Coke properties in simulated blast furnace conditions:investigation on hot strength, chemical reactivity and reaction mechanism

Abstract The blast furnace – basic oxygen furnace route remains the most utilised process route in the production of steel worldwide. Coke is the main fuel of the blast furnace process, however, coke producers and blast furnace operators are facing significant challenges due to increased demands on coke quality and decrease of prime coking coals. The estimation of coke performance in the industrial process through accurate laboratory analyses is of increasing importance. In this doctoral thesis, the aim was to study phenomena related to coke properties and its analysis methods in blast furnace simulating conditions. A new method was introduced to measure the hot strength of coke using a Gleeble 3800 thermomechanical simulator. The hot strengths of industrial cokes were determined at various temperatures and several coke properties, which were believed to affect hot strength, were determined. The effect of H₂ and H₂O in the blast furnace shaft gas were determined in relation to coke reactivity, threshold temperature, and the gasification mechanism. The results obtained by this thesis show that the Gleeble device is suitable for study of coke hot strength. The coke strength was significantly decreased for all three coke grades at temperatures of 1600 °C and 1750 °C when compared to room temperature or 1000 °C. The deformation behaviour of coke was fragile up to 1000 °C, but became at least partially plastic at 1600 °C, and the plasticity further increased at 1750 °C. Notable changes were observed in the deformation behaviour between coke grades at high temperatures. The presence of H₂ and H₂O in the BF shaft gas strongly increased coke reactivity and changed the reaction mechanism of coke to be more surface centric in a specific temperature range. The reactivity of coke in the conditions 100 vol-% CO₂ did not directly correlate with reactivity in a simulated blast furnace shaft gas, which suggest that the widely utilised CRI test does not accurately estimate coke reactivity in the industrial blast furnace process.Tiivistelmä Masuuni – konvertteri yhdistelmä on edelleen käytetyin prosessireitti teräksen tuotantoon ympäri maailman. Koksi on masuunin tärkein polttoaine. Koksintuottajat ja masuunioperaattorit ovat suurten haasteiden edessä johtuen koksin kasvaneista laatuvaatimuksista ja parhaiden koksautuvien kivihiilten ehtymisestä. Koksin suoriutumisen arviointi masuunin olosuhteissa tarkoilla laboratorioanalyyseillä on yhä merkittävämmässä roolissa. Tässä väitöskirjassa tavoitteena oli tuottaa uutta tietoa koksin ominaisuuksista ja sen analyysimenetelmistä simuloiduissa masuunin olosuhteissa. Uusi metodi esitettiin koksin kuumalujuuden määrittämiseksi Gleeble 3800 termomekaanisella simulaattorilla. Teollisten koksilaatujen kuumalujuuksia määritettiin eri lämpötiloissa ja useita koksin mitattiin, joilla uskottiin olevan vaikutus kuumalujuuteen. Lisäksi työssä tutkittiin masuunin kuilun kaasuatmosfäärissä H2 ja H2O kaasujen vaikutusta koksin kemialliseen reaktiivisuuteen, kaasuuntumisen kynnyslämpötilaan ja reaktiomekanismiin. Tässä työssä esitetyt tulokset osoittavat että Gleeble soveltuu koksin kuumalujuuden määritykseen. Koksin lujuus aleni merkittävästi kaikilla kolmella koksilaadulla kuumennettaessa 1600 ja 1750 °C lämpötiloihin verrattuna huoneenlämpötilaan tai 1000 °C lämpötilaan. Koksin muodonmuutos oli haurasta aina 1000 °C lämpötilassa, mutta muuttui osittain plastiseksi 1600 °C lämpötilassa ja plastisuus kasvoi kun lämpötilaa nostettiin 1750 °C:een. Huomattavia eroja havaittiin eri koksilaatujen muodonmuutoskäyttäytymisessä korkeissa lämpötiloissa. H₂ ja H₂O kaasujen läsnäolo kuilun kaasuatmosfäärissä kasvatti voimakkaasti koksin reaktiivisuutta ja muutti kaasuuntumismekanismia pintakeskisemmäksi rajatulla lämpötila-alueella. Koksin reaktiivisuus 100 % CO₂ kaasussa ei korreloinut suoraan simuloidun masuunin kuilun kaasuatmosfäärin kanssa. Tämä tulos indikoi sitä että maailmalla yleisesti käytetty CRI testi ei ennusta tarkasti koksin reaktiivisuutta masuunissa

Oxide scale formation of stainless steels with different heating methods:effect of hydrogen as fuel

Abstract The evolution from natural gas usage to new technologies, such as the use of hydrogen as fuel or electricity-based heating, strongly influences the oxidation of the stainless steel surface in the reheating furnace. Thermogravimetric tests using different simulated combustion and induction reheating conditions are performed for austenitic AISI 301, AISI 304, and ferritic AISI 444 steel grades. Simulated furnace atmospheres in combustion methods are based on methane–air, methane–oxygen, hydrogen–oxygen, and methane–hydrogen–oxygen combinations. For induction simulations, air and nitrogen are used as furnace atmospheres. The results indicate that changes in heating conditions to H2-fueled combustion or induction only have a minor influence on the oxidation of the ferritic grade; whereas, their effects on the austenitic grades are more pronounced. The transition from a methane–air to H2–oxyfuel combustion increases the total oxidation by 1.7 and 4 times for steel grades 304 and 301, respectively; therefore, grade 304 can be considered better suited for transition for H2–oxyfuel use. The shorter induction heating considerably decreases the amount of oxide scale for austenitic grades, but the nitrogen atmosphere produces a subscale inside the steel matrix, which can hinder the descaling process

Water-gas shift reaction in an olivine pellet layer in the upper part of blast furnace shaft

Abstract In order to reduce CO₂ emissions in the iron and steel industry, the utilization of H₂ gas as a reducing agent is a feasible option. The use of hydrogen bearing injectants in the lower blast furnace (BF) area increases H₂O concentration in the upper part of the BF shaft and the charging of moist burden has a similar effect as well. For efficient BF operation, it is important to investigate the effect of high H2 and therefore high H₂O concentrations in the reducing gas. This study focuses on the upper BF shaft area where hematite to magnetite reduction takes place and temperature is in the range of the forward water-gas shift reaction (WGSR). The effect of the WGSR on the composition of the reducing gas was estimated by experimental methods. A layer furnace (LF) was used to determine the temperature for the occurrence of the WGSR under simulated BF shaft conditions. The feed gas conversion was investigated in an olivine pellet layer. The WGSR was observed in an empty LF with CO–H₂O–N₂ gas at 500°C. With CO–CO₂–H₂O–N₂ gas the WGSR was observed in an olivine pellet layer at 400–450°C and in a pre-reduced magnetite pellet layer at 300–400°C indicating the catalyzing effect of magnetite on the WGSR. The results offer additional information about the effect of high H₂O concentration on the composition of the reducing gas through the WGSR. The occurrence of the WGSR in the actual BF and its effects were discussed