Το ηλεκτροπαραγωγικό δυναμικό της ΔΕΗ περιλαμβάνει άνω των 40 πετρελαϊκών σταθμών συνολικής ισχύος 2100MW και οι μεγαλύτεροι είναι του διασυνδεδεμένου συστήματος και λειτουργούν στο Λαύριο και το Αλιβέρι. Οι υπόλοιποι λειτουργούν στο αυτόνομο σύστημα των νησιών του Αιγαίου και Κρήτης. Κατά τους καθαρισμούς των προθερμαντών αέρος και των δεξαμενών μαζούτ των μονάδων αυτών παράγονται σήμερα άνω των 500t στερεών καταλοίπων ετησίως με αυξητική τάση. Τα κατάλοιπα αυτά χαρακτηρίζονται σύμφωνα με την Ευρωπαϊκή οδηγία ως επικίνδυνα. Σύμφωνα με τους κανονισμούς της Ε.Ε. είναι υποχρεωτική η αδρανοποίησή τους και η διασφάλιση της ασφαλούς τους απόθεσης. Στα πλαίσια της παρούσας διατριβής πραγματοποιήθηκε πλήρης χαρακτηρισμός προεπεξεργασμένων και μη στερεών καταλοίπων. Προσδιορίστηκε ότι τα κατάλοιπα αυτά περιέχουν 1.6-13.4%V και 0.8-5.5%Ni, δηλαδή αποτελούν πολύ πλουσιότερες πρώτες ύλες από τα αντίστοιχα κοιτάσματα μεταλλευμάτων βαναδίου και νικελίου. Για παράδειγμα τα Ελληνικά νικελιούχα σιδηρομεταλλεύματα που καμινεύονται στη Λάρυμνα έχουν περιεκτικότητα μόλις 0.93-1.02% σε νικέλιο. Δεν ανιχνεύθηκε οργανικό φορτίο στα κατάλοιπα και το βανάδιο εντοπίστηκε σ’ αυτά στη μορφή VO2. Βασικός στόχος της διατριβής ήταν η ανάπτυξη μεθόδου, που να συνδυάζει την αδρανοποίηση των καταλοίπων με την ανάκτηση των περιεχόμενων μετάλλων. Η μέθοδος περιλαμβάνει και στάδιο πυροσυσσωμάτωσης των ανεπεξέργαστων καταλοίπων, στοχεύοντας στη συσσωμάτωση και εμπλουτισμό τους στα πολύτιμα κραματικά μέταλλα. Εξασφαλίζεται παράλληλη αποθείωση, απανθράκωση και ξήρανσή τους. Τα συσσωματώματα περιέχουν μέχρι και 6.0% Ni και 14.7% V, δηλαδή επιτυγχάνεται ο εμπλουτισμός τους κατά 8% σε Ni και κατά 10% σε V, με ταυτόχρονη απομάκρυνση θείου και άνθρακα σε ποσοστά 73 και 85% αντίστοιχα. Η πυροσυσσωμάτωση λειτουργεί ως αυτογενής διεργασία με την πλήρη ενεργειακή εκμετάλλευση της χημικής ενέργειας του άνθρακα και του θείου. Αποτελεί δε ταυτόχρονα το πρώτο βήμα για την ανάκτηση των περιεχόμενων μετάλλων. Συνακόλουθα, η εξασφάλιση ασφαλούς απόθεσης των αδρανοποιημένων και iii εμπλουτισμένων στα πολύτιμα μέταλλα καταλοίπων δίνει τη δυνατότητα δημιουργίας σοβαρού αποθέματος σωρεύοντας υλικό από το εσωτερικό αλλά και εισάγοντας παρόμοιου τύπου κατάλοιπα από ομοειδή εργοστάσια του εξωτερικού. Έτσι μια μεταλλουργική μονάδα ανάκτησης των μετάλλων θα μπορεί να εξασφαλίζει τη λειτουργία της με οικονομικότητα. Η εκτίμηση των επιπτώσεων της υπαίθριας απόθεσης των μελετούμενων στερεών αποβλήτων και των πυροσυσσωματωμάτων αποτελεί αδήριτο ανάγκη. Προς τούτο πραγματοποιήθηκε προσομοίωση της διεργασίας της έκπλυσής τους από τα όμβρια ύδατα. Το μοντέλο με την υπόθεση του μη αντιδρώντος πυρήνα, φαίνεται να περιγράφει με επαρκή ακρίβεια τη διεργασία. Οι σταθερές και ο πλήρης μηχανισμός του μοντέλου προσδιορίσθηκαν και επιβεβαιώθηκαν πειραματικά. Κατά την έναρξη της διεργασίας φαίνεται ότι η χημική αντίδραση αποτελεί το ρυθμορυθμιστικό βήμα για τη μεταφορά των μετάλλων στην υγρή φάση. Με την πρόοδό της έκπλυσης ελέγχεται από φαινόμενα διάχυσης. Την πρακτική εφαρμογή των μοντέλων που καταστρώθηκαν αποτέλεσε η πρόβλεψη των μακροχρόνιων επιπτώσεων της υπαίθριας απόθεσης των ανεπεξέργαστων και πυροσυσσωματωμένων καταλοίπων. Φάνηκε ότι απαιτείται μεγάλο χρονικό διάστημα, κατ’ ελάχιστο 10 έτη για την μείωση των συγκεντρώσεων των μετάλλων σε επιτρεπτά επίπεδα στον υδροφόρο ορίζοντα. Το τελευταίο στάδιο της προτεινόμενης μεθόδου περιλαμβάνει την αναγωγική τήξη των καταλοίπων. Πραγματοποιήθηκε σειρά πειραματικών χυτηρίων σε χωνευτήριο γραφίτη σε κάμινο Tammann. Μελετήθηκε η διεργασία αναγωγής των μεταλλοξειδίων καθώς και προσδιορίσθηκε η θερμοδυναμική ισορροπία των ετερογενών δράσεων μεταξύ ρευστής σκωρίας και μετάλλου σε θερμοκρασίες 1375-1600οC. Προσδιορίσθηκαν πειραματικά οι θερμοδυναμικές συναρτήσεις ισορροπίας για τα μεταλλοξείδια του βαναδίου, σιδήρου και νικελίου. Τα πειραματικά χυτήρια έδωσαν τελικούς βαθμούς ανάκτησης μετάλλων 85-98% για το Ni και 78-95% για το V, με παράλληλη παραγωγή αδρανοποιημένης σκωρίας κατάλληλης για απόθεση ή άλλες χρήσεις. Οι συνθήκες οι οποίες μεγιστοποιούν τις ανακτήσεις των Ni και V όπως έδειξαν οι πειραματικές δοκιμές είναι:  υψηλές θερμοκρασίες  χρήση χωνευτηρίου γραφίτη iv  προσθήκη σιδηροπυριτίου ως αναγωγικού μέσου Αντίθετα από την επικρατούσα άποψη, αποδείχθηκε, ότι επιτυγχάνονται υψηλοί βαθμοί ανάκτησης σε υψηλά επίπεδα βασικότητας CaO/SiO2>2, κάτι, που εξασφαλίζει την πυρίμαχη επένδυση της καμίνου και την περαιτέρω χρήση της παραγόμενης σκωρίας. Εναλλακτικά, μελετήθηκε και η απευθείας αναγωγική τήξη των φυσικοχημικά προεπεξεργασμένων καταλοίπων. Σημαντικό είναι το εύρημα, ότι η προσθήκη βωξίτη βοημιτικού τύπου σε μικρά ποσοστά προσθηκών μέχρι 10% δρα ενισχυτικά στις ανακτήσεις του νικελίου και του βαναδίου με βαθμούς ανάκτησης άνω του 98%. Διερευνήθηκαν επίσης η κινητική της αναγωγής των οξειδίων του σιδήρου και του βαναδίου από την σκωρία στο λουτρό σιδήρου και προσδιορίστηκαν οι αντίστοιχες σταθερές και τα ρυθμορυθμιστικά βήματα. Συνολικά, προτείνεται μια ολοκληρωμένη μέθοδος ανακύκλωσης των στερεών καταλοίπων πετρελαϊκών σταθμών παραγωγής ενέργειας σε συνδυασμό με υψηλότατους βαθμούς ανάκτησης των περιεχόμενων σε αυτά πολύτιμων κραματικών στοιχείων νικελίου και βαναδίου αποφεύγοντας την εξουδετέρωσή τους με ακριβές μεθόδους αδρανοποίησης. Με αυτόν τον τρόπο εξασφαλίζεται η εξουδετέρωση των επικίνδυνων αυτών υλικών με σημαντικά οικονομικά οφέλη από την ανάκτηση των μετάλλων. / The power generating installations of P.P.C. include m ore than 40 oil-fired power stations of about 2100MW total capacity. The mos t important stations are those of the interconnected system that ope rate in L avrio and Aliv e ri. The rest operate in the autonom ous system of the A eg e an islands and Cre te . M ore than 500t of solid w aste s are produce d annually during the w ashing proce sses of the air pre -he aters and the crude oil tanks of the aforementioned units w ith increasing te nden cy. These residue s are classifie d as hazardous according to the Europe an directive s. The ir neu tralizati on and safe de position is c om pulsory according to the E.U. re gulations. In the current the sis, complete characte rization of pretre ate d and untre ated re sidues was carried out. It w as found that the re sidues exa mined contained 1.6-13.4 %V and 0.8-5.5%Ni, being the refore a conside rably richer raw material than the vanadium and nickel ore deposits. For instance, the H elle nic nicke lferrous ore s, that are smelted in L arym na contain only 0.93-1.02% Ni. No organic compounds w ere de te cte d in the re sidues and the presence of vanadium was identified as VO 2. The fundam ental task of the thesis w as the de ve lopment of a method that com bine s the neutralization of the re sidue s with the recovery of the me tals containe d. The propose d me thod includes also a sinte ring stage of the untre ated residues, aiming at their agg lom e ration and e nrichm e nt in the pre cious alloying metals. The re sidues de sulphurization, de carburization and drying is achieved sim ultaneously. The sinter products contain up to 6.0% Ni and 14.7 % V, sugge sting that en richment of 8% in N i and 10 % in V w as achiev ed, with simultaneous loss of sulphur and carbon in the rates of 73 and 85% respe ctive ly. S inte ring, acts as an indigen ous process with total exploitati on of the che mical en e rgy of carbon and sulphur. It also rep re sents the first ste p for the re covery of the m etals containe d in the residues. Mo reov e r, provided the safe depo sition of the neutralize d and en riche d in valuable m e tals re sidue s, it is possible to ge ne rate a significant stock by piling m aterial from the indige nous sou rce s and imports of such residues. Thus a me tallurgical unit of m e tals re covery could operate at profit. The e valuation of the effects of the ground disposal of the investigate d solid re sidue s and sinte r produ cts is a mus t. The simulation of their le aching by rainfall wa s thus vii conducted. The hypothesis of the unreacted core mode l see ms to describe the proce ss ade que ntl y. The mode l constants and its complete m e chanism we re de te rmined and confirm ed expe rimentall y. Initially chem ical re action se ems to be the rate-de te rmining ste p for the transfe r of me tals in the liquid phase. W ith the e lution prog re ss the me chanism is controlled by diffusion phenomen a. The prediction of the long -te rm effects of the ground de position of the untre ate d and sinte red residue s w as att empted by applying the sugge sted models . It was shown that substantia l amount of time, 10 ye ars minim um, is ne e de d for the drop of the m e tals conce ntrations in the leachate to allowa ble lev e ls. The final stage of the proposed method contains the red uction smelting of the re sidues. A serie s of tests w as conducted in graphite crucibles in Tam mann furnace. The metal oxides re duction proce ss w as investi gated and the the rmod ynamic equilibrium of the hete rogen e ous actions betw e en liquid slag and me tal w as de te rmined in tempe ratures ranging from 1375 to 1600 oC. The therm od ynam ic equilibria functions conce rning the nickel, vanadium and iron oxides w ere exper ime ntally dete rmined. The e xpe rimental test heats yie lded final me tals recove ry rates of 85-98% for Ni and 78-95% for V , with simultaneous production of ne utralized slag suitable for deposition or othe r usage . The conditions that ma ximize the Ni and V re cove ries according to the expe rime ntal findi ngs we re:  the high tempe ratures  the use of graphite crucible  the Fe S i addi tions as re ductant In contrast to the dominating opinion, it w as shown that high rec ove ry rate s w e re achieved in high basicity rates of CaO/Si O 2>2, ensuring the re fractory lining of the furnace and the furthe r use of the produced slag. Alternatively, the direct re duction smelting of the physicochemic ally pretre ated re sidues was inve stigated. The finding that the small a dditions up to 10 % of boe hm itic type of bauxite improve the rec ove ries of nickel and in rate s highe r than 98% is ve ry important. The kinetics of the redu ction of iron and vanadium oxide s from the slag to the iron bath w ere also inve sti gate d and the corresponding constants and rate de te rmining ste ps we re de te rmined. viii A holisti c method of recycling the solid residue s of the oil-fire d stati ons is propose d The propose d me thod, in addition to high re cove ry rate s of the valuable alloying eleme nts containe d (nickel and vanadium) avoids the re sidue s treatment with expe nsive neutralization me thods. Mo reov e r, the ne utralization of these hazardous ma terials is achiev ed w ith substantial financial profit from the me tals re cove ry at the same time.

Thesis (M. Tech.(Chemistry)--Vaal University of Technology)), 2010 / Mining industry produces metals which are economical and serve as high valuable commodities in South Africa. This country is regarded as the world leading producer of precious metals such as platinum group metals (PGMs). Silver (Ag), which is also a precious metal, contribute to the country’s economy wealth due to its significance during industrial applications. Base metals such as copper (Cu) and nickel (Ni), though they are low valued, play a significant role in the republics economic wealth. Mining wastewater contains some of these metals, which end up polluting the environment. A possibility to recover this was investigated using NF membranes. Mine effluent was simulated by using relevant reagents. Characterization of NF90, NF- and NF270 membranes, was done by using scanning electron microscopy (SEM), clean water permeability, single charged salts of NaCl and MgCl2 and binary mixture of NaCl/MgCl2 studies. All the rejection experiments were conducted at pH 2.0 with varying pressure and concentrations. Flux measurements indicated that water permeability through the membranes trend, NF270 > NF90 > NF-. The experiments were performed at pressures of 5 bar, 10 bar, 15 bar and 20 bar. For NF90 membrane, a rejection of Na+ monovalent ion in 20 ppm solution was less than of Mg2+ (divalent) ion. Percentage rejections of 90% (Na+) and 98% (Mg2+) were achieved. NF- had rejection of 83% and 90% for Na+ and Mg2+, respectively. In the case of NF270, the membrane had rejection of 92% (Na+) and 94% (Mg2+), respectively. At 100 ppm, all three membranes showed a decreasing trend in rejection while increasing pressure. For binary-solution mixture, Mg2+ ion still had the highest rejection compared to Na+ ion with about 94% and 85% on NF90 than on NF270 and NF-. The high rejection of divalent ion as compared to monovalent ion for charged solutes was due to solute size and electrostatic interaction between the membrane surface layer and the solute. In the case of transition metal rejection studies, Pd2+ ion had an average of 90%, with Ni2+ ion ≈ 95% and Cu2+ ion ≈ 98% as single salts on NF90 compared to NF270 and NF-. However, as for binary and trinary solution mixture, the competition amongst ions was high, where Pd2+ ion rejection was ≈ 99,0%, while Ni2+ and Cu2+ ions was > 90% on NF90 and NF-. Therefore it was excluded from the tests. For the monovalent metal ions (Ag+ and Cu+), the rejection was > 90% in almost all concentrations mixtures. During membrane fouling evaluation, AgCl salt fouled the most, compared to other metal ions, forming a concentration polarization accumulation on the membrane surface for both 20 and 100 ppm solutions. This situation leads to cake layer formation which causes a flux decline, reduces membrane life time and lowers the rejection performance of NF membranes. The aim of this study was to evaluate the performance of three commercial polymeric membranes (NF90, NF270 and NF-) during rejection of the metal

No presente trabalho foi avaliado o potencial do reator anaeróbio de leito fixo-estruturado e fluxo descendente (down-flow fixed strucutured bed reactor – DFSBR) para o tratamento de drenagens ácidas de minas (DAM) com vistas à recuperação de metais. Vinhaça de cana-de-açúcar foi utilizada como doador de elétrons para bactérias redutoras de sulfato (BRS) e ferro (Fe2+) foi adicionado como metal de referência. Em associação com a sulfetogênese, produção de metano foi promovida pela relação DQO/SO42- de 2,0, maior que a relação estequiométrica de oxidação da matéria orgânica via redução de SO42- (0,67). Concentrações afluentes de DQO e SO42- da ordem de 4000 mg.L-1 e 2000 mg.L-1, respectivamente, foram mantidas durante todo o período experimental (547 dias), sendo o reator operado com TDH de 20 h. Durante a ETAPA 1 (277 dias) o DFSBR foi alimentado com substrato sintético simulando a fração solúvel da vinhaça e recebeu cargas crescentes de ferro (0,07 a 0,51 g Fe2+.L-1.d-1) para avaliação do potencial de remoção de metais. Foram obtidas eficiências de remoção de DQO e SO42- de 94±2% e 97±3%, respectivamente. Remoção de ferro de 95±5% foi alcançada, assim como proporções crescentes de ferro (de até 55%) nas cinzas do precipitado. Ao longo da ETAPA 2 (100 dias) vinhaça foi utilizada como único doador de elétrons e diferentes razões de recirculação foram estudadas (0, 50, 100 e 150 vezes), com velocidades superficiais do escoamento variando de 0,03 a 5,20 m.h-1. A eficiência de remoção de DQO de 82±6% foi atribuída à presença de compostos recalcitrantes na vinhaça, ao passo que a remoção de SO42- permaneceu próxima da alcançada na ETAPA 1 (95±5%). Uma produção volumétrica de metano da ordem de 390 mL CH4.L-1.d-1 foi obtida (CNTP). A despeito da variação nas taxas de reciclo, maior estabilidade e eficiência de remoção de ferro (96±3%) foram determinadas na ausência de recirculação, com ganhos econômicos para o processo. Durante a ETAPA 3 (170 dias) a diminuição gradativa do pH afluente de 6,30 para 3,50 foi realizada. Apesar da supressão de alcalinidade, o sistema atingiu eficiências de remoção de SO42- de 97±1% e remoção de ferro de 95±4%. Foram observados efeitos adversos sobre o metabolismo metanogênico, com queda na produção de metano de 380 para 230 mL CH4.L-1.d-1, acompanhada por aumento da DQO residual no efluente (1500 mg DQO.L-1). Ainda assim, o DSFBR foi capaz de elevar o pH da água residuária de 3,5 para 6,9, confirmando o potencial do sistema para a neutralização de DAM. A caracterização da comunidade microbiana por análise do sequenciamento do gene RNAr 16S indicou predominância dos gêneros Desulfovibrio e Methanosaeta, comprovando o estabelecimento simultâneo dos processos sulfetogênicos e metanogênicos. Por fim, os resultados apontaram perspectivas promissoras de aplicação do DFSBR ao tratamento de DAM via redução de SO42- favorecendo a precipitação e separação de metais em reator de único estágio. A vinhaça de cana-de-açúcar também se mostrou um adequado doador de elétrons para o processo. / This work evaluated the potential of the down-flow fixed-structured bed anaerobic reactor (DFSBR) for the treatment of acid mine drainage (AMD) aiming at metals recovery. Sugarcane vinasse was used as electron donor for sulfate-reducing bacteria (BRS) and iron (Fe2+) was added as reference metal. In association with sulfidogenesis, methane production was promoted by the applied COD/SO42- ratio of 2.0, which is higher than the stoichiometric ratio for organic matter oxidation solely by SO42- reduction (0.67). Affluent concentrations of COD and SO42- were kept close to 4000 mg.L-1 and 2000 mg.L-1, respectively, over the entire experimental time (547 days). The reactor was operated with HRT of 20 h. During STAGE 1 (277 days) the DFSBR was fed with synthetic substrate simulating the soluble fraction of vinasse and received increasing iron loads (0.07 to 0.51 g Fe2+.L-1.d-1) to verify the potential for metal removal. COD and SO42- removal efficiencies were 94±2% and 97±3%, respectively. Iron removal of 95±5% was achieved, as well as increasing proportions of iron (up to 55%) were observed in the ashes of precipitate. Throughout STAGE 2 (100 days) sugarcane vinasse was used as unique electron donor whereas different recirculation ratios were studied (0, 50, 100 and 150 times), with superficial flow velocities ranging from 0.03 to 5.20 m-1. COD removal efficiency of 82±6% was attributed to the presence of recalcitrant compounds in the vinasse, while the removal of SO42- remained close to that previously achieved during STAGE 1 (95±5%). Volumetric methane production near of 390 mL CH4.L-1.d-1 was obtained (STP). Although the variation in the recycle rates, greater stability and efficiency of iron removal (96±3%) were determined in the absence of recirculation, with economic gains for the process. During the STAGE 3 (170 days) gradual decrease of the pH affluent from 6.30 to 3.50 was performed. Despite the alkalinity suppression, the system achieved SO42- removal efficiencies of 97±1% and iron removal close to 95±4%. Adverse effects over methanogenic metabolism were observed once methane production decreased from 380 to 230 mL CH4.L-1.d-1, which was followed by a residual COD increase in the effluent (1500 mg COD.L-1). Nevertheless, the DSFBR was able to raise the pH of the wastewater from 3.5 to 6.9, indicating the potential of such system for AMD neutralization. 16S rRNA gene sequencing analysis for microbial community characterization showed predominance of the genera Desulfovibrio and Methanosaeta, confirming the simultaneous establishment of sulfidogenic and methanogenic processes. Finally, the results presented promising perspectives for the DFSBR application to the AMD treatment via SO42- reduction, also favoring metals precipitation and separation in a single-stage reactor. Sugarcane vinasse was also considered a suitable electron donor for the process.