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Non-geological hydrogen storage for fossil-free steelmaking
KTH, School of Engineering Sciences in Chemistry, Biotechnology and Health (CBH), Chemical Engineering, Energy Processes.ORCID iD: 0000-0002-7129-0223
2022 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

In the last half-century, global steel use has increased more than threefold and further growth is expected, particularly in developing economies. However, steelmaking is currently responsible for 7% of the global net carbon dioxide (CO2) emissions, and any substantial further optimization of existing processes that utilize fossil fuels for iron ore reduction is infeasible. Therefore, steelmaking must change for climate change mitigation targets to be achievable. Hydrogen (H2) steelmaking using H2 produced via electrolysis is one way forward. A challenge is the substantial electricity demand of electrolysis. H2 storage may lower the electricity cost of electrolysis by allowing a larger share of H2 to be produced when the electricity price is low. Existing experience with large-scale H2 storage is limited to salt caverns and the construction of such caverns requires suitable geological formations, which are neither ubiquitous nor well-distributed. However, geologically-independent H2 storage technologies have not previously been evaluated for integration with H2 steelmaking. This is the aim of this thesis. H2 storage technologies were reviewed and liquid H2 carriers were identified as the most techno-economically feasible non-geological options. Out of these liquid carriers, methanol (CH3OH) was found particularly promising for H2 steelmaking due to the low heat demand of its dehydrogenation, its low-cost storage, and the high technological readiness of plants for both its production and dehydrogenation. A complete CH3OH-based H2 storage concept was developed, including processes for CO2 and heat supply. Its ability to reduce the H2 production cost in a H2 steelmaking process was evaluated via a deterministic optimization method based on historical electricity prices. Results indicate that CH3OH-based storage may be competitive with geological storage options, especially for cases with long-duration electricity price patterns.  The option to also sell off accumulated CH3OH from the storage was investigated. Such steel and CH3OH co-production may improve storage utilization and reduce the risk of investment into H2 storage as it allows for profitability to be reached under a more diverse set of electricity market conditions.

Abstract [sv]

Den globala stålanvändningen har mer än tredubblats under de senaste 50 åren och ytterligare tillväxt förväntas, framförallt i utvecklingsländer. Ståltillverkning står dock för 7 % av de globala nettoutsläppen av koldioxid (CO2) och möjligheter till ytterligare optimering av nuvarande processer för järnmalmsreduktion baserade på fossila bränslen är begränsade. Nya ståltillverkningsmetoder krävs därför för att etablerade klimatmål ska kunna uppnås. En väg framåt är järnmalmsreduktion med vätgas (H2) producerad via elektrolys. En utmaning är elektrolysens stora elbehov. Ett H2-lager kan reducera elkostnaden för elektrolys genom att tillåta att en större andel H2 produceras när elpriset är lågt. Befintlig erfarenhet av storskalig H2-lagring är helt begränsad till saltkaverner i geologiska saltformationer och dessa finns inte att tillgå överallt. Icke-geologiska H2-lagringstekniker har dock inte tidigare utvärderats för H2-baserad ståltillverkning, vilket är syftet med denna avhandling. Flytande H2-bärare identifierades som de mest tekno-ekonomiskt gångbara alternativen för icke-geologisk H2-lagring. Av dessa bärare befanns metanol (CH3OH) vara särskilt lovande för H2-baserad ståltillverkning på grund av det låga värmebehovet för dess dehydrogenering, dess låga lagringskostnad och för att processer för både dess produktion och dehydrogenering har en hög teknisk mognadsgrad. Ett komplett CH3OH-baserat lagringskoncept för H2-baserad ståltillverkning utvecklades, inklusive processer för CO2- och värmeförsörjning. Detta koncepts förmåga att minska kostnaden för H2-baserad ståltillverkning utvärderades via en deterministisk optimeringsmetod baserad på historiska elpriser. Resultat indikerar att H2-lagring i CH3OH kan vara konkurrenskraftigt med geologisk lagring, särskilt i särskilt i scenarier med ihållande perioder med höga elpriser.  Vidare undersöktes även möjligheter att inkludera försäljning av CH3OH i lagringskonceptet. Resultat visar att sådan försäljning kan minska risken för investering i ett CH3OH-baserat H2-lager som en del av en H2-baserad ståltillverkningsprocess då det gör det möjligt för lagret att nå lönsamhet under mer varierade elmarknadsförhållanden.

Place, publisher, year, edition, pages
Kungliga Tekniska högskolan, 2022. , p. 104
Series
TRITA-CBH-FOU ; 2022:21
Keywords [en]
hydrogen storage, fossil-free, steelmaking, industrial decarbonization, hydrogen direct reduction
National Category
Chemical Engineering Energy Systems
Research subject
Chemical Engineering
Identifiers
URN: urn:nbn:se:kth:diva-309735ISBN: 978-91-8040-162-3 (print)OAI: oai:DiVA.org:kth-309735DiVA, id: diva2:1643654
Public defence
2022-04-08, Kollegiesalen, Brinellvägen 8, Zoom: https://kth-se.zoom.us/j/66521083318, Stockholm, 14:00 (Swedish)
Opponent
Supervisors
Funder
Swedish Energy Agency, HYBRIT RP1
Note

QC 2022-03-10

Available from: 2022-03-10 Created: 2022-03-10 Last updated: 2025-02-18Bibliographically approved
List of papers
1. Large-scale storage of hydrogen
Open this publication in new window or tab >>Large-scale storage of hydrogen
2019 (English)In: International journal of hydrogen energy, ISSN 0360-3199, E-ISSN 1879-3487, Vol. 44, no 23, p. 11901-11919Article in journal (Refereed) Published
Abstract [en]

The large-scale storage of hydrogen plays a fundamental role in a potential future hydrogen economy. Although the storage of gaseous hydrogen in salt caverns already is used on a full industrial scale, the approach is not applicable in all regions due to varying geological conditions. Therefore, other storage methods are necessary. In this article, options for the large-scale storage of hydrogen are reviewed and compared based on fundamental thermodynamic and engineering aspects. The application of certain storage technologies, such as liquid hydrogen, methanol, ammonia, and dibenzyltoluene, is found to be advantageous in terms of storage density, cost of storage, and safety. The variable costs for these high-density storage technologies are largely associated with a high electricity demand for the storage process or with a high heat demand for the hydrogen release process. If hydrogen is produced via electrolysis and stored during times of low electricity prices in an industrial setting, these variable costs may be tolerable.

Place, publisher, year, edition, pages
Elsevier Ltd, 2019
Keywords
Chemical hydrides, Hydrogen storage, Large-scale, Liquefaction, Metal hydrides, Ammonia, Cost accounting, Costs, Hydrides, Liquefied gases, Chemical hydride, Electricity demands, Engineering aspects, Geological conditions, Industrial settings, Storage of hydrogen
National Category
Energy Engineering
Identifiers
urn:nbn:se:kth:diva-252445 (URN)10.1016/j.ijhydene.2019.03.063 (DOI)000468710100050 ()2-s2.0-85063499997 (Scopus ID)
Note

QC 20190715

Correction in: 

 International Journal of Hydrogen Energy, 2022, Volume 47, issue:2, Pages:1406-1406, DOI:10.1016/j.ijhydene.2021.11.020. WOS: 000736926400006, Scopus 2-s2.0-85121574051

Available from: 2019-07-15 Created: 2019-07-15 Last updated: 2022-09-19Bibliographically approved
2. Methanol as a carrier of hydrogen and carbon in fossil-free production of direct reduced iron
Open this publication in new window or tab >>Methanol as a carrier of hydrogen and carbon in fossil-free production of direct reduced iron
2020 (English)In: Energy Conversion and Management: X, E-ISSN 2590-1745, Vol. 7, no 100051Article in journal (Refereed) Published
Abstract [en]

Steelmaking is responsible for around 7% of the global emissions of carbon dioxide and new steelmaking processes are necessary to reach international climate targets. As a response to this, steelmaking processes based on the direct reduction of iron ore by hydrogen produced via water electrolysis powered by renewable electricity have been suggested. Here we present a novel variant of hydrogen-based steelmaking incorporating methanol as a hydrogen and carbon carrier together with high-temperature co-electrolysis of water and carbon dioxide and biomass oxy-fuel combustion. The energy and mass balances of the process are analyzed. It is found that this methanol-based direct reduction process may potentially offer a number of process-related advantages over a process based on pure hydrogen, featuring several process integration options. Notably, the electricity and total energy use of the steelmaking process could be reduced by up to 25% and 8% compared to a reference pure-hydrogen process, respectively. The amount of high-temperature (>200 °C) heat that must be supplied to the process could also be reduced by up to approximately 34%, although the demand for medium-temperature heat is substantially increased. Furthermore, the suggested process could allow for the production of high-quality direct reduced iron with appropriate carburization to alleviate downstream processing in an electric arc furnace, which is not the case for a process based on pure hydrogen.

Place, publisher, year, edition, pages
Elsevier, 2020
Keywords
Direct reduced iron; Fossil-free steelmaking; Methanol; Electrolysis; Hydrogen storage; Industrial decarbonization
National Category
Energy Systems Chemical Engineering
Identifiers
urn:nbn:se:kth:diva-280481 (URN)10.1016/j.ecmx.2020.100051 (DOI)000658394300008 ()2-s2.0-85088268604 (Scopus ID)
Funder
Swedish Energy Agency, Hybrit RP1
Note

QC 20210720

Available from: 2020-09-09 Created: 2020-09-09 Last updated: 2025-02-18Bibliographically approved
3. Integration of water electrolysis for fossil-free steel production
Open this publication in new window or tab >>Integration of water electrolysis for fossil-free steel production
2020 (English)In: International journal of hydrogen energy, ISSN 0360-3199, E-ISSN 1879-3487, Vol. 45, no 55, p. 29966-29977Article in journal (Refereed) Published
Abstract [en]

This study investigates the integration of water electrolysis technologies in fossil-free steelmaking via the direct reduction of iron ore followed by processing in an electric arc furnace (EAF). Hydrogen (H2) production via low or high temperature electrolysis (LTE and HTE) is considered for the production of carbon-free direct reduced iron (DRI). The introduction of carbon into the DRI reduces the electricity demand of the EAF. Such carburization can be achieved by introducing carbon monoxide (CO) into the direct reduction process. Therefore, the production of mixtures of H2 and CO using either a combination of LTE coupled with a reverse water-gas shift reactor (rWGS-LTE) or high-temperature co-electrolysis (HTCE) was also investigated. The results show that HTE has the potential to reduce the specific electricity consumption (SEC) of liquid steel (LS) production by 21% compared to the LTE case. Nevertheless, due to the high investment cost of HTE units, both routes reach similar LS production costs of approximately 400 €/tonne LS. However, if future investment cost targets for HTE units are reached, a production cost of 301 €/tonne LS is attainable under the conditions given in this study. For the production of DRI containing carbon, a higher SEC is calculated for the LTE-rWGS system compared to HTCE (4.80 vs. 3.07 MWh/tonne LS). Although the use of HTCE or LTE-rWGS leads to similar LS production costs, future cost reduction of HTCE could result in a 10% reduction in LS production cost (418 vs. 375 €/tonne LS). We show that the use of HTE, either for the production of pure H2 or H2 and CO mixtures, may be advantageous compared to the use of LTE in H2-based steelmaking, although results are sensitive to electrolyzer investment costs, efficiencies, and electricity prices.

Place, publisher, year, edition, pages
Elsevier Ltd, 2020
Keywords
Carbon dioxide, Co-electrolysis, Direct reduction, Hydrogen, Integration possibilities, Steel production, Carbon monoxide, Cost reduction, Direct reduction process, Electric arcs, Electric furnaces, Electric power utilization, Electrolysis, Investments, Iron ore reduction, Iron ores, Low temperature production, Metallurgical furnaces, Mixtures, Water gas shift, Direct-reduced irons, Electric arc furnace, Electricity demands, Electricity prices, Electricity-consumption, High temperature electrolysis, Reverse water gas shift, Water electrolysis, Hydrogen production
National Category
Energy Engineering Energy Systems
Identifiers
urn:nbn:se:kth:diva-285305 (URN)10.1016/j.ijhydene.2020.08.116 (DOI)000582322100005 ()2-s2.0-85090487660 (Scopus ID)
Note

QC 20201202

Available from: 2020-12-02 Created: 2020-12-02 Last updated: 2024-01-10Bibliographically approved
4. Application of Liquid Hydrogen Carriers in Hydrogen Steelmaking
Open this publication in new window or tab >>Application of Liquid Hydrogen Carriers in Hydrogen Steelmaking
2021 (English)In: Energies, E-ISSN 1996-1073, Vol. 14, no 5, p. 1392-Article in journal (Refereed) Published
Abstract [en]

Steelmaking is responsible for approximately one third of total industrial carbon dioxide (CO2) emissions. Hydrogen (H2) direct reduction (H-DR) may be a feasible route towards the decarbonization of primary steelmaking if H2 is produced via electrolysis using fossil-free electricity. However, electrolysis is an electricity-intensive process. Therefore, it is preferable that H2 is predominantly produced during times of low electricity prices, which is enabled by the storage of H2. This work compares the integration of H2 storage in four liquid carriers, methanol (MeOH), formic acid (FA), ammonia (NH3) and perhydro-dibenzyltoluene (H18-DBT), in H-DR processes. In contrast to conventional H2 storage methods, these carriers allow for H2 storage in liquid form at moderate overpressures, reducing the storage capacity cost. The main downside to liquid H2 carriers is that thermochemical processes are necessary for both the storage and release processes, often with significant investment and operational costs. The carriers are compared using thermodynamic and economic data to estimate operational and capital costs in the H-DR context considering process integration options. It is concluded that the use of MeOH is promising compared to the other considered carriers. For large storage volumes, MeOH-based H2 storage may also be an attractive option to the underground storage of compressed H2. The other considered liquid H2 carriers suffer from large thermodynamic barriers for hydrogenation (FA) or dehydrogenation (NH3, H18-DBT) and higher investment costs. However, for the use of MeOH in an H-DR process to be practically feasible, questions regarding process flexibility and the optimal sourcing of CO2 and heat must be answered

Place, publisher, year, edition, pages
MDPI AG, 2021
Keywords
fossil-free steel, hydrogen storage, liquid hydrogen carriers, hydrogen direct reduction, industrial decarbonization
National Category
Energy Systems
Research subject
Energy Technology
Identifiers
urn:nbn:se:kth:diva-291668 (URN)10.3390/en14051392 (DOI)000628142600001 ()2-s2.0-85106297247 (Scopus ID)
Projects
Hybrit RP-1
Note

QC 20210406

Available from: 2021-03-17 Created: 2021-03-17 Last updated: 2023-08-28Bibliographically approved
5. A comparison of two hydrogen storages in a fossil-free direct reduced iron process
Open this publication in new window or tab >>A comparison of two hydrogen storages in a fossil-free direct reduced iron process
2021 (English)In: International journal of hydrogen energy, ISSN 0360-3199, E-ISSN 1879-3487, Vol. 46, no 56, p. 28657-28674Article in journal (Refereed) Published
Abstract [en]

Hydrogen direct reduction has been proposed as a means to decarbonize primary steelmaking. Preferably, the hydrogen necessary for this process is produced via water electrolysis. A downside to electrolysis is the large electricity demand. The electricity cost of water electrolysis may be reduced by using a hydrogen storage to exploit variations in electricity price, i.e., producing more hydrogen when the electricity price is low and vice versa. In this paper we compare two kinds of hydrogen storages in the context of a hydrogen direct reduction process via simulations based on historic Swedish electricity prices: the storage of gaseous hydrogen in an underground lined rock cavern and the storage of hydrogen chemically bound in methanol. We find the methanol-based storages to be economically advantageous to lined rock caverns in several scenarios. The main advantages of methanol-based storage are the low investment cost of storage capacity and the possibility to decouple storage capacity from rate capacity. Nevertheless, no storage option is found to be profitable for historic Swedish electricity prices. For the storages to be profitable, electricity prices must be volatile with relatively frequent high peaks, which has happened rarely in Sweden in recent years. However, such scenarios may become more common with the expected increase of intermittent renewable power in the Swedish electricity system.

Place, publisher, year, edition, pages
Elsevier BV, 2021
Keywords
Direct reduced iron, Methanol, Electrolysis, Hydrogen storage, Fossil-free, Steelmaking
National Category
Energy Engineering
Identifiers
urn:nbn:se:kth:diva-299970 (URN)10.1016/j.ijhydene.2021.06.092 (DOI)000683067100009 ()2-s2.0-85110362023 (Scopus ID)
Note

QC 20210823

Available from: 2021-08-23 Created: 2021-08-23 Last updated: 2022-06-25Bibliographically approved
6. Improving the economics of fossil-free steelmaking via co-production of methanol
Open this publication in new window or tab >>Improving the economics of fossil-free steelmaking via co-production of methanol
(English)Manuscript (preprint) (Other academic)
Abstract [en]

Steelmaking is responsible for 7% of the global net emissions of carbon dioxide and heavily reducing emissions from currently dominating steelmaking processes is difficult and costly. Recently, new steelmaking processes based on the reduction of iron ore with hydrogen (H2) produced via water electrolysis have been suggested. If the electricity input to such processes is fossil-free, near-zero carbon dioxide emissions steelmaking is achievable. However, the high electricity demand of electrolysis is a significant implementation barrier. A H2 storage may alleviate this via allowing a larger share of H2 to be produced at low electricity prices. However, accurately forecasting the dynamics of electricity markets is challenging. This increases the risk of investment in a H2 storage. Here we evaluate a novel methanol-based H2 storage concept for a H2-based steelmaking process that also allows for the co-production of methanol. During electricity price peaks, the methanol can be reformed to produce H2 for the steelmaking process. During prolonged periods of low electricity prices, excess methanol can be produced and sold off, thus improving the prospects of storage profitability. We use historical electricity prices and a process model to evaluate methanol-fossil-free steel co-production schemes. Methanol co-production has the potential to improve the economics of H2 supply to a fossil-free steelmaking process by up to an average of 0.40 €/kg H2 across considered scenarios, equivalent to a reduction in H2 production electricity costs of 25.0%.

Keywords
fossil-free steelmaking, hydrogen storage, methanol, electrolysis, industrial decarbonization.
National Category
Energy Engineering Chemical Engineering
Research subject
Energy Technology
Identifiers
urn:nbn:se:kth:diva-309721 (URN)
Projects
HYBRIT RP1
Funder
Swedish Energy Agency, HYBRIT RP1StandUp
Note

QC 20220309

Available from: 2022-03-09 Created: 2022-03-09 Last updated: 2025-02-18Bibliographically approved

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Andersson, Joakim

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