Bioreducer use in blast furnace ironmaking in Finland:techno-economic assessment and CO₂ emission reduction potential

Abstract Most of the steel produced in the world is based on the integrated blast furnace-converter route, which is based on the use of virgin raw materials. Large amounts of fossil-based, carbon containing reductants are used in blast furnaces, which results in carbon dioxide emissions into the atmosphere. Fossil carbon dioxide emissions from steel production can be reduced by new technologies or moving from non-renewable to renewable energy sources. Biomass-based reductants could be one way to reduce the specific emissions from blast furnace-based steel production. The aim of this thesis was to examine the techno-economic and CO₂ mitigation potentials of using bioreducers in blast furnace ironmaking. Bioreducer feasibility was analyzed in the Finnish context, but the research methods used can be applied more widely. The metallurgical properties of bioreducers were evaluated and compared to fossil-based reductants. The impact of bioreducers on blast furnace behavior and on other steel plant processes was evaluated, with an emphasis on the reductions achieved in CO₂ emissions at the plant scale. The CO₂ emissions, energy consumption and production costs of bioreducers were evaluated, as was the availability of energy wood for bioreducer production. The results show that solid, liquid and gaseous bioreducers can be produced with thermochemical conversion technologies. However, their suitability for blast furnace use varies greatly. The highest substitution of fossil-based reductants in a blast furnace is achieved with charcoal injection. The carbon footprint of torrefied wood, charcoal and Bio-SNG is moderate compared to fossil-based reducing agents and their production is energetically feasible. The economic feasibility of bioreducers is currently weak in comparison to fossil-based reducing agents, but competitive when compared to other CO₂ emission reduction measures such as carbon capture and storage. The biomass availability assessment revealed that sufficient amount of energy wood could be available for bioreducer production in the areas where Finnish steel plants are situated. The feasibility of bioreducer production could be improved by producing a number of products from the biomass and taking advantage of the process of integration possibilities.Tiivistelmä Suurin osa maailmassa tuotetusta teräksestä valmistetaan integroidulla masuuni-konvertteri reitillä, joka perustuu neitseellisten raaka-aineiden käyttöön. Masuuniprosessissa käytetään suuri määrä fossiilisia, lähinnä hiilipohjaisia pelkistimiä, jotka aiheuttavat hiilidioksidipäästöjä ilmakehään. Fossiilisia hiilidioksidipäästöjä voidaan teräksenvalmistuksessa vähentää uusilla teknologioilla tai siirtymällä uusiutumattomista energialähteistä uusiutuviin. Biomassasta valmistetut pelkistimet voisivat olla yksi mahdollinen keino alentaa masuunipohjaisen teräksenvalmistuksen ominaispäästöjä. Tämän työn tavoitteena oli tarkastella biopelkistimien käytön teknistaloudellista potentiaalia masuunikäytössä ja aikaansaatavia hiilidioksidipäästövähenemiä eri systeemirajauksilla. Työssä keskityttiin tarkastelemaan biopelkistimien hyödynnettävyyttä lähinnä Suomen tasolla, vaikka käytetyt tutkimusmetodit ovat sovellettavissa myös laajemmin. Työssä arvioitiin biopelkistimien metallurgisia ominaisuuksia, niiden vaikutusta masuuniprosessiin ja laajemmin muihin terästehtaan prosesseihin, pääpainon ollessa saavutettavan CO₂ päästövähenemän tarkastelussa. Työssä tarkasteltiin biopelkistimien valmistuksen CO₂ päästöjä, energiankulutusta ja tuotantokustannuksia sekä energiapuun saatavuutta biopelkistimien tuotantoon. Tulokset osoittavat, että biomassasta voidaan valmistaa kiinteitä, nestemäisiä ja kaasumaisia pelkistimiä termokemiallisilla konversioteknologioilla, joiden soveltuvuus masuunikäyttöön vaihtelee suuresti. Masuuniprosessissa suurin fossiilisten pelkistimien korvaavuus saavutetaan käyttämällä puuhiili-injektiota. Torrefioidun puun, puuhiilen ja Bio-SNG:n hiilijalanjälki on varsin maltillinen verrattuna fossiilisiin pelkistimiin ja niiden tuotanto on energeettisesti järkevää. Biopelkistimien taloudellinen kannattavuus verrattuna fossiilisiin pelkistimiin on tällä hetkellä heikko, mutta kilpailukykyinen verrattuna muihin CO₂ päästöjen vähennyskeinoihin, kuten hiilidioksidin talteenottoon ja -varastointiin. Energiapuun saatavuus biopelkistimien valmistukseen on suurin alueilla, jotka sijaitsevat lähellä Suomen terästehtaita. Biopelkistimien tuotannon kannattavuutta voitaisiin parantaa tuottamalla useita tuotteita ja hyödyntämällä prosessi-integraatiota

Interaction between coal and lignin briquettes in co-carbonization

Abstract The utilization of bio-based side streams in metallurgical coke making promotes two major factors in the mitigation of climate impact in the steel industry. Circular economy as the waste material from biorefinery industry is utilized as a raw material in the steel industry, and mitigation of the production of fossil-based CO2 emissions. In this work, lignin from the hydrolysis process was used in a briquetted form as part of the raw material blend in metallurgical coke making. For the experiments and analyses, lignin briquettes were pyrolyzed at 450, 600 and 1200 °C, while one sample was left non-pyrolyzed. In the co-carbonization of briquetted lignin, lignin chars and bituminous coal, the focus was to evaluate the interaction between char and coal in the carbonization. This was studied by thermogravimetric analysis (TGA), optical dilatometry, and light optical microscopy. The results suggested that the interaction between the coal and lignin reduced when the pyrolysis temperature of the briquettes, prior to co-carbonization, was elevated. This was due to the decrease of overlapping of the pyrolysis rates of chars and coking coal. Combined with the dilation and shrinking behaviour of the chars, presented in this paper, separate char and coke structures were formed in the final coke in co-carbonization

Evolution of biocarbon strength and structure during gasification in CO₂ containing gas atmosphere

Abstract This work focuses on the properties of hydrolysis lignin biocarbons with a perspective on utilizing the biocarbons in pyrometallurgical processes. Even if the blast furnace and basic oxygen furnace (BF-BOF) process route was replaced by emerging technologies with lower CO₂ emissions in the future, the need for carbonaceous materials in the iron and steel making industry will still exist. Most of these applications do not require as high standards for the properties of carbonaceous materials as BF but the requirements are still similar to those for BF. The most important properties of carbonaceous materials are the mechanical strength and suitable reactivity. In the case of biocarbon, the apparent density is also considered important. The reactivity and strength properties are investigated with isothermal reactivity tests and compression strength tests for the non-gasified and pre-gasified biocarbon and reference coke samples. The mass loss rate of coke gasification (-0.069%/min) was considerably lower than that of least reactive biocarbon L1200 (-0.18%/min). Regarding the compression strength of the samples, the strength of coke dropped by 56.44% for the samples of pre-gasification level of 50% compared to non-gasified samples while the drop was only 40.68% for the L1200 biocarbon samples. The level of gasification was found to have direct correlation with pore area percentage with R² value 0.92 in case of L1200 and 0.98 in case of coke. Further, the pore area percentage correlated with the compression strength with R²of 0.93 in case of L1200 and 0.98 in case of coke

A thermogravimetric analysis of lignin char combustion

Abstract Understanding the combustion behavior is the basic requirement for a new resource to be used as an alternative fuel for the industrial design of the future plants. In this article, thermogravimetric analysis (TGA) of lignin char combustion in different heating rates (5, 10 and 15 °C/min) was investigated. Extracted combustion indices showed increased weight loss rate, peak temperature and burnout temperature but no change in ignition temperature for all samples when the heating rate increased. Lignin chars containing higher volatile material illustrated higher combustibility through the low ignition and burnout temperatures. Kinetic parameters of lignin combustion were also obtained by the Coat-Redfern method in the first-order kinetic model. High combustibility of high volatile sample (L300: vol%=41) was also confirmed by its low activation energy which was 46.68 compared to 150.34 for L500 (vol%=18) and 174.37 kJ/mol for L650 (vol%=5.1). The pre-exponential factor was also measured to be 2.61E-01, 8.15E+06 and 1.21E+08 min-1for L300, L500 and L650 respectively

Lignin from bioethanol production as a part of a raw material blend of a metallurgical coke

Abstract Replacement of part of the coal in the coking blend with lignin would be an attractive solution to reduce greenhouse gas emissions from blast furnace (BF) iron making and for obtaining additional value for lignin utilization. In this research, both non-pyrolyzed and pyrolyzed lignin was used in a powdered form in a coking blend for replacing 5-, 10- and 15 m-% of coal in the raw material bulk. Graphite powder was used as a comparative replacement material for lignin with corresponding replacement ratios. Thermogravimetric analysis was performed for all the raw materials to obtaining valuable data about the raw material behavior in the coking process. In addition, chemical analysis was performed for dried lignin, pyrolyzed lignin and coal that were used in the experiments. Produced bio cokes were tested in a compression strength experiment, in reactivity tests in a simulating blast furnace shaft gas profile and temperature. Also, an image analysis of the porosity and pore shapes was performed with a custom made MatLab-based image analysis software. The tests revealed that the pyrolysis of lignin before the coking process has an increasing impact on the bio coke strength, while the reactivity of the bio-cokes did not significantly change. However, after certain level of lignin addition the effect of lignin pyrolysis before the coking lost its significance. According to results of this research, the structure of bio cokes changes significantly when replacement of coal with lignin in the raw material bulk is at a level of 10 m-% or more, causing less uniform structure thus leading to a less strong structure for bio cokes

Effect of charcoal and Kraft-lignin addition on coke compression strength and reactivity

Abstract The aim of this research was to investigate the effects of charcoal and Kraft-lignin additions on the structure, cold compression strength, and reactivity of bio-cokes produced at the laboratory scale. Bio-cokes were prepared by adding charcoal and Kraft-lignin (2.5, 5.0, 7.5, and 10.0 wt %) to medium-volatile coal and coking the mixture with controlled heating rate (3.5 °C/min) up to 1200 °C. In addition, four particle sizes of charcoal were added with a 5 wt % addition rate to investigate the effect of particle size on the compression strength and reactivity. Thermogravimetric analysis was used to evaluate the pyrolysis behavior of coal and biomasses. Optical microscopy was used to investigate the interaction of coal and biomass components. It was found that by controlling the amount of charcoal and Kraft-lignin in the coal blend, the compression strength of the bio-cokes remains at an acceptable level compared to the reference coke without biomass addition. The cold compression strength of the charcoal bio-cokes was higher compared to Kraft-lignin bio-cokes. The reactivity of the bio-cokes with charcoal addition was markedly higher compared to reference coke and Kraft-lignin bio-cokes, mainly due to the differences in the physical properties of the parental biomass. By increasing the bulk density of the coal/biomass charge, the cold compression strength of the bio-cokes can be improved substantially

Slow pyrolysis of by-product lignin from wood-based ethanol production:a detailed analysis of the produced chars

Abstract Slow pyrolysis as a method of producing a high-quality energy carrier from lignin recovered from wood-based ethanol production has not been studied for co-firing or blast furnace (BF) applications up to now. This paper investigates fuel characteristics, grindability, moisture uptake and the flow properties of lignin chars derived from the slow pyrolysis of lignin at temperatures of 300, 500 and 650 °C (L300, L500 and L650 samples respectively) at a heating rate of 5 °C min−1. The lignin chars revealed a high mass and energy yield in the range of 39–73% and 53–89% respectively. Pyrolysis at 500 °C or higher, yielded lignin chars with low H/C and O/C ratios suitable for BF injection. Furthermore, the hydrophobicity of lignin was improved tremendously after pyrolysis. Pyrolysis at high temperatures increased the sphericity of the lignin char particles and caused some agglomeration in L650. Large and less spherical particles were found to be a reason for high permeability, compressibility and cohesion of L300 in contrast to L500 and L650. L300 and L500 chars demonstrated high combustibility with low ignition and burnout temperatures. Also, rheometric analysis showed that L500 has the best flow properties including low aeration energy and high flow function

Use of biomass in integrated steelmaking:status quo, future needs and comparison to other low-CO₂ steel production technologies

Abstract This paper provides a fundamental and critical review of biomass application as a reducing agent and fuel in integrated steelmaking. The basis for the review is derived from the current process and product quality requirements that also biomass-derived fuels should fulfill. The availability and characteristics of different sources of biomass are discussed and suitable pretreatment technologies for their upgrading are evaluated. The existing literature concerning biomass application in bio-coke making, blast furnace injection, iron ore sintering and production of carbon composite agglomerates is reviewed and research gaps filled by providing insights and recommendations to the unresolved challenges. Several possibilities to integrate the production of biomass-based reducing agents with existing industrial infrastructures to lower the cost and increase the total efficiency are given. A comparison of technical challenges and CO₂ emission reduction potential between biomass-based steelmaking and other emerging technologies to produce low-CO₂ steel is made