Στην διάρκεια της παρούσας εργασίας μελετήθηκε η ικανότητα ρόφησης CΟ2 καθώς και η απομείωση (attrition) δώδεκα υλικών (8 ασβεστίτες και 4 δολομίτες) τόσο πριν όσο και αφού είχαν υποστεί θερμική διάσπαση-ενανθράκωση. Σύμφωνα με τα αποτελέσματα τα μη θερμικά κατεργασμένα υλικά επέδειξαν μικρότερα ποσοστά απομείωσης συγκριτικά με τα θερμικά κατεργασμένα. Το ποσοστό απομείωσης των υλικών χωρίς θερμική κατεργασία δεν αποτελεί μέτρο πρόβλεψης του ποσοστού απομείωσης του υλικού μετά από θερμική κατεργασία. Στην συνέχεια μελετήθηκε η επίδραση των συνθηκών θερμικής διάσπασης (θερμοκρασία και διάρκεια) του υλικού Α1 με αρχικό μέγεθος κόκκων 0.71mm<d<1.4mm τόσο στην ικανότητα ρόφησης διοξειδίου του άνθρακα όσο και στον ποσοστό απομείωσης (attrition). Τα αποτελέσματα έδειξαν ότι όταν τα υλικά διασπόνται έντονα θερμικά (Τ>900οC και t>2h) παρουσιάζουν μειωμένη ικανότητα ρόφησης CΟ2 . Αναφορικά με την απομείωση, θερμική κατεργασία σε υψηλή θερμοκρασία και για παρατεταμένη χρονική περίοδο, οδηγεί σε υψηλά ποσοστά λεπτόκοκκου υλικού μετά την ενανθράκωση. Πιθανοί λόγοι είναι η θραύση των κόκκων λόγω της ανισότροπης δομής των υλικών η ή πυροσυσσωμάτωση (sintering). Τέλος μελετήθηκε η επίδραση υλικών επικάλυψης όπως η αλούμινα και η σίλικα στην ικανότητα ρόφησης CΟ2 καθώς και στο ποσοστό απομείωσης του υλικού Α1 για αρχικό μέγεθος κόκκων 0.5mm<d<0.6mm και 0.71mm<d<1.4mm. Τα αποτελέσματα έδειξαν ότι και στις δύο μελετηθείσες κοκκομετρίες η διεργασία της επικάλυψης δεν έδωσε θετικά αποτελέσματα στο ποσοστό απομείωσης του υλικού. Μικρότερο ποσοστό απομείωσης παρουσίασε το υλικό Α1 όταν επικαλύφθηκε με 0,5% Al2O3 . Κανένα θετικό αποτέλεσμα σχετικά με το ποσοστό απομείωσης του υλικού Α1 και στις δύο κοκκομετρίες δεν επιτεύχθηκε ούτε όταν την διεργασία της επικάλυψης ακολουθούσε και διεργασία έντονης θερμικής κατεργασίας. Η ικανότητα ρόφησης διοξειδίου του άνθρακα του υλικού δεν επηρεάζεται από την διεργασία της επικάλυψης ούτε και από τον συνδυασμό επικάλυψης έντονης θερμικής κατεργασίας. / Testing of the attrition resistance and CO2 absorption capacity were done for twelve raw and calcined/recarbonated materials. Attrition performance was tested with a simple method employing a small scale fluidized bed at room temperature. Eight materials were characterized as calcites and four as dolomites with XRD technique. Calcined-recarbonated materials showed higher attrition than raw ones. Excellent attrition performance of a raw material does not mean same performance after calcination and recarbonation. Investigation of the effect of calcination condition (temperature, time) on the absorptive and mechanical properties of materials A1, A7, A8, Δ1, Δ2, Δ3 and Δ4 was carried out. It was found that the conditions of calcination do not have an important effect on attrition behavior. On the other hand the severity of calcination has a clear negative effect on CO2 absorption capacity for all materials tested. This is a direct consequence of the sintering and densification that takes place at high temperatures and long calcination times. In order to improve attrition performance some coating experiments were performed with A1 material for initial particle size fraction of 0.5mm<d<0.6mm and 0.71mm<d<1.4mm. Commercially available silica (two types) and alumina (one type) in the form of aqueous colloidal solutions with neutral/basic pH in the case of silica and acidic in the case of alumina were used in coating experiments. Coating with silica (two types) did not prove to have either positive or negative effect on both CO2 absorption capacity and attrition performance for A1 material with initial particle size fraction of either 0.5mm<d<0.6mm or 0.71mm<d<1.4mm. A small positive effect on attrition performance for A1 material was noticed when it was coated with 0.5% alumina. Combination of coating with intense calcination conditions (950οC for 6h) did not have any positive effect on attrition performance for A1 material with initial particle size fraction of either 0.5mm<d<0.6mm or 0.71mm<d<1.4mm.

Στην παρούσα εργασία μελετήθηκε η Ηλεκτροχημική Ενίσχυση της αντίδρασης της υδρογόνωσης του CO2. Ο καταλύτης που χρησιμοποιήθηκε ήταν Ru σε β"-Al2O3, ένας αγωγός ιόντων νατρίου. Το θερμοκρασιακό εύρος που εξετάστηκε ήταν από 200-320oC με διάφορες αναλογίες των αερίων τροφοδοσίας (PH2/PCO2 = 14 , 7, 2.3) και σε πιέσεις 1-5 bar. Η μελέτη αφορά τη συμπεριφορά των καταλυτικών ρυθμών σχηματισμού των προϊόντων τόσο σε καθαρή από Na+ επιφάνεια, όσο και κατά την παροχή ιόντων νατρίου σε αυτήν με επιβολή ενός σταθερού αρνητικού ρεύματος ή δυναμικού. Αρχικά στην Εισαγωγή θα αναφερθούμε στο φαινόμενο του θερμοκηπίου και στο πρόβλημα που δημιουργείται από τις εκπομπές του CO2 στην ατμόσφαιρα. Στη συνέχεια, στο Κεφάλαιο 1 θα περιγραφεί το φαινόμενο της Ηλεκτροχημικής Ενίσχυσης της Κατάλυσης (EPOC ή φαινόμενο NEMCA) και στο Κεφάλαιο 2 θα γίνει μια βιβλιογραφική ανασκόπηση της αντίδρασης της υδρογόνωσης του CO2 τόσο καταλυτικά όσο και ηλεκτροκαταλυτικά. Στο Κεφάλαιο 3 θα περιγραφεί ο τρόπος παρασκευής του καταλύτη και ο χαρακτηρισμός του και θα παρουσιαστεί η πειραματική διάταξη και ο αντιδραστήρας που χρησιμοποιήθηκε. Στο Κεφάλαιο 4, θα παρουσιαστούν τα αποτελέσματα όλων των πειραμάτων που έγιναν (θερμοκρασιακά, κινητικά, δυναμικής απόκρισης των ρυθμών σχηματισμού των προϊόντων και επίδρασης του αρνητικού ρεύματος στους ρυθμούς και στην κάλυψη των Na+) και τέλος, θα παρουσιαστούν τα συμπεράσματα της έρευνας αυτής. / In this study, we examine the phenomenon of Electrochemical Promotion of the catalytic hydrogenation of CO2. The catalyst used was ruthenium on β-Al2O3, a sodium conductor. The temperature range examined was 200-320oC, in different gas compositions (PH2/PCO2=14,7,2.3) and pressures up to 5 bar. This study concerns the behaviour of the production rates of the products in a clean surface and under sodium pumping by applying a negative potential or current. In the introduction there is a description of the greenhouse effect and the disaster caused by the emissions of the CO2 and in CHAPTER 1 the Phenomenon of Electrochemical Promotion (EPOC, NEMCA) is being described. In Chapter 2 there is an overview of the hydrogenation of CO2, whereas in Chapter 3, we describe the preparation and characterization of the catalyst along with the experimental set up. In Chapter 4 the results of all the experiments are presented (light off, kinetics, transients) and finally, we present the conclusions of this study.

Dimethylether is a non-toxic liquefied gas, which is projected to become one of the fundamental chemical feedstock in the future. Dimethylether can be produced from syngas via a two-step (indirect) process that involves synthesis of methanol by hydrogenation of CO/CO2 over a copper based catalyst and subsequent dehydration of methanol to DME over an acidic catalyst. Alternatively, DME can be produced in an one-step (direct) process using a hybrid (bifunctional) catalyst system that permits both methanol synthesis and dehydration in a single process unit. In the present research work the production of DME has been studied by applying both the indirect and direct processes. Firstly, the methanol synthesis and methanol dehydration reactions involved in the indirect process have been studied separately. Afterwards, these two reactions have been combined in the direct DME production process by using a hybrid catalyst comprising a methanol synthesis and a methanol dehydration component. The methanol synthesis by CO2 hydrogenation has been investigated over commercial and home-made CuO/ZnO/Al2O3 catalysts with the aim to identify optimal experimental conditions (CO2:H2 ratio, flow rate, temperature) that could be then used in the direct conversion of CO2/H2 mixtures into methanol/DME. Obtained results reveal that the conversion of CO2 and the yields of reaction products (CH3OH and CO) increase when the concentration of H2 in the feed and the reaction contact time are increased. It was found that both Cu+/Cu0 species are important for the conversion of CO2/H2, although the presence of Cuo seems to be more important for selectivity/yield of methanol. The stability of the CuO/ZnO/Al2O3 catalyst has been also investigated. It was observed that the main reason for the deactivation of catalyst is the water produced via the methanol synthesis and reverse water gas shift reactions. However, the catalytic activity and products selectivity were recovered slowly to their original levels after applying a regeneration procedure, indicating that deactivation by water is reversible. The dehydration of methanol to dimethylether (DME) has been investigated over a range of catalysts including alumina, silica-alumina and zeolites with different physicochemical characteristics. The effects of temperature and the presence of water vapour in the feed on catalytic performance have been studied in detail. The reactivity of catalysts has been evaluated by determining the reaction rates per gram of catalyst per acid site (total: Brönsted+Lewis) and per Brönsted/Lewis mole ratio. In addition, the reaction mechanism has been investigated over a selected catalyst, with the use of transient-MS and in situ DRIFTS techniques. Results obtained for alumina catalysts show that the catalytic activity and selectivity are determined to a large extent by the textural properties, degree of crystallinity and total amount of acid sites of catalysts. In particular, the methanol conversion curve shifts toward lower reaction temperatures with an increase of specific surface area. However, the enhanced catalytic activity of high-SSA samples cannot be attributed solely to the higher amount of surface acid sites, implying that the reaction rate is determined to a large extent from other parameters, such as textural properties and degree of crystallinity. Results of mechanistic studies indicate that interaction of methanol with the Al2O3 surface results in the formation of two kinds of methoxy groups of different adsorption strength. Evidence is provided that DME evolution is associated with methoxy species that are weakly adsorbed on the Al2O3 surface, whereas more strongly held species decompose to yield surface formate and, eventually, CH4 and CO in the gas phase. Results obtained over zeolite catalysts show that catalytic performance depends on the topology of zeolites due to differences in micropore structure and Si/Al ratio as well as on the number, strength and nature of active acid sites. The activity of zeolite catalysts for the methanol dehydration to DME follows the order ZSM-5 > Ferrierite > Mordenite ~ Beta ~ USY > H-Y. The strong Brönsted acid sites of ZSM-5 zeolites with relatively high Si/Al ratio represent the most active sites in methanol dehydration to DME reaction. However, the overall reactivity of the ZSM-5 zeolites is also affected by the balance of the Brönsted to Lewis acid sites. The activity of Beta and USY zeolites is determined by both Lewis and Brönsted acid sites. The moderate/low reactivity of Ferrierite, Mordenite and H-Y zeolite are determined by the abundant Brönsted acid sites of relatively weak/moderate strength. The direct CO2 hydrogenation to methanol/DME has been investigated using admixed catalysts comprising a methanol synthesis (commercial copper based catalyst: CZA1) and a methanol dehydration component (different alumia/zeolite catalysts: γ-Al2O3, ZSM-5, W/γ-Al2O3, USY(6), Ferrierite(10)). It has been revealed that the conversion of CO2 is always lower than the corresponding equilibrium values predicted by thermodynamics, indicating operation in the kinetic regime. The nature of the methanol dehydration component of the admixed catalysts was found to be important for both CO2 conversion and methanol dehydration. In particular, DME selectivity/yield, depends strongly on the nature of acid sites (both Lewis and Brönsted) as well as the textural (meso/macro porosity) and topological properties of methanol dehydration component of the admixed catalysts. The yield of DME obtained at a temperature of 250oC decreases following the order CZA1/ZSM-5, CZA1/USY(6) > CZA1/Ferrierite(10) > CZA1/ W/γ-Al2O3 >> CZA1/γ-Al2O3. The long-term stability experiments conducted over selected bifunctional catalytic systems revealed that the catalysts deactivate with time-on-stream, mainly due to water produced via methanol synthesis, methanol dehydration and reverse water gas shift reactions. In case of the CZA1/ZSM-5 admixed catalyst the catalytic activity and products selectivity were almost recovered after regeneration indicating that deactivation by water is reversible. / --