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.

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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.

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Combining intermittent renewable electricity (IRE) with carbon capture and utilisation is urgently needed in the chemical sector. In this context, microbial electrosynthesis (MES) has gained attention. It can electrochemically produce hexanoic acid, a value-added chemical, from CO₂. However, there is a lack of understanding regarding how the intermittency of renewable electricity could impact the design of a MES plant. We studied this using Aspen Plus models. A MES plant that was powered by constant grid electricity could operate from 100% down to 70% of its nominal capacity, at which point the heat exchangers and the internal geometrical design of the distillation towers became bottlenecks. The levelised production cost of hexanoic acid (LPC_C6A) was estimated at 4.0 €/kg. Switching to IRE supply increased LPC_C6A to 5.3 €/kg (for wind electricity) and 4.7 €/kg (for hybrid renewable electricity). A battery energy storage system (BESS) was deployed. The lowest LPC_C6A was found at a BESS installation of 29 GJ/h for wind electricity (5.1 €/kg) and at 12 GJ/h for hybrid renewable electricity (4.7 €/kg). In both situations, the volume flexibility of the MES plant was not improved. At the investigated market and operating conditions, coupling IRE to the MES plant was economically infeasible.

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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.

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The petrochemical industry needs to reduce the use of fossil fuel as carbon feedstock to reduce its CO2 emissions. Several alternative carbon sources (ACSs), such as biomass, CO2 and plastic waste are being proposed to replace fossil carbon. As each of these ACS process routes has its tradeoffs, it is essential to identify the defossilization pathways that will have the most significant impact. In this work, a superstructure-based optimization approach is presented that can be used to assess defossilization pathways in existing petrochemical clusters. The small case study shows that CO₂ is a promising ACS to replace fossil fuel as the main carbon source but requires a large amount of green hydrogen and significant modifications to the existing cluster.

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Electrifying the utility supply of existing petrochemical processes is a potential measure for CO₂ emission reduction in the chemical industry. With an increasing share of variable renewable energy sources in the electricity grid, electricity price fluctuations will become more frequent. However, most existing petrochemical processes operate continuously and, therefore, require a constant supply of utilities. In this paper, we model an electrified utility system that includes different types of storage units to explore how a constant utility demand could be supplied under fluctuating electricity prices. To achieve this, we model a utility system that provides electricity and heat to an olefins plant in the Port of Rotterdam and use mathematical optimisation to capture optimal hourly operations of the plant under fluctuating prices. We find that the cost-optimal utility system consists of electric boilers, integrated thermal energy storage, and technologies for storing and using hydrogen produced on-site. With data for prices of the Dutch electricity grid in 2022, the electrified utility system results in higher costs than a fossil-based system. Increasing price fluctuation levels would lead to lower operational costs as the system's flexibility enables shifting the electricity consumption to the hours with the lowest electricity prices.

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CO2 electroreduction driven by renewable energy is a promising technology for defossilizing the chemical industry, but intermittency challenges its operation. This work aims to understand the impacts of intermittency on the design, volume flexibility, and scheduling of a microbial electrosynthesis (MES) plant that converts CO2 to hexanoic acid. A battery and a storage tank were considered to buffer the intermittency. Explorative case studies showed that batteries were economically unfavorable. Restricted by the downstream processing (DSP) flexibility, a storage tank with optimized size combined with optimal scheduling, under the assumed conditions in this work, improved the plant’s volume flexibility only by 10%. The carbon footprint became 3 times lower when switching from grid to renewable electricity, but the levelized production cost of hexanoic acid increased. Hence, coupling with renewable electricity was not economically but environmentally favorable. Developing more flexible DSP technologies or synthesizing higher-purity chemicals are needed to enhance MES’s attractiveness.@en

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.

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The petrochemical industry is composed of several interconnected processes that use fossil-based feedstock for producing chemicals. These processes are typically geographically clustered and often belong to different parties. Reducing the environmental impacts of the petrochemical industry is not straightforward due to, on the one hand, their reliance on fossil fuels for energy and as a feedstock and, on the other hand, the significant level of interconnected energy and material flows among processes. Current methods for analyzing changes to existing processes cannot capture the multitude and level of interactions. The goal of this paper is to create a model of a petrochemical cluster and analyze its physical characteristics and performance. This paper addresses this goal by developing an assessment method that combines process simulations, multiplex graph analysis, and key performance indicators. The method is applied to a case study based on the petrochemical cluster in the Port of Rotterdam, resulting in a uniquely highly detailed model of a petrochemical cluster. The network analysis results show that only some of the processes are very interconnected. From the performance analysis, it can be observed that the olefins process is the most carbon-intense and has high CO₂ emissions. Additionally, the results showed the importance of considering existing interconnections when assessing the current performance of existing petrochemical clusters or the performance due to future changes to chemical processes. For instance, some changes would occur to an industrial cluster by introducing alternative carbon sources, such as biomass or CO₂.

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The reliance of the petrochemical industry on fossil-based sources will need to be reduced by the introduction of Alternative carbon sources (ACS). Introducing ACS in a petrochemical cluster will require existing processes to be modified or replaced, potentially affecting other chemical processes within the cluster due to existing material and energy interconnections. Therefore, it is important to understand the current level of interconnections, functioning, and performance of the petrochemical cluster before introducing ACS. In this work, a representative cluster model based on the petrochemical cluster of the Port of Rotterdam was developed and considered as a case study. This model was analyzed using complex network analysis and environmental and technical key performance indicators. The selected key performance indicators (KPIs) provide insight into the performance of a petrochemical cluster, while the network properties give an understanding of the exchange of material and energy in an industrial cluster.@en

Steam generating heat pumps show great potential for reducing carbon emissions in the industrial sector. However, predicting their performance is challenging as the exergy destruction of e.g., compressors and expansion valves increases with the temperature lift and condenser temperature. With over seventy design improvements mentioned in the literature, selecting the most effective design improvements is crucial. In this study, energy and exergy-based methods were compared in their ability to identify design improvements for a single stage subcritical heat pump to produce steam from hot condensate. The energy-based method suggested the addition of a sequential compressor with an intermediate cooler; however, this design did not improve the heat pump's techno-economic performance. The suggestion of adding either an internal heat exchanger or a flash vessel by exergy-based methods did lead in both cases to improved techno-economic performance. The internal heat exchanger performed best and increased the coefficient of performance from 2.3 to 2.8 and reduced operational costs by 0.8 M€ after 5 years of operation. Additionally, the initial investment decreased by 135 k€, and the total costs of operation decreased from 10.3 M€ to 8.7 M€. These findings show that exergy-based methods are the way forward in identifying effective design improvements for steam generating heat pumps.

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Electrochemical reduction of CO2 (CO2ER) is an emerging technology with the potential to limit the use of fossil-based feedstocks in the petrochemical industry by converting CO2 and renewable electricity into useful products such as syngas. Its successful deployment will depend not only on the technology's performance but also on its integration into the supply chain. In this work, a facility location model is used to gain insights regarding the capacity of CO2ER plants that produce syngas and the implications for the central/decentral placement of these CO2-based syngas plants. Different optimal configurations are examined in the model by changing the syngas transport costs. In this exploratory case, the results indicate that centralization is only an option when the syngas and CO2 transport costs are similar. When syngas transport is more expensive, decentralizing CO2-based syngas plants in the supply chain appears more feasible.@en

Self-organized industrial symbiosis (IS) starts with one actor's decision to invest in a waste recovery plant and the other actors' decision to buy the recovered flow. Technical and institutional conditions of the cluster influence actors' decisions. This paper explores the emergence of IS collaborations in industrial clusters under different techno-economic conditions in the long term. We propose a mixed-integer linear programming model that incorporates costs and constraints associated with waste recovery and exchange to study actors' investment decisions and investigate shaped symbiotic exchanges under rising energy prices and limited electricity supply. The approach is implemented in Iran's Persian Gulf Mining and Metals Special Economic Zone as a case study. The results revealed that changes in internal or external condition simultaneously influence the industrial and waste recovery plants. For instance, increasing energy prices without raising product prices significantly decreased the production level of industrial plants and, consequently, heat recovery potential. Furthermore, the waste heat recovery plants' contribution to improving the cluster's economic and environmental performance was not the same. Electricity recovery from a power plant's waste heat can result in 55 PJ grid electricity intake reduction and 720 M€ cluster cash flow increase. Recovered cooling or electricity from the steelmaking plant waste heat was consumed internally rather than shaping IS. These model outcomes show its capability to study IS within the socio-technical structure of the cluster, not a standalone phenomenon. Implemented conceptualization offers a novel system-level approach, which could be adjusted to assess other industrial development strategies.@en

Reaching our climate goals will require urgent advancements in the development of fossil-free technologies. Solid-oxide electrolysis (SOE) at high-temperature is a promising candidate for combining CO₂ utilization and renewable electricity use. Explorative techno-economic analyses are being performed to understand the full plant design requirements for integrated SOE systems. However, there is still a lack of understanding of the potential impact that the pre-treatment of CO₂ will have on the overall design and economics of a SOE-based system. To address this knowledge gap, as a first step, the process model of the pre-treatment units needed to purify CO₂ from a bioethanol plant is developed in Aspen Plus in the current work. Based on the preliminary results of this paper, the equipment costs mainly stem from the units related to the removal of sulfur (~65%) and alcohols (~32%). The energy costs are almost entirely related to the cryogenic distillation step required for the removal of non-condensable gases (~96%).@en

Negative emission technologies such as biomass with carbon capture and storage (bioCCS) may become an important instrument to limit global warming. Currently, estimates of CO2 avoidance cost for bioCCS vary widely. Using a case study of a cement plant, this paper illustrates how this variance is partially attributable to the system boundary choices made by modellers. The estimated avoidance cost for the bioCCS-in-cement plant ranged from 48-321€2017/t CO2(eq) and the net CO2(eq) from -660 to 16 kg CO2(eq)/t cement, without any change in the technological model, equipment and input costs, or lifecycle emissions, but by changing the system boundaries used for cost and emission accounting, reflecting the different boundaries seen in bioCCS literature. To allow for more comparable bioCCS cost estimates, studies should always account for costs and emissions of both biomass production and the full chain of carbon capture, transport, and permanent storage, as both are fundamental to the role of bioCCS as a potential “negative emission technology”. We also advocate for clear decomposition of metrics, separation of “avoided emissions” from physical flows of greenhouse gases; and explicit consideration of the temporality of the bioCCS system. With these guidelines, the range of avoidance cost of the bioCCS-in-cement plant shrinks to 157-193€2017/t CO2(eq) for near-term estimates and to 89-107€2017/t CO2(eq) for longer-term estimates.@en

Using alternative carbon sources (ACS) to produce downstream derivatives (DDs) is a promising option for defossilising the chemical industry. However, the potential consequences of using ACS in interconnected petrochemical clusters are generally overlooked. This paper aims to develop a methodological approach for systematically analysing defossilisation impacts at the value chain level. For this, a single value chain for producing methyl-tert-butyl-ether (MTBE) was used as a case study. The individual components of the value chain were modelled in Aspen Plus v12. Both ACS- and fossil-based value chains were compared in terms of (i) changes in the structure of the value chain and (ii) the magnitude of the impacts. The results show that the defossilisation of a single value chain causes additional impacts at the cluster level.@en

Carbon capture and storage (CCS) is an essential technology to mitigate global CO2 emissions from power and industry sectors. Despite the increasing recognition of its importance to achieve the net-zero target, current CCS deployment is far behind targeted ambitions. A key reason is that CCS is often perceived as too expensive. The costs of CCS have however traditionally been looked at from the industrial plant perspective, which does not necessarily reflect the end user’s one. This paper addresses the incomplete view by investigating the impact of implementing CCS in industrial facilities on the overall costs and CO2 emissions of end-user products and services. As an example, we examine the extent to which an increase in costs of raw materials (cement and steel) due to CCS impacts the costs of building a bridge. Results show that although CCS significantly increases cement and steel costs, the subsequent increment in the overall bridge construction cost remains marginal (∼1%). This 1% cost increase, however, enables a deep reduction in CO2 emissions (∼51%) associated with the bridge construction. Although more research is needed in this area, this work is the first step to a better understanding of the real cost and benefits of CCS.@en

Electrification of processes and utilities is considered a promising option towards the reduction of greenhouse gas emissions from the chemical industry. Therefore, electricity demand is expected to increase steeply. Since the sources of future low-carbon electricity are variable in nature, there is a need for strategies to match availability and demand. Literature identified the flexibility of chemical processes as one promising strategy to address variability. This study aims to provide insights into how stakeholders from the power sector and the chemical industry consider flexibility in chemical processes and to identify key benefits and bottlenecks. For this article, we combined a review of peer-reviewed and grey literature with stakeholder interviews to map and describe the state of the art of flexible chemicals production, and to identify requirements for further research. The main drivers to investigate the flexibility potential are first, the contribution to energy system reliability, and second, potential cost savings for the industry. Main limitations are considered to be first, the uncertain economic performance of flexible processes due to investment costs, reduced production and uncertain revenues from flexible operation, and second, the complexity of the implementation of flexibility.@en

Due to the heavy dependence on fossil-fuels as raw materials, the defossilization of feedstocks in the petrochemical industry represents a challenge. A large number of possible process routes that use alternative carbon sources (ACS) like CO2, biomass, and waste are being developed for the feedstock replacement. For instance, to produce ethylene, more than 40 ACS process routes were identified. These multiple options make the selection of the promising process route a complex task. By replacing feedstocks, a process can change significantly and the impacts related to these changes in a highly interconnected industrial cluster can create cascading effects due to system interdependencies. This work aims to understand the cascading impacts in carbon flows and prices of implementing an ACS production process in an ethylene cluster. The results show that PVC will be the highest impacted and defossilizing one value-chain can have cascading effect on other value-chains as observed for PET.@en