Passive reactive filters have the potential to provide effective phosphorus (P) removal from stormwater or agricultural drainage, or to act as an add-on P-removal technology for decentralized or small community wastewater treatment systems. Passive filters require minimal energy consumption and human maintenance. Direct-reduced iron (DRI), a steel-making intermediate, was investigated as a passive filter media for wastewaters phosphorus reduction. Phosphorus is a biologically active element that is in excess in many natural waterways due to intensive human activity. Eutrophication can occur when P concentrations exceed 0.02 mg/L in freshwater lakes and rivers. The harmful consequence of this phenomenon includes oxygen deprivation, fish death and cyanobacteria-produced toxins. There is a pressing need to limit phosphorus over-discharge into natural waterways. DRI is a novel media in the application of wastewater treatment and was characterized to have a porous structure with high metallic iron content. The phosphorus retaining mechanisms in batch and column studies suggest a combination of adsorption and surface crystal formation as the dominant removal mechanisms. Batch studies demonstrated increasing removal capacity with P concentration with a plateau observed at 21 mg P/g DRI relating to initial 3000 mg P/L. Media rejuvenation was investigated through chemical treatment with two iron solutions (Fe2(SO4)3, FeCl3) and two acidic solutions (H2SO4 and HCl) at varying molarity. P removal capacity could be fully recovered with 0.05 M Fe3+ or 0.4 N H+ (HCl/H2SO4), while a 37.6% P recovery was also achieved in an acidic solution at 1.2 N H+ (HCl/H2SO4). A column study utilizing three media sizes of DRI (3.5, 11, 19 mm) and one media size of activated alumina (AA) (7.5 mm) was conducted for 315 days using synthetic P solution varying from 2 to 10 mg/L and hydraulic retention times (HRTs) varying from 0.7 – 15 h. The results demonstrated that removal efficiency increased with HRT and decreased with increasing media size and concentration with minimum HRTs to maintain an 80% removal efficiency varying from 4.4 to 15 hrs for DRI and 3.9 hrs for AA for influent P concentrations of 10 mg/L and below. After 1 year of column operation, the DRI media had demonstrated a minimum removal capacity of 1.82 mg P/g DRI, which can be used as a conservative design parameter. A short duration column study (34 days) utilizing municipal lagoon effluent exhibited similar removal efficiencies to the synthetic column study under the same operational conditions. The 10 years lifespan DRI filter with 80% removal rate in the treatment of stormwater, municipal lagoon effluent, septic tank effluent and dairy wastewater application would have been estimated to have filter volumes of 0.24, 4.69, 15.3 and 36.2 m3, respectively.

Direct Reduced Iron (DRI) is used as an alternative feedstock in electric arc furnaces, making up 50% or more of the total iron charge. DRI produced with coal based reductants (for example in rotary kilns) make up roughly 25% of DRI produced in the world. It was found that SL/RN DRI samples from a kiln cooler had high nitrogen contents (50-250ppm, depending on particle size), higher than DRI from gas-based reduction. The higher nitrogen content of SL/RN DRI would increase the levels of nitrogen of liquid steel produced in the EAFs. The problem is exacerbated by the fact that the SL/RN DRI contains virtually no carbon (which would aid in preventing nitrogen pickup). The proposed mechanism of nitrogen pick-up by the SL/RN DRI is one where nitrogen present within the atmosphere of the rotary cooler (where hot DRI, discharged at 1000°C from the rotary kiln, is cooled to approximately 100 °C in ca. two hours) penetrates the solids bed and nitrides DRI particles. Possible rate-determining steps for nitriding in the cooler have been evaluated. Nitriding of DRI particles is predicted to be rapid: the most plausible location for rapid nitrogen pickup is the first 5 meters of the rotary cooler, where the high temperature, nitrogen-rich gas atmosphere and rapid solids bed mixing are conducive to nitriding; solid-state and pore diffusion of nitrogen into DRI particles are predicted to be rapid too. The most plausible rate determining step for nitriding of DRI particles is that of nitrogen dissociation on the DRI surface, which can be further retarded by the presence of sulphur. A strong correlation was found between the amount of “melt-in” carbon in the liquid steel and the final tap nitrogen content, with 0.3% C resulting in nitrogen levels as low as 50 ppm (80 ppm or less is desired on the plant in question) at tap, even with DRI material that is high in nitrogen and contains virtually no carbon. Proposals to increase the melt-in carbon are included. / Dissertation (MEng)--University of Pretoria, 2013. / gm2014 / Materials Science and Metallurgical Engineering / unrestricted

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Thesis (MScEng) --University of Stellenbosch, 2010. / ENGLISH ABSTRACT: This thesis deals with the development of a new process for the production of Direct Reduced Iron (DRI), intended for use specifically by small scale Electric Arc Furnace (EAF) based steel mills, who require small volumes of DRI. The term development as used here is taken to include such aspects as conceptual design, theoretical verification and initial practical testing. The rise of EAF steelmaking brought about the metamorphosis of steel scrap from a waste product into a valuable raw material. Scrap prices rose steeply during the period 1995 to 2009 compelling EAF steelmakers, wishing to have more control over the cost of their input material, to seek for scrap supplements or alternatives. DRI has become an accepted and sought after supplement, or even complete alternative, to steel scrap. Adding DRI to an EAF charge has a range of advantages, including the dilution of tramp elements and possible cost benefits, but it does have negative effects. These include the lowering of the scrap to liquid metal yield and an increase in power consumed. The effect of charging DRI to a small EAF is quantified. The maximum DRI that may be added to the burden whilst still maintaining the present steelmaking volume, is shown to be as high as 50% if charged continuously, and the maximum price payable for DRI, is shown to be approximately 80% of base grade scrap price. Finally other requirements unique to small scale EAF operators are considered in order to prepare a schedule of requirements for a DRI plant specifically for small scale EAF steel mills. A review of published information on existing DRI production technology, processes and plants is undertaken is establish the fit of existing processes to the requirements set. Initially the thermodynamics and kinetics of iron ore reduction and coal gasification, specifically downdraft gasification are reviewed. Thereafter existing processes are reviewed. Shaft based processes and rotary kiln based processes are identified as possible suitors to the requirements. Limitations of these processes, specifically heat transfer in rotary kilns and the pressure drop over a reduction shafts are investigated. Finally a typical process in each of the main process classes is adjudicated against the set requirements. None is found to match the set requirements. A new process is proposed that is claimed to better suit to small scale operation. The uniqueness of the process is embodied in the combination of existing technologies of downdraft gasification and iron ore reduction in a shaft, in a single reactor. The process consists of two shafts, one placed above the other. Iron ore is charged into the top shaft, called the pre-heat shaft, where it is pre-heated and lightly reduced to wustite with gas from the bottom shaft, called the reduction shaft. The pre-heated ore is then charged together with coal into the reduction shaft. Gasification air is drawn into the top of the reduction shaft where the coal is gasified in a downdraft gasifier, generating reduction gas which reduces the ore as the gas moves concurrently with the iron ore. The exit gas is cleaned and pumped to the pre-heat shaft where it combusted with air to pre-heat the iron ore in the pre-heat shaft. The concept is analysed thermodynamically using amongst others, FactSage, and is shown to be thermodynamically viable. To test the concept process concept practically, an extremely small pilot plant with a production rate of 2kg DRI/h, consisting of only a gasifier/reduction shaft, was designed and constructed using reduction rate data obtained from literature supplemented with data obtained from thermogravimetric analysis of CO reduction of lump Sishen hematite. Pilot Plant trials were performed using various reductant sources. The degree of metallizaion was analysed using visual inspection of cut and polished samples compared to calibrated standards. Analysis of the results indicate that coal rate and production rate influence the degree of reduction positively and negatively. The conclusions arrived at include the fact that the process is thermodynamically viable, that it was possible to reduce iron ore in a simplified pilot plant, and that the process was found to be stable and controllable. It is recommended that a larger scale pilot plant, embodying the full proposed flow sheet be erected to test the process more completely. / AFRIKAANSE OPSOMMING: Die tesis handel oor die the ontwikkeling van ‘n nuwe proses vir die vervaardiging van sponsyster. Die proses is beoog spesifiek vir gebruik deur kleinskaalse Elektriese Boogoond (EBO) gebaseerde staal aanlegte, wat kleiner hoeveelhede sponsyster benodig. Die term ontwikkeling soos hier gebruik word aanvaar om aspekte soos konseptuele ontwerp, teoretiese verifikasie en aanvanklike toetsing te behels. Die vinnige groei van EBO staalvervaardiging het skroot getransformeer van weggooiproduk tot waardevolle grondstof. Die prys van skroot het skerp gestyg gedurende die periode 1995 to 2009. EBO gebaseerde staal produsente, in ‘n poging om meer beheer te hê oor die koste van hul insetmateriaal, het hul in ‘n toenemende mate tot skrootalternatiewe gewend. Sponsyster het ‘n aanvaarde en gewaardeerde byvoeging, en selfs alternatief tot staalskroot geword. Die byvoeging van sponsyster by die lading van ‘n tipiese EBO het besliste voordele, maar het dit ook nadelige effekte. Die voordele sluit die verdunning van reselemente en moontlike kostevoordele in, terwyl van die nadele die verlaging van die skroot tot vloeistaal opbrengs, en ‘n verhoging in kragverbruik, is. Die effek van die byvoeging van sponsyster tot ‘n EBO lading word gekwantifiseer. Daar word getoon dat die maksimum hoeveelheid sponsyster wat by ‘n EBO lading gevoeg kan word terwyl die hoeveelheid staal geproduseer konstant gehou word, ongeveer 50% is indien die sponsyster kontinue gelaai word, en die maksimum prys wat vir die sponsyster betaal kan word, word bereken op ongeveer 80% van die prys van basisgraad skroot. Ander vereistes uniek aan kleinskaal EBO bedrywers word oorweeg ten einde ‘n lys van vereistes vir ‘n sponsysteraanleg, uniek aan kleinskaal EBO bedrywers, te kan bepaal. ‘n Oorsig van gepubliseerde inligting oor sponsysterproduksietegnologie word onderneem ten einde die passing van bestaande prosesse met die gestelde vereistes te kan bepaal. Nadat die termodinamika en kinetika van ysterertsreduksie en steenkoolvergassing be-oordeel is, word bestaande sponsysterprosesse beskou. Skag- en Roterende oond gebaseerde prosesse word as moontlik gepaste prosesse identifiseer. Hitte-oordrag en die drukval oor gepakte beddens, synde tipiese beperkings eie aan die twee prosesse, woord beskou. Tipiese prosesse in elk van die hoofklasse van prosesse word ten laaste be-oordeel aan die gestelde kriteria. Daar word bevind dat geeneen van die bestaande prosesse aan die vereistes voldoen nie. ‘n Nuwe proses, wat skynbaar die behoefte van kleinskaalse EBO gebaseerde staalprodusente beter bevredig, word voorgestel. Bestaande tegnolgie word in ‘n unieke opstelling geïntegreer. Reduksie word in ‘n reduksiekag gedoen as gevolg van die ooglopende massa- en hitte-oordragvoordele van ‘n skag. Reduksiegas word verkry van steenkoolvergassing in ‘n afstroomvergasser ten einde teerverwydering in ‘n naverwerkingsstap oorbodig te maak. Die uniekheid van die proses is beliggaam in die kombinasie van ‘n steenkoolvergasser en reduksieskag in ‘n enkele reaktor. Die proses bestaan uit twee skagte, een bo die ander. Ystererts word in die boonste skag, wat die voorverhitskag genoem word, gelaai. Hier word die erts voorverhit en moontlik lig gereduseer tot wustiet met gas van die onderste skag, wat die reduksieskag genoem word. Die voorverhitte erts word saam met steenkool in die reduksieskag gelaai. Vergassingslug, word in die reduksieskag gesuig waar die steenkool in ‘n afstroomvergasser vergas word. Hierdeur word reduksiegas gegenereer wat die erts verder reduseer soos dit saamstromend met die erts af beweeg. Die uitlaatgas word gesuiwer en na die voorverhitskag gepomp waar dit verbrand word om die erts te voorverhit. Die konsep is termodinamies analiseer met gebruikmaking van onder andere FactSage, en werkbaar bevind. ‘n Baie klein, vereenvoudigde proefaanleg, met ‘n produksievermoë van 2kg DRY/uur, bestaande uit slegs ‘n reduksiekag, is ontwerp en gebou met gebruikmaking van kinetika inligting uit die literatuur aangevul met inligting uit termogravimetriese analise van die CO reduksie van Sishen hematiet. Proefaanleglopies is uitgevoer met ‘n reeks reduktantbronne. Die metallisasiegraad is bepaal deur visuele inspeksie van gesnyde, gepoleerde monsters wat vergelyk is met gekalibreerde standaarde. Analise van die resultate toon dat die steenkoolkoers ‘n positiewe verband, en die produksiekoers ‘n negatiewe verband met die metallisasiegraad het. Die slotsom waartoe gekom is, is dat die proses termodinamies werkbaar is, dat reduksie van ystererts in ‘n vereenvoudigde proefaanleg bewerk kon word, en dat die prose stabiel en beheerbaar voorgekom het. Die aanbeveling word gemaak dat ‘n groter proefaanleg wat die volledige voorgestelde vloeiskema verteenwoordig, opgerig behoort te word, ten einde die proses meer volledig te kan toets.

År 2022 stod järn- och stålindustrin för ca 12,5% av Sveriges totala CO2-utsläpp, där den främsta utsläppskällan är reduktion av järnmalm i masugn. En attraktiv väg för att minska utsläppen från masugnen är att ersätta denna med direktreduktion med vätgas för att producera järnsvamp, som sedan kan smältas i en ljusbågsugn. Denna teknik har potentialen att minska CO2-utsläppen med upp till 98% jämfört med masugnsprocessen. För att minska utsläppen ytterligare kan tekniker för CO2-avskiljning implementeras.  Syftet med detta arbete är att undersöka hur CO2-avskiljning kan implementeras i ett system som använder direktreduktion med vätgas, samt smältning av järnsvamp i ljusbågsugn. Målen med arbetet har varit att formulera ett processkoncept för detta system, för att sedan modellera denna process och utföra en tekno-ekonomisk analys. Arbetets frågeställningar har varit ifall det var mer fördelaktigt med hög eller låg CO2-halt i rökgaserna, ifall ett uppkolningssteg är mer fördelaktigt än uppkolning i ljusbågsugnen, samt ifall den avskilda koldioxiden bör lagras eller återanvändas i processen. En ytterligare frågeställning var även hur lönsamheten av CO2-avskiljning påverkas med avseende på kostnad för utsläppsrättigheter för CO2.  Systemets omfattning sträckte sig från direktreduktionsschaktet till uppvärmningsugnen innan valsning. De CO2-innehållande rökgaserna från de olika processtegen skickades in i en kalciumloopingenhet, som var den valda tekniken för CO2-avskiljning. Ett basfall utan CO2-avskiljning samt åtta scenarion med CO2-avskiljning ställdes upp baserat på frågeställningarna, där dessa sedan modellerades i Microsoft Excel. Resultaten från modellen utvärderades utifrån energirelaterade och ekonomiska prestandaindikatorer där alla scenarion jämfördes mot varandra, samt mot basfallet. Resultaten från arbetet visade att CO2-avskiljning med kalciumlooping kan minska CO2-utsläppen från detta system med 90-91%. Energianvändningen ökade för alla fall som använder CO2-avskiljning, där den lägsta ökningen jämfört med referensfallet var med 4% och den högsta med 40%. Alla scenarion medförde ökade kostnader för systemet jämfört med basfallet. Det scenario där endast koldioxidavskiljning adderades hade lägst kostnad av dessa fall. Detta scenario medförde en ökad produktionskostnad på 240 SEK/ton stål och det skulle krävas en kostnad för utsläppsrätter på 2200 SEK/ton CO2 för att investeringen ska uppnå en återbetalningstid på 25 år.  Utifrån analysen av arbetets olika scenarion, är det mest fördelaktigt att endast addera kalciumloopingtekniken på den befintliga processen. Att stänga ugnarna är fördelaktigt ur ett energiperspektiv, men blir kostsamt ekonomiskt. Därför kan detta vara ett bra alternativ om en ny anläggning ska byggas att då bygga ugnarna stängda. Ett separat uppkolningssteg kan vara ett alternativ för att uppkolning i ljusbågsugnen, men medför både ökad energianvändning samt ökade kostnader. Metanisering visade sig inte vara fördelaktigt utifrån ett ekonomiskt och energiperspektiv på grund av det stora elbehovet som detta medför, dock ger återanvändning av CO2 stora möjligheter till recirkulering av kol i processen vilket gör att upp till 92% av kolbehovet kan täckas av återanvänt kol. / In 2022, the iron and steel industry accounted for approximately 12.5% of Sweden's total CO2 emissions, with the primary source of emissions being the reduction of iron ore in a blast furnace. An attractive way to reduce emissions from the blast furnace is to replace it with direct reduction using hydrogen to produce direct reduced iron, which can then be melted in an electric arc furnace. This technology has the potential to reduce CO2 emissions by up to 98% compared to the blast furnace process. To further reduce emissions, carbon capture technologies can be implemented. The purpose of this work is to investigate how carbon capture can be implemented in a system that uses hydrogen direct reduction and melting of direct reduced iron in an electric arc furnace. The objectives of this work were to formulate a process concept for this system, then model this process and perform a techno-economic analysis. The research questions addressed whether it was more advantageous to have a high or low CO2 concentration in the flue gases, whether a separate carburizing step was more advantageous than carburizing the steel in the electric arc furnace, and whether the captured CO2 should be stored or reused in the process. An additional research question was how the profitability of carbon capture is affected by the cost of CO2 emission allowances. The scope of the system extended from the direct reduction shaft to the reheating furnace before rolling. The CO2 containing flue gases from the various process steps were fed into a calcium looping unit, which was the chosen technology for carbon capture. One base case without carbon capture and eight scenarios with carbon capture were set up based on the research questions, and these were then modeled in Microsoft Excel. The results from the model were evaluated based on energy-related and economic performance indicators, with all scenarios compared against each other and against the base case. The results of this work showed that carbon capture with calcium looping can reduce CO2 emissions from this system by 90-91%. Energy demand increased for all cases using carbon capture, with the lowest increase compared to the reference case being 4% and the highest 40%. All scenarios resulted in increased costs for the system compared to the base case. The scenario where only carbon capture was added had the lowest cost among these cases. This scenario resulted in an increased production cost of 240 SEK/ton of steel, and a CO2 emission allowance cost of 2200 SEK/ton CO2 would be required for the investment to achieve a payback time of 25 years. Based on the analysis of the various scenarios, it is most advantageous to only add the calcium looping technology to the existing process. Closing the furnaces is advantageous from an energy perspective but becomes costly economically. Therefore, this could be a good option if a new plant is to be built, as the furnaces could then be built closed. A separate carburizing step could be an alternative to carburizing in the electric arc furnace, but it entails both increased energy demand and higher costs. Methanation proved not to be advantageous from an economic and energy perspective due to the large electricity demand it entails, but the reuse of CO2 offers great possibilities for carbon recycling in the process, which means that up to 92% of the carbon demand can be covered by reused carbon.

Steel has played an indispensable role in shaping our contemporary world  and will persist to play that role for the foreseeable future. However, the steel industry currently is responsible for 7% of the global CO2-emissions, primarily due to the conventional carbon-based reduction process of iron ore. Fossil-free steel manufacturing, such as hydrogen direct reduction,  could essentially make the  CO2-emissions from primary steel production obsolete. The product from hydrogen-based direct reduction of iron ore is H-DRI, which subsequently are molten in an EAF to produce crude steel. Due to H-DRI  being   a   novel   product,   its   thermophysical   properties   are   not   well documented,  which  are  essential  when  investigating  the  heating  and dissolution behavior.  When  feeding  H-DRI  to  an  EAF,  ferrobergs  may  form,  which  consist  of unmolten material that interrupts the continuous melting process. It is not established whether the heat transfer of the pellets or the heat transfer to the pellets is the leading cause of ferroberg-formation. Modelling the melting process in an EAF is considered near impossible, therefore a simplified heating model of H-DRI was required. In the present thesis, H-DRI pellets were examined with heating experiments in a lab-scale vertical tube furnace to 1500°C  while  the  surface- and center  temperatures  of  the  pellets were  measured.  The measured  surface  temperatures  were  applied  as  varying boundary  conditions  in COMSOL  Multiphysics  heat transfer simulations of  H-DRI  and H-HBI.  The  thermal conductivity  function  was  utilized  as  an  adjustable  parameter to  fit  the  theoretical center temperatures from the heat transfer simulations with the experimental center temperatures to acquire the temperature dependent effective heat conductivity and thermal diffusivity of H-DRI. By establishing an estimate correlation between the heat conductivity of H-DRI and H-HBI, the thermal conductivity and thermal diffusivity of H-HBI could also be obtained. The experiments together with the heat transfer simulations proved to be effective and yielded successful results of the effective heat conductivity and thermal diffusivity of H-DRI  and  H-HBI,  which  can  be  used  in  process  design,  future  models,  and simulations. Furthermore, it is unlikely that ferroberg-formation is caused by slow heat transfer of the H-DRI. It is more likely that it is due to slow heat transfer to the H-DRI. Therefore, the focus should be to increase the heat transfer to the H-DRI pellets while melting in an EAF to avoid ferrobergs. / Stål har haft en oumbärlig roll i att forma vår samtida värld och kommer att fortsätta att inneha  den  rollen  under  en  överskådlig  framtid.  Men  stålindustrin  ansvarar närvarande  för  7%  av  den  totala  globala  CO2-utsläppen,  främst  på  grund  av den konventionella kolbaserade reduktionsprocessen av järnmalm. Fossilfri ståltillverkning, som direktreduktion av järnmalm med vätgas, kan i princip göra CO2-utsläppen   från   primärståltillverkning föråldrat.   Produkten   från   vätgasbaserad direktreduktion  av järnmalm  är  H-DRI,  som  sedan  smälts  i  en  ljusbågsugn  för att producera  råstål. Eftersom  H-DRI  är  en  ny  produkt  så  är  dess  termofysiska egenskaper,  som  är väsentliga  när  man  undersöker  dess  uppvärmnings-  och smältbeteende, inte väl dokumenterat. Vid matning av H-DRI till en ljusbågsugn kan det bildas  ferroberg  som består  av  osmält  material  som  hindrar  den  kontinuerliga smältningsprocessen. Det är inte fastställt om det är värmeöverföringen i pelletsen eller värmeöverföringen  till pelletsen  som  är  den  främsta  orsaken  till  att  ferroberg bildas. Modellering  av  smältprocessen  i  en  ljusbågsugn  anses  nästintill  omöjlig, därför krävdes en förenklad uppvärmningsmodell av H-DRI. I detta examensarbete undersöktes H-DRI-pellets med uppvärmningsexperiment i en vertikal rörugn till 1500°C samtidigt som yt- och centrumtemperaturerna för pelletsen mättes. De uppmätta yttemperaturerna  användes  som  varierande  randvillkor  i  COMSOL Multiphysics värmeöverföringssimuleringar  av  H-DRI  och  H-HBI.  Den  termiska konduktiviteten användes som en justerbar parameter för att anpassa de teoretiska centrumtemperaturerna från värmeöverföringssimuleringarna med de experimentella centrumtemperaturerna  för  att  erhålla  den  temperaturberoende effektiva  termiska konduktiviteten och termiska diffusiviteten för H-DRI. Genom  att   fastställa   en uppskattad korrelation mellan värmeledningsförmågan för H-DRI och H-HBI, kunde även den termiska konduktiviteten och termiska diffusiviteten för H-HBI erhållas. Experimenten  tillsammans  med  värmeöverföringssimuleringarna  visade  sig  vara effektiva och gav framgångsrika resultat av den effektiva termiska konduktiviteten och termiska  diffusiviteten  hos H-DRI och H-HBI,  som  kan  användas  i  processdesign, framtida modeller och simuleringar. Det är osannolikt att ferrobergbildning orsakas av långsam värmeöverföring  i H-DRI, utan det är mer troligt att det beror  på långsam värmeöverföring till H-DRI. Därför bör fokus vara att öka värmeöverföringen till H-DRI pellets i en ljusbågsugn för att undvika ferrobergbildning.