Periodic Reporting for period 1 - MINICOR (MILD Combustion with Nitrogen and Carbon Dioxide Reforming)
Periodo di rendicontazione: 2023-11-01 al 2024-10-31
Reduced net emissions of carbon dioxide (CO2) are necessary to achieve the IPCC goals of limiting global warming and ensuring a sustainable future for our society. The natural balance of CO2 via photosynthesis is insufficient to compensate for the anthropogenic emissions, and active measures are thus necessary. MINICOR aims to develop a versatile process for managing and valorizing CO2 and nitrogen while efficiently deploying renewable resources.
The process utilizes renewable biomass feedstock that undergoes pyrolysis and releases water, gas, and organic compounds, forming bio-oil, also known as pyrolysis oil. While this pyrolysis gas represents a relatively low heating value fuel, it can be combusted under Moderate or Intense Low-oxygen Dilution (MILD) conditions for energy conversion. The heat from the combustion supplies dry reforming of CO2 with bio-oil to generate hydrogen-containing syngas for further energy conversion or chemical production. Solid biochar from the pyrolysis can be upgraded by activation with CO2 and nitrogen adsorption, and further used for soil amendment restoring nitrogen balance. The concept adopts a circular approach to address the challenges of handling CO2 emissions and nitrogen imbalance in our environment.
Development of the process will initially have a scientific impact, targeting the research community and industrial users, e.g. by
• generic knowledge of biomass conversion.
• numerical models of the processes.
• a new concept for syngas production via CO2 reforming.
• development of biochar materials for soil amendment.
These developments can, in turn, have an economic impact as
• they contribute to a circular economy by efficiently utilizing resources.
• the numerical models provide cost-effective optimization tools for biomass conversion.
• the biochar provides a new potential material feedstock.
The project results thus potentially target industry end-users in multiple sectors such as energy, chemical production, and agriculture.
The outcomes also have a societal impact as they address the UN Agenda 2030 sustainable development goals
• Reduced climate impact from energy production with reduced CO2 emissions (Goal#13).
• Clean energy by increasing and optimizing renewable energy sources utilization (Goal #7).
• The production of energy from renewable biomass sources contributes to responsible consumption and production (Goal #12).
• Sustainable food production using biochar for soil amendment to enhance agricultural productivity (Goal #2).
• Sustainable supply of energy, feedstock for chemicals (syngas), and fertilizer production promote the development of a sustainable industry (Goal #9).
The project’s pathway to societal impact involves interaction with policymakers, decision-making bodies, and the general public.
The process utilizes renewable biomass feedstock that undergoes pyrolysis and releases water, gas, and organic compounds, forming bio-oil, also known as pyrolysis oil. While this pyrolysis gas represents a relatively low heating value fuel, it can be combusted under Moderate or Intense Low-oxygen Dilution (MILD) conditions for energy conversion. The heat from the combustion supplies dry reforming of CO2 with bio-oil to generate hydrogen-containing syngas for further energy conversion or chemical production. Solid biochar from the pyrolysis can be upgraded by activation with CO2 and nitrogen adsorption, and further used for soil amendment restoring nitrogen balance. The concept adopts a circular approach to address the challenges of handling CO2 emissions and nitrogen imbalance in our environment.
Development of the process will initially have a scientific impact, targeting the research community and industrial users, e.g. by
• generic knowledge of biomass conversion.
• numerical models of the processes.
• a new concept for syngas production via CO2 reforming.
• development of biochar materials for soil amendment.
These developments can, in turn, have an economic impact as
• they contribute to a circular economy by efficiently utilizing resources.
• the numerical models provide cost-effective optimization tools for biomass conversion.
• the biochar provides a new potential material feedstock.
The project results thus potentially target industry end-users in multiple sectors such as energy, chemical production, and agriculture.
The outcomes also have a societal impact as they address the UN Agenda 2030 sustainable development goals
• Reduced climate impact from energy production with reduced CO2 emissions (Goal#13).
• Clean energy by increasing and optimizing renewable energy sources utilization (Goal #7).
• The production of energy from renewable biomass sources contributes to responsible consumption and production (Goal #12).
• Sustainable food production using biochar for soil amendment to enhance agricultural productivity (Goal #2).
• Sustainable supply of energy, feedstock for chemicals (syngas), and fertilizer production promote the development of a sustainable industry (Goal #9).
The project’s pathway to societal impact involves interaction with policymakers, decision-making bodies, and the general public.
Year 1
WP1 - Pyrolysis
A survey was conducted on biomass resources and pyrolysis studies in the literature. Straw, hardwood, softwood, and nitrogen-rich coffee silverskin were selected as biomass feedstock. Since low pyrolysis temperature and heating rate are suitable for producing biochar for nitrogen adsorption, pyrolysis of biomass in N2 and CO2 has been investigated for temperatures of 360, 450, and 600 °C and a heating rate of 10 °C/min. Experimental studies have been made to verify conditions that suit the MINICOR process steps and to obtain data for the development and validation of numerical models. Data on the biochar product will further serve as input for project WP5.
The experimental studies have been carried out using various techniques to assess pyrolysis product yields and compositions. These include
- Thermogravimetric analysis to analyze biomass decomposition versus time and temperature by monitoring mass loss due to the release of volatiles.
- Techniques to analyze various aspects of chemical composition
- Calorimetry techniques to determine heating values.
WP2 -MILD combustion/dry reforming
Bio-oil oxidation and reforming studies were initiated in M6 with preparations of experimental work planned for the following period. Thermal conversion of bio-oil will be investigated by studying selected chemical components and the experimental facility has been adapted accordingly. Initial runs were made on gases, and a preliminary analysis was carried out. A reactor has also been adapted for further studies at higher temperatures.
A numerical study of dry reforming was carried out for different hydrocarbons, and the temperature corresponding to 10% of CO2 captured was evaluated using kinetic models. Methane requires the highest temperature to achieve 10% CO2 conversion, whereas heavier and more complex molecules, which could represent bio-oil, e.g. guaiacol and butanol, require lower temperatures.
The overall goal of the project is to demonstrate a combined pyrolysis/MILD system. As a first step to address this objective, process simulations were made using the Aspen Plus V.14 software to evaluate the impact of the MINICOR concept on the carbon and nitrogen cycles, analyze energy and carbon flows, and identify operational conditions to maximize syngas production. In addition, the study addressed integration strategies and valorization of waste heat. The results indicate that up to 65% of the carbon going into the process can be sequestered through the optimization of pyrolysis for bio-oil production and, subsequently, syngas yield in CO2 reforming.
WP1 - Pyrolysis
A survey was conducted on biomass resources and pyrolysis studies in the literature. Straw, hardwood, softwood, and nitrogen-rich coffee silverskin were selected as biomass feedstock. Since low pyrolysis temperature and heating rate are suitable for producing biochar for nitrogen adsorption, pyrolysis of biomass in N2 and CO2 has been investigated for temperatures of 360, 450, and 600 °C and a heating rate of 10 °C/min. Experimental studies have been made to verify conditions that suit the MINICOR process steps and to obtain data for the development and validation of numerical models. Data on the biochar product will further serve as input for project WP5.
The experimental studies have been carried out using various techniques to assess pyrolysis product yields and compositions. These include
- Thermogravimetric analysis to analyze biomass decomposition versus time and temperature by monitoring mass loss due to the release of volatiles.
- Techniques to analyze various aspects of chemical composition
- Calorimetry techniques to determine heating values.
WP2 -MILD combustion/dry reforming
Bio-oil oxidation and reforming studies were initiated in M6 with preparations of experimental work planned for the following period. Thermal conversion of bio-oil will be investigated by studying selected chemical components and the experimental facility has been adapted accordingly. Initial runs were made on gases, and a preliminary analysis was carried out. A reactor has also been adapted for further studies at higher temperatures.
A numerical study of dry reforming was carried out for different hydrocarbons, and the temperature corresponding to 10% of CO2 captured was evaluated using kinetic models. Methane requires the highest temperature to achieve 10% CO2 conversion, whereas heavier and more complex molecules, which could represent bio-oil, e.g. guaiacol and butanol, require lower temperatures.
The overall goal of the project is to demonstrate a combined pyrolysis/MILD system. As a first step to address this objective, process simulations were made using the Aspen Plus V.14 software to evaluate the impact of the MINICOR concept on the carbon and nitrogen cycles, analyze energy and carbon flows, and identify operational conditions to maximize syngas production. In addition, the study addressed integration strategies and valorization of waste heat. The results indicate that up to 65% of the carbon going into the process can be sequestered through the optimization of pyrolysis for bio-oil production and, subsequently, syngas yield in CO2 reforming.
Biomass pyrolysis studies have applied an ensemble of experimental methods for the analysis of yields and composition. In particular, state-of-the-art Raman spectroscopy with a multipass cavity for sensitive concentration measurements in the gas phase has been arranged for measurements in a pyrolysis reactor.
Experimental studies have been made on dry reforming based on methane and biogas. These have been complemented with simulations that include more complex hydrocarbon compounds mimicking biooil.
The combined process of biomass pyrolysis, MILD combustion, dry reforming, and biochar sequestration have been simulated using Aspen Plus software to track energy and carbon flows. Simulations suggest up to 65% overall carbon sequestration of the process.
Experimental studies have been made on dry reforming based on methane and biogas. These have been complemented with simulations that include more complex hydrocarbon compounds mimicking biooil.
The combined process of biomass pyrolysis, MILD combustion, dry reforming, and biochar sequestration have been simulated using Aspen Plus software to track energy and carbon flows. Simulations suggest up to 65% overall carbon sequestration of the process.