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

Enhancing packaging board properties using micro- and nanofibers prepared from recycled board

Abstract In this study, cellulose microfibers and cellulose nanofibers (CNF) prepared from recycled boxboard pulp using a mechanical fine friction grinder were used as reinforcements in a board sheet. Micro- and nanofibers manufactured by mechanical grinding have typically broad particle size distribution, and they can contain both micro- and nano-sized fibrils. Deep eutectic solvent of choline chloride and urea was used as a non-hydrolytic pretreatment medium for the CNF, and reference CNF were used without any chemical pretreatment. The CNF were ground using three grinding levels (grinding time) and their dosage in the board varied from 2 to 6 wt%. The results indicate that the board properties could be tailored to obtain a balance between the processability and quality of the products by adjusting the amount of CNF that was added (2–6 wt%). A preliminary cost assessment indicated that the most economical way to enhance the board strength properties was to add around 4% of CNF with a moderate grinding level (i.e., grinding energy of 3–4 kWh/kg). Overall, the strength properties of the manufactured board sheets improved by several dozen percentages when CNF was used as the reinforcement

Cationic nanocelluloses in dewatering of municipal activated sludge

Abstract This study used cationic nanocelluloses (CNFC I and II) produced by nanofibrillizing periodate oxidized and aminoguanidine hydrochloride reacted wood cellulose as flocculation agents for municipal activated sludge. For both CNFC I and II, the diameters ranged from about 2–8 nm. Lengths ranged from hundreds of nanometers for CNFC I and about 50–100 nm for CNFC II. The charge densities for CNFC I and II were 1.07 and 1.70 meq g−1, respectively. The study examined the flocculation performance of the two CNFCs in the conditioning treatment of municipal activated sludge and compared the results with the performance of both a commercial coagulant and polyelectrolyte (polyacrylamide). Results showed that both CNFC I and II were able to flocculate activated sludge efficiently at effective doses similar to those of the commercial cationic polymer and at doses lower than the reference coagulant. Their efficiency in reducing turbidity was nearly as good as that of the synthetic reference polymer, and their COD was even better than that of the synthetic reference polymer. The performance of CNFC II was slightly better than that of CNFC I. In centrifugation analyses, the use of both CNFCs resulted in dense sludge cakes with moderate swelling and good colloidal-removal efficiency

Nanofibrillation of deep eutectic solvent-treated paper and board cellulose pulps

Abstract In this work, several cellulose board grades, including waste board, fluting, and waste milk container board, were pretreated with green choline chloride-urea deep eutectic solvent (DES) and nanofibrillated using a Masuko grinder. DES-treated bleached chemical birch pulp, NaOH-swollen waste board, and bleached chemical birch pulp were used as reference materials. The properties of the nanofibrils after disc grinding were compared with those obtained through microfluidization. Overall, the choline chloride-urea DES pretreatment significantly enhanced the nanofibrillation of the board pulps in both nanofibrillation methods—as compared with NaOH-treated pulps—and resulted in fine and long individual nanofibrils and some larger nanofibril bunches, as determined by field emission scanning electron microscopy and transmission electron microscopy. The nanofibril suspensions obtained from the DES pretreatment had a viscous, gel-like appearance with shear thinning behavior. The nanofibrils maintained their initial crystalline structure with a crystallinity index of 61%–47%. Improved board handsheet properties also showed that DES-treated and Masuko-ground waste board and paper nanocellulose can potentially enhance the strength of the board. Consequently, the DES chemical pretreatment appears to be a promising route to obtain cellulose nanofibrils from waste board and paper

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

One-step twin-screw extrusion process to fibrillate deep eutectic solvent-treated wood to be used in wood fiber-polypropylene composites

Abstract Bio-based wood materials are preferable for composites because of their sustainability, but adequately dispersing wood fibers in polymers can be difficult and costly. Our approach was to pretreat the wood with a green solvent system, allowing the composite to be extruded in a single step, simplifying the process, and reducing the overall cost. This study investigates the fibrillation of untreated wood sawdust (W) and deep eutectic solvent-treated wood sawdust (DESW) using a one-step twin-screw extrusion (TSE) process. The results of the analysis of wood fractions and optical microscopy confirmed that the one-step extrusion process resulted in fibrillation of both treated and untreated wood material. The width of the original wood particles was reduced by more than 99% after a one-step TSE for both untreated and DES-treated wood. The size reduction of the DESW was slightly greater than that of the untreated wood, and fibrillation was further confirmed by rheological analysis. The fibrillated wood was then compounded with polypropylene (PP) to produce a wood fiber-polypropylene composite with 50 wt % wood content. The elastic modulus of both untreated and treated extruded composites was higher than that of neat PP. The tensile strength and strain at break for the DESW-PP composite slightly increased in comparison to the untreated W-PP composite. Furthermore, DES treatment of wood resulted in a darker color and increased hydrophobicity of the material

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

Conversion of landscapewaste into bio-coke solid fuel

A rapid increase in organic wastes requires an integrated management system that enhances the use of such wastes to achieve sustainable waste management. Among that, landscape waste is an organic yard or garden waste such as leaves and plant trimmings (excluded grass clippings, sod and dirt). The landscape wastes that are dumped or buried in the landfill takes a period of time to decompose but the wastes are increasing from day to day. This research was aimed to study on the abandon landscape waste at the landscape landfill in Universiti Teknologi Malaysia (UTM); the pattern of landscape wastes generation in each zone in UTM region; and the suitable evaluation using bio-coke as a newtreatment option to treat the landscape wastes. Landscapewaste collection formwas distributed to all the contractors in each zone to collect the data of the five types of waste; dry leaves, twigs, branches, palm front, and wood. The data analysis obtained show that the dry leaves are the major landscape waste at the UTM landscape landfill which was left abandoned without proper treatment. Finally, the empty fruit bunch (EFB) and dry leaves (combined ina three different aspect ratio of 90:10, 50:50, 0:100) were pyrolyzed at a highly compressed state and at moderate temperature (160 °C). The calorific analyses revealed that bio-coke (Product 1, Product 2, Product 3) had an energy density of 17520.7 J/g, 17338 J/g, and 17186.6 J/g, respectively. Conversion of the landscape waste into solid fuel; bio-coke is the best way to treat the abandon landscape waste

Acidic and alkaline deep eutectic solvents in delignification and nanofibrillation of corn stalk, wheat straw, and rapeseed stem residues

Abstract In this work, six different deep eutectic solvent (DES) treatments—five acidic (natural organic acid–choline chloride) and one alkaline (K₂CO₃–glycerol)—were used and compared in delignification and nanofibrillation of agricultural by-products from wheat straw, corn stalk, and rapeseed stem. The DES treatments were performed at 100 °C for 8 h, at 100 °C for 16 h, and at 80 °C for 24 h. The yield of cellulose and lignin fractions was obtained gravimetrically, and a more detailed composition of fractions was obtained for the 16 h treatment. All the samples were further nanofibrillated, and the properties of nanocelluloses and their nanopapers were measured. Acidic lactic acid–choline chloride and alkaline K₂CO₃–glycerol DESs resulted in the highest delignification yields (11.8–5.7 wt-%), nanocellulose viscosity (1360–555 Pa s), and crystallinity index (54–38 %), but the strength properties of nanopapers from alkaline DES treatment (170–132 MPa) were better compared to acidic DESs (132–24 MPa). A plausible explanation for this difference may be that the alkaline DES also dissolved waxes and proteins, which can mitigate the adhesion and network formation between the nanofibers. It was also observed that the separated lignin fractions from acidic and alkaline DES treatments had different characteristics as determined by FTIR