e+04 3.000e+04

(kcalkmol)
AHT

(kcaLkmol)

-8.000e+03 -5.226e+03 -2.331e+04 -1.000e+04 -1.851e+04 -1.000e+04 -1.505e+04 -1.345e+04

AH

H,

(kcal/kmol)
AHH1s

2.314e+04 -2.183e+04 -2.052e+04 -2.501e+04 -1.894e+04 -. -1.081e+04 -2.481e+04 -2.999e+04

(kcal/kmol)

-1.879e+04 -1.245e+04 -2.764e+04 -1.043e+04 -1.729e+04 -1.778e+04-1.333e+04-2.900e+04

181