Μοντελοποίηση, προσομοίωση, αριστοποίηση διεργασιών καθαρισμού αερίων με αμίνες

Abstract

The present work refers to the modeling, simulation and optimization of the gas sweetening processes that use aqueous amine solutions. Especially, it refers to the hydrocarbon vapors’ purification from H2S and CO2 using aqueous monoethanolamine (ΜΕΑ) solutions.The work is divided into five general work packages which are respectively described in the five main chapters of the thesis. Especially, chapters ΙΙ, ΙΙΙ and ΙV are divided into three general sections: Literature Review, Current Contribution and Conclusions. The sixth chapter contains a summary of the conclusions and lists suggestions for further research, while the appendix to the thesis includes the input and output files from the PIGASOS simulation package, developed in the frame of the present work.Within Chapter One an extensive review of the relevant literature is presented (over 600 scientific papers and tenths of specialized books are reviewed and classified in a special literature database. Sixty seven (67) different gas sweetening processes are recognized and classified in an original way. The problem of acid gas purification as well as the most widely used gas sweetening process using amines, the GIRBOTOL process, are described in detail.In Chapter Two, the collection and correlation of more than two thousand (2000) experimental data of equilibrium in the H2S and/or CO2 – aqueous ΜΕΑ solution system, is first described. The development of a new equilibrium model for the prediction of the partial pressures of H2S and CO2 in the H2S and/or CO2 – aqueous ΜΕΑ solution system is presented. The prediction ability of the new model developed is demonstrated. The accuracy verification and validation of the new model prediction is made in comparison to all available 2000 experimental measurements, as well as against the prediction results of the other equilibrium models presented up to now in the reference literature. The evaluation of the new model is concluded by applying it in the simulation of the operation of known industrial installations.In Chapter Three the development of a new system of models and algorithms for the rigorous simulation of the gas purification processes is described. Special emphasis is given to the regeneration column, which presents significant peculiarities in its operating conditions and geometry. The novel “5Ν-θ-method” of convergence, developed for dealing with complex, reversible chemical reactions, is presented. The validation of the new simulation method is made in comparison to commercially available simulators and industrial data, while an operation analysis of the process using the new computer package DESORB, is also described in chapter three.In Chapter Four, the procedure developed for the amine sweetening process optimization in the amine solution regeneration column, is described. Models for the estimation of investment and operation costs were developed, the objective function was formulated, the computer package OPTIM was created and the optimal operation range was defined as a function mainly of steam and materials of construction costs, as well as in relation to the desired desorption rate of H2S and/or CO2.In Chapter Five the computer package PIGASOS is presented, developed for the simulation and optimization of the operation of the gas sweetening plants which use amine solutions. The computer package PIGASOS was originated by incorporating all model and algorithms developed within the framework of this study. It is an integrated process simulator developed to allow rigorous or short-cat calculations for design, rating, costing and optimization of gas sweetening plants, which use aqueous amine solutions.In Chapter Six, the conclusions of this study are summarized and suggestions for further research on this particular subject are formulated.

Η παρούσα εργασία αφορά στη μοντελοποίηση, προσομοίωση και βελτιστοποίηση της διεργασίας καθαρισμού αερίων από H2S και CO2 με χρήση υδατικών διαλυμάτων αμινών και ειδικότερα μόνοαιθανολαμίνης (ΜΕΑ).Χωρίζεται σε πέντε γενικές ενότητες εργασίας, οι οποίες περιγράφονται αντίστοιχα στα πέντε κύρια κεφάλαια της διατριβής. Ιδικά, τα κεφάλαια ΙΙ, ΙΙΙ και ΙV χωρίζονται σε τρείς επί μέρους ενότητες: βιβλιογραφική ανασκόπηση, παρούσα συμβολή και συμπεράσματα. Στο έκτο κεφάλαιο συνοψίζονται τα συμπεράσματα και καταγράφονται προτάσεις για περαιτέρω έρευνα ενώ στο παράρτημα της διατριβής περιλαμβάνονται τα φύλλα δεδομένων και αποτελεσμάτων του πακέτου προσομοίωσης PIGASOS.Στα πλαίσια του πρώτου κεφαλαίου γίνεται διεξοδική διερεύνηση της βιβλιογραφίας (πάνω από 600 άρθρα και δεκάδες βιβλία) τα οποία αποδελτιώνονται και ταξινομούνται σε ειδική βάση βιβλιογραφικών δεδομένων. Αναγνωρίζονται και ταξινομούνται με πρωτότυπο τρόπο 67 διαφορετικές διεργασίες καθαρισμού αερίων και περιγράφεται αναλυτικά το πρόβλημα του καθαρισμού των αερίων και η πλέον διαδεδομένη διεργασία καθαρισμού αερίων με χρήση αμινών, η διεργασία GIRBOTOL.Στο δεύτερο κεφάλαιο περιγράφεται η συλλογή και η επεξεργασία δύο χιλιάδων (2000) πειραματικών μετρήσεων ισορροπίας στο σύστημα H2S ή / και CO2 – υδατικό διάλυμα ΜΕΑ, η ανάπτυξη νέου μοντέλου πρόρρησης των τιμών της μερικής πίεσης του H2S και του CO2 στο σύστημα H2S ή / και CO2 – υδατικό διάλυμα ΜΕΑ και η πιστοποίηση της ικανότητας πρόρρησης του νέου μοντέλου σε σύγκριση με όλες τις διαθέσιμες πειραματικές μετρήσεις, τα άλλα μοντέλα της βιβλιογραφίας. Η αξιολόγηση του νέου μοντέλου ολοκληρώνεται με την χρήση του σε προσομοίωση της λειτουργίας των βιομηχανικών εγκαταστάσεων.Στο τρίτο κεφάλαιο περιγράφεται η ανάπτυξη συστήματος μοντέλων και αλγορίθμών για την προσομοίωση με ακρίβεια των διεργασιών καθαρισμού αερίων. Δόθηκε ιδιαίτερη έμφαση στη στήλη αναγέννησης που παρουσιάζει σημαντικές ιδιαιτερότητες στις συνθήκες λειτουργίας και την γεωμετρία. Παρουσιάζεται η νέα «5Ν-θ-μέθοδος» σύγκλισης που ανα-πτύχθηκε για την αντιμετώπιση των αμφίδρομών χημικών αντιδράσεων. Ο έλεγχος της ακρί-βειας της νέας μεθόδου προσομοίωσης γίνεται σε σύγκριση με προσομοιωτές της αγοράς και βιομηχανικά στοιχεία ενώ με χρήση του πακέτου προγραμμάτων DESORB που αναπτύχθηκε γίνεται λειτουργική ανάλυση της διεργασίας. Στο τέταρτο κεφάλαιο περιγράφεται η διαδικασία που ακολουθήθηκε για την βελτιστοποίηση της διεργασίας στη στήλη αναγέννησης. Αναπτύχθηκαν μοντέλα υπολογισμού κόστους επένδυσης και λειτουργίας, σχηματίστηκε η αντικειμενική συνάρτηση δημιουργήθηκε το πακέτο προγραμμάτων OPTIM, και προσδιορίσθηκε η περιοχή βέλτιστης λειτουργίας σε συνάρτηση με το κόστος του ατμού και των υλικών καθώς επίσης σε σχέση με τον επιθυμητό βαθμό απόδοσης σε H2S και CO2.Στο πέμπτο κεφάλαιο παρουσιάζεται το πακέτο προγραμμάτων PIGASOS για την προσομοίωση και αριστοποίηση της λειτουργίας των μονάδων καθαρισμού αερίων από H2S και CO2. Το PIGASOS δημιουργήθηκε με ενσωμάτωση όλων των μοντέλων και αλγορίθμών που αναπτύχθηκαν στα πλαίσια της παρούσας εργασίας. Είναι ένα ολοκληρωμένο πακέτο προσομοίωσης και μπορεί να χρησιμοποιηθεί για τον σχεδιασμό την λειτουργική ανάλυση και την αριστοποίηση των μονάδων καθαρισμού αερίων με χρήση υδατικών διαλυμάτων αμινών. Στο έκτο κεφάλαιο συνοψίζονται τα συμπεράσματα της παρούσας εργασίας και διατυπώνονται προτάσεις για περαιτέρω εργασία στο συγκεκριμένο αντικείμενο.

Lucrarea se referă la modelarea, simularea și optimizarea proceselor de purificare a gazelor care utilizează soluții apoase de amine şi în special, monoetanolamină (ΜΕΑ).Lucrarea este împărțita în cinci secții generale de lucru, care sânt, respectiv, descrise în cele cinci capitole principale ale tezei. Mai ales, capitolele ΙΙ, ΙΙΙ și ΙV sunt împărțite în trei secțiuni generale: Literatura de specialitate, Contribuția actuală și Concluzii. Al șaselea capitol conține un rezumat al concluziilor și sugestii pentru cercetări în continuare, în timp ce anexa la teza include fișierele de intrare și de ieșire ale pachetului de simulare PIGASOS, dezvoltat în cadrul prezentei lucrări.În cadrul capitolului întâi o verificare extensivă a literaturii de specialitate este prezentată (peste 600 de lucrări științifice și zeci de cărți de specialitate sunt analizate și clasificate într-o bază de date de literatură creată in special. Şaizeci și șapte (67) diferite procese de purificare a gazelor sunt recunoscute și clasificate într-un mod original. Problema de purificare a gazelor acide, precum și procesul de desulfurare a gazelor, cel mai utilizat pe scară largă folosind amine, procedeul GIRBOTOL, sunt descrise în detaliu.La capitolul doi, colectarea și corelarea a mai mult de două mii (2000), de date experimentale de echilibru în sistemul H2S și / sau CO2 - soluție apoasă de ΜΕΑ, este descrisă mai întâi. Dezvoltarea unui nou model de echilibru pentru predicție a presiunilor parțiale ale H2S și CO2 în sistemul H2S și / sau CO2 - soluție apoasă de ΜΕΑ este prezentat. Capacitatea de predicție a noului model dezvoltat este demonstrată. Verificarea preciziei și validarea noului model de predicție se face în comparație cu toate 2000 măsurătorile experimentale disponibile, precum și în raport cu rezultatele de predicție ale altor modele de echilibru prezentate până acum în literatura de specialitate de referință. Evaluarea noului model se încheie prin aplicarea lui în simularea funcționării instalațiilor industriale cunoscute.În capitolul trei este descrisă dezvoltarea unui nou sistem de modele și algoritmi de simulare riguroasă a proceselor de purificare a gazelor. Atenţie deosebită este dată în coloana de regenerare, care prezintă particularități semnificative în condițiile sale de funcționare și in geometrie. Nouă "metoda 5Ν-θ" de convergență este prezentată, dezvoltată pentru a trata in acelaşi timp bilanţurile de masă și de energie cu complexul de reacțiile chimice reversibile. Validarea noii metode de simulare se face în comparație cu simulatoare disponibile comercial și a datelor industriale, în timp ce o analiză a modului de operare a procesului, folosind nou pachet de programe dezvoltat DESORB, este de asemenea descrisă în capitolul trei.În capitolul patru, procedura dezvoltată pentru optimizarea procesului în coloana de regenerare a soluției de amină, este descrisă. Modele pentru estimarea costurilor de investiție și de exploatare au fost elaborate, funcția obiectiv a fost formulată, pachetul OPTIM de programe de calculator a fost creat și a fost definit intervalul de operare optimă in funcție cu costul aburului și ale materialelor de construcție ale coloanei, precum și în relaţie cu gradul de desorbție de H2S și / sau CO2 dorit.În capitolul cinci este prezentat pachetul de programe PIGASOS, dezvoltat pentru simularea și optimizarea funcționării instalațiilor de purificare gazelor naturale sau industriale care utilizează soluții apoase de amine. Pachetul PIGASOS a fost creat prin încorporarea a tuturor modelelor și algoritmilor dezvoltate în cadrul acestui studiu. Este un simulator de proces integrat, dezvoltat pentru a permite calcule riguroase sau simplificate pentru proiectare, analiza operaţională și optimizarea instalațiilor de purificare a gazelor, care utilizează soluții apoase de amine.În capitolul șase, sunt sintetizate concluziile acestui studiu și sunt formulate sugestii pentru continuarea cercetări cu privire la acest subiect particular.