Defossilizing feedstocks of industrial clusters has increasingly attracted attention due to potential impacts on climate change mitigation targets. However, the transition from fossil-based feedstocks to alternative carbon sources (ACS) presents both environmental and economic challenges in terms of performance and feasibility. One issue is the large uncertainties regarding the techno-economic feasibility in terms of investment decisions, which has been barely studied in the literature at cluster level. This study considers market price fluctuations of raw materials, products and energy over time to evaluate the profit and risk associated with individual plants for decision-making purposes. By adopting Modern Portfolio Theory (MPT), a portfolio optimization problem is defined to provide a risk-return-based guidance framework for transitioning to alternative carbon feedstocks. The proposed optimization model obtains investment portfolios and corresponding production capacity distributions based on the optimal constituents among fossil-based and ACS-based plants. The Port of Rotterdam, the Netherlands, is considered as a case study to assess the defossilization of feedstocks at the cluster level. The results show that integrating ACS-based plants into the cluster requires substantial capital investment, and reduces the Return on Investment (RoI) relative to the associated risk, making full defossilization economically challenging to achieve. However, applying a price-allocation method for re-costing ACS-based (by-)products considering governmental financial supports, the transition to alternative carbon sources can become attractive to investors at specific production capacities, as identified through optimal risk–return portfolios.

The petrochemical industry must transition its material and energy sources from fossil-based sources to more sustainable alternatives. While decarbonizing the energy source is challenging, defossilization of the material feedstock is significantly more difficult. In this work, we present a superstructure-based, multi-period, multi-objective optimization framework to address this problem. This framework focuses on minimizing the use of fossil carbon and modifications to petrochemical clusters while explicitly controlling the order of appearance of new processes. The combination of process options becoming available to the solution space over time and the cluster being locked in a path-dependent transition allows the framework to capture realistic transformation pathways. We demonstrate the framework with a small-scale case study of 10 fossil-based and 6 alternative processes. The results demonstrate the ability of the framework to select optimal defossillization pathways while simultaneously considering the impacts on mass and energy flows across the cluster.

Ethylene production processes using alternative carbon sources like biomass or CO₂ could have great potential for the olefins industry. Comparing the benefits and pitfalls of different process routes is challenging due to the vastly different feedstocks and key conversion technologies involved. Here, we performed an ex-ante techno-economic and environmental assessment to explore potential trade-offs of three low technology readiness level ethylene production processes. The three routes were: 1) biobased syngas fermentation to ethanol followed by ethanol dehydration, 2) direct electrochemical conversion of CO₂, and 3) indirect CO₂ and H₂O electrolysis to form syngas followed by a Fischer-Tropsch step. This study found three main takeaways. Firstly, the biobased route significantly outperforms the direct and indirect routes in terms of techno-economic and carbon footprint performance. Secondly, the electrolyzer unit is the main factor limiting the techno-economic performance of the direct and indirect cases, reemphasizing the need for continued technological advancements and cost reductions by researchers in this domain. Finally, the indirect plant design, incorporating two electrolyzers and a Fischer-Tropsch step, is not techno-economically feasible for ethylene production, underscoring the need for further research on Fischer-Tropsch plant designs to advance the replacement of traditional fossil-based refineries.

The rising pressure to defossilize the chemical industry has driven research toward producing chemicals that use alternative carbon sources (ACS). However, the challenges and impacts of replacing already implemented processes and symbiotic relationships remain largely underexplored. This paper systematically assesses the impacts of defossilizing existing processes, both individually and simultaneously, in a propylene cluster in the Port of Rotterdam, the Netherlands. Nine fossil-based processes and three ACS-based processes (i.e., CO₂-based polyol, biopropylene glycol (bio-PG), and biomethyl-tert-butyl-ether (bio-MTBE)) were included in the assessment. Integrating a single ACS-based process enlarges the propylene cluster and results in an excess of upstream chemicals that are no longer required by the ACS processes. Still, relatively simple technologies can reduce total energy and water use, resulting in lower direct CO₂emissions and water consumption of the cluster. Deploying multiple processes in parallel can drive the full defossilization of the cluster, but it requires a complete overhaul. The results illustrate the extent to which combining ACS-based processes could change the layout of an existing petrochemical cluster, affecting its performance. The paper stresses the importance of assessing such deployments, considering the existing conditions in industrial clusters.

Industrial greenhouse gas emissions, primarily carbon dioxide, constitute about one-third of global emissions, and 75% are caused by the generation of heat from fossil fuels. Therefore, a key decarbonisation strategy is electrifying heat generation using renewable sources and power-to-heat technologies. This study explores the impact of the energy price on the optimal choice and sizing of power-to-heat and storage technologies in existing energy-intensive industries with a variable heat demand. A mixed integer linear program is used to determine the technology portfolio and size of the equipment that leads to the lowest total annual cost of the utility system while ensuring that heat demand is always fulfilled. The results of a case study in the Netherlands show that adding power-to-heat and storage technologies to a fossil fuel-based combined heat and power plant is economically viable under all explored scenarios. The mean and the variance of electricity prices significantly influence the sizing of heat pumps, electric boilers, and thermal energy storage. High and stable electricity prices lead to larger heat pump capacities compared to scenarios with low and more variable electricity prices. Electric boilers are primarily sized based on the variance of electricity prices and the capacity of thermal energy storage, which plays a crucial role in managing electricity price fluctuations. The study emphasises the potential for cost-effective electrification and provides valuable insights for reducing industrial CO₂ emissions.

The electrification of utility systems in energy-intensive plants is a promising measure for decarbonising the chemical industry in the short term. However, with the increasing deployment of renewable energy sources, the variability of electricity prices will become a challenge for plants with continuous and constant energy demand. It is thus uncertain whether electrification can become financially viable. This work models the electrification of utility systems in combination with storage technologies for five chemical plants with existing fossil fuel-based utility generation and uses historical data as energy price scenarios. The results show that partial electrification is cost-effective when using electricity is cheaper than natural gas for more than 600 h. Regarding the portfolio of technologies, electric boilers are installed first, followed by thermal energy storage and batteries. Hydrogen is not cost-effective in any of the scenarios explored. This is independent of the type of plant, the available grid connection capacity, and the minimal load of existing fossil fuel-based utility generation. This work thus highlights the potential for electrifying industrial utility systems and the role that electric boilers and energy storage units can play in electrification.

Alternative carbon sources (ACS) are increasingly considered necessary for the defossilisation of fossil-based chemicals. However, the potential and impacts of integrating ACS-based processes in existing petrochemical clusters are often overlooked. This paper aims to systematically analyse key techno-economic and environmental indicators associated with producing bio-based isobutene as an option to defossilise the production of methyl-tert-butyl-ether (MTBE) in the Port of Rotterdam, the Netherlands. The assessment is conducted at process and cluster levels. For this, the bio-isobutene (bio-IBN) process (358 kt/y of product), along with the existing fossil-based processes involved in MTBE production (i.e. the MTBE cluster), were modelled in Aspen Plus v12. The results show that under current conditions, although bio-IBN production could defossilise the MTBE cluster by c.a. 80 %, it is not cost-competitive compared to the current fossil-based process. Furthermore, deploying the bio-IBN process would significantly change the structure of the existing MTBE cluster, increasing by a factor of two or larger electricity, cooling water and bare land requirements. These requirements would affect the economic and environmental performance of the full cluster. The results emphasise the critical role of strategic change of new processes within existing petrochemical clusters.

Syngas production via high-temperature co-electrolysis of CO₂ (CO₂E) shows great potential to reduce the reliance on fossil fuels within the chemical industry. This paper presents an optimization model (MILP) to investigate syngas production from CO₂ in the European chemical sector. The model assesses the economic performance of CO₂E in prospective supply chains and explores alternative supply chain configurations under different syngas market sizes. The results reveal that the optimal placement of the CO₂ electrolysis plant in the supply chain is co-located or decentralized at the product location. This configuration reduces the need for syngas transportation by delivering CO₂ to the demand site, which is typically more cost-effective. At a syngas market fulfillment of 2 %, the lowest levelized cost of syngas is achieved at 673 EUR₂₀₁₈/tonne, with electrolysis plants averaging a production capacity of 100 ktonne syngas/year. This levelized cost is between 1.5 and 4 times higher than the fossil-based reference.

Heat pumps are a promising option to decarbonize the industrial sector. However, their performance at a plant-level can be affected by other process changes. In this work, process changes that improve the heat pump's performance have been identified using Process Change Analysis (PCA), where the background pinch point is used as a reference point for appropriate placement. The effects of the process changes on the heat pump's work requirements are studies by introducing exergy to PCA to form the split exergy grand composite curve. This graph shows the work potential of the streams connected to the heat pump and therefore its work targets. The framework is demonstrated in two case studies. In a biodiesel production plant, it allowed to identify technologies that enhance heat pump performance while reducing overall heating requirements. Here, a heat pump transfers 1.9 MW with a COP of 4.2 but incurs a 40 kW penalty for transferring heat above the background process's pinch temperature. Replacing the wet water washer with a membrane separation unit avoided this penalty, while drastically reducing energy requirements from 0.9 MW to 0.3 MW. in a vinyl chloride monomer-purification process, PCA showed how the extraction of heat by the heat pump impacted the formation of the background pinch, from which an implementation strategy was derived that increased the heat pump's plant-level performance by 6.5% with respect to standard implementation.

Microbial electrosynthesis (MES) is a novel carbon utilisation technology aiming to contribute to a circular economy by converting CO₂ and renewable electricity into value-added chemicals. This study presents a cradle-to-gate life cycle assessment (LCA) of hexanoic acid (C6A) production using MES, comparing this production with alternative technologies. It also includes a cradle-to-grave LCA for potentially converting C6A into a neat sustainable aviation fuel (SAF). On a cradle-to-gate basis, MES-based C6A exhibits a carbon footprint at 5.5 t CO₂eq/tC6A, similar to fermentation- and plant-based C6A. However, its direct land use is more than one order of magnitude lower than plant-based C6A. On a cradle-to-grave basis, MES-based neat SAF emits 325 g CO₂eq/MJ neat SAF, which is significantly higher than the counterparts from currently certified routes and conventional petroleum-derived jet fuel. However, its negligible indirect land use change emissions might potentially make it competitive against neat SAFs originating from first-generation biomass.

This research uses system optimization to assess short, medium, and long-term scenarios to achieve the committed CO₂-emission goals of Ecopetrol while minimizing potential adverse impacts such as incremental operational costs and utility demand. Two Colombian refineries are used as a case study: a medium-complexity and a high-complexity refinery. The study explores whether the level of complexity plays a significant role in the results. Potential technologies were ranked using a multi-criteria decision analysis. The system analysis and optimization were done in Linny-R, a mixed integer linear programming software package developed by TU Delft. In the short-term (2030) scenario, the selected technologies include low-carbon H₂ produced from Steam Methane Reformer units with carbon capture and storage and H₂ produced from renewable electricity sources. The medium and long-term (2050) scenario also included biomass gasification, naphtha reforming, and the cracking unit, all with carbon capture and storage. The refineries were modelled using on-site company data. The results indicate that using low-carbon H₂ and carbon capture and storage to flue gases would allow to reach the net zero target. Furthermore, the results show that the level of complexity in a refinery significantly impacts the decarbonization deployment pathways. The high-complexity refineries benefited from using low-carbon H₂ as feedstock while the medium-complexity refinery relied on a combination of carbon capture and low-carbon H₂ as an alternative fuel. This research highlights the potential to achieve substantial CO₂ emissions reductions with less impact on the total operational cost by using the amount of excess refinery gas generated when H₂ is used as fuel in boilers and process furnaces. A significant challenge remains in identifying suitable applications for surplus refinery fuel gas beyond its conventional use in combustion within boilers and furnaces.

This paper evaluates the potential impacts of introducing low-carbon intensity hydrogen technologies in two oil refineries with different complexity levels, emphasizing the role of hydrogen production in reducing CO₂ emissions. The novelty of this work lies in three key aspects: Comprehensive system analysis of refinery complexity using real site data, integration of low-carbon Hydrogen technologies, long-term and short-term strategies. Two Colombian refineries serve as case studies, with technological solutions adapted to their complexity levels. The methodology involves evaluating different options for hydrogen production, accounting for improvement in technological efficiency over time. The refinery systems were evaluated in a cost-optimization model built in Linny-r. Three different scenarios were considered, Business-As-Usual (BAU), high, and low-ambitions decarbonization scenarios, focusing on the time horizons of 2030 and 2050. When comparing the two case studies, the preferred decarbonization strategy for both facilities involves the substitution of SMR technology with water electrolyzers powered by renewable electricity. Post-2030, biomass-based hydrogen technology is still a costly alternative; however, to achieve CO₂ neutrality, negative emissions storage of biogenic CO₂ emerges as an achievable alternative. Our results indicate the achievability of CO₂ reduction objectives in both refineries. Our results show that achieving long-term CO₂ neutrality requires both refineries to increase renewable electricity production by 5 to 6 times for powering water electrolyzers, steam production by 2 to 2.5 times for CO₂ capture, and supply of dry biomass by 2.6 to 4.5 kt/d. The two most significant factors influencing the refining net margin in the decarbonization scenarios are primarily the CO₂ and the renewable electricity prices. The short-term horizon emerges as the pivotal period, particularly within the high-ambition decarbonization scenarios. In this context, the medium complexity refinery demonstrates economic viability until a CO₂ price of 140 €/t CO₂, while the high complexity refinery endures up to 205 €/t CO₂. The high complexity refinery is better prepared to face the challenges of decarbonization and the impacts generated on the refining margin. Compared to the BAU scenario, the high complexity refinery shows a negative impact on the net margin that corresponds to a 40 % and 5 % reduction in the short and long term, respectively. Meanwhile, for the medium complexity refinery, the impact on net margin amounts to a 52 % reduction in the short term and a 27 % improvement in the long term. Furthermore, our research highlights the significant potential for reducing CO₂ emissions by fully eliminating the use of refinery gas as fuel, providing alternative applications for it beyond combustion.

Different alternative carbon sources like CO₂, biomass and plastic waste, can be used to replace fossil carbon as feedstock in the production of methanol. Based on current literature, the plastic-based methanol route is the most competitive one among the three based on price indicator, but there is still a lack of comprehensive understanding of the techno-economic differences between alternative feedstock technologies. In this study, three technologies from each alternative feedstock were assessed to evaluate the techno-economic trade-offs between them. The research shows that even though currently the plastic-based route is comparatively cost competitive with the conventional route of producing methanol, the CO₂-based methanol route can also be competitive with green hydrogen prices in the range of 1400-1100 EUR/t. While the biomass-based route showed superior energy performance compared to the other two.