Biofuels - 11 on-going projects

Continuous production of high yield liquid jet fuel - B2A, Biomass to Aviation fuels, NFR Project

PhD student: Albert Miro i Rovira; Supervisor: prof. De Chen

Senior Researcher: Kumar R. Rout

My current research project is framed inside the Biomass to Aviation Fuel Project (B2A), particularly I will work in the fourth work package (WP4) of the B2A project. The objective of this work package is the experimental proof of continuous production of high yield liquid jet fuel. To accomplish this objective, the selected catalysts obtained from WP2 will be scaled up, by implementing a large batch synthesis procedure. Additionally, other operational parameters, like temperature, pressure and gas flow will be carried out and tested in the mini-pilot plant found in Hall D (rig 2.0B) with a biomass feeding capacity of 1kg/hour to evaluate the catalyst performance in these conditions. Therefore, the catalyst stability will be tested (for > 100 hours) in both integrated CFHP and CVU as well as high-pressure HDO reactors. As evidence of successfully accomplishing the objective of this work package it is established a goal of producing more than 5 liters of biofuels.

Conversion of synthesis gas from fish waste gasification over cobalt catalysts - Bio4Fuels, NFR Project

PhD student: Oscar Ivanez; Supervisor: prof. Edd Blekkan

Master student 2021/22: Anette Synnøve Groven

Senior Researcher: Kumar R. Rout

The increasing development of the global industry demands further energy production. The main source of energy are the fossil fuels and their use has been increasing every year. In 2016, more than 80% of primary energy in the world was provided by fossil fuels. The new policies and future scenarios, where the increased prices of the fossil fuels and the demand of cleaner fuels, make necessary alternatives of fuel production. Within these alternatives, the interest in the Fischer Tropsch Synthesis (FTS) increased in recent years. The FTS converts synthesis gas to hydrocarbons. The selectivity of the FTS can be optimized in order to obtain different products.  Among these products, light olefins represent added value compared to fuels, which always will be the main product.

The syngas can be produced from different sources such as natural gas, coal or biomass. One interesting feedstock for the syngas is the biomass. This renewable energy source is abundant and opens the possibility to improve the total yield of different industries by using waste as a feedstock for the FTS. The total aquaculture production in Norway in 2018 was 1.354.941 tons, with 68% of the amount being editable. This represents an opportunity to valorize the fish waste in order to reduce the economic loses and improve the efficiency of the industries.

In this context, cobalt-based catalysts are going to be studied in the FTS with emphasis on olefin selectivity from biomass, BTL. The catalysts are going to be prepared by different synthesis methods, characterized by several standard and advance techniques, and tested in the FTS. The reaction condition choose for the project will favor the light olefin production. Due to the selection of fish waste as feedstock for the syngas, the project will be focused on the effect of several components present on this syngas source, which could affect the performance of the catalytic activity and selectivity. In addition, in order to improve the catalytic activity and selectivity, different metal oxides and noble metals will be studied as catalysts promoters.

Catalytic upgrading of bio-oil to aviation fuels - B2A, Biomass to Aviation fuels, NFR Project

PhD student: Petter Tingelstad; Supervisor: prof. De Chen

Master student 2021/22: Adrian Madsen Lager

Senior Researcher: Kumar R. Rout

The project objective is to produce sustainable aviation fuel from lignocellulosic biomass. We will achieve this by fast hydropyrolysis of pine wood followed by hydrodeoxygenation of the produced bio oil to increase the heating value as well as stabilization of the product by removing unwanted heteroatoms.

Petter's contribution to the project will mainly be process design, process optimization, practical experiments, and techno-economical evaluations of the project.

Catalyst development for biomass to aviation fuels - B2A, Biomass to Aviation fuels, NFR Project

PhD student: Kishore Rajendran; Supervisor: prof. De Chen

Master student 2021/22: Karthikai Selvan Sivasamy 

Senior Researcher: Kumar R. Rout

The PhD project focus on the theme to produce two cheap catalyst which is active in carbon-carbon coupling and HDO reaction resp. The novelty here lies in the process developed specifically for allowing an economically means to produce bio-jet fuel. The ultimate goal is to produce jet-fuel from biomass in a price range (<0.78 Euro/L) competitive to the present state of art minimum fuel selling price reported in the literature from biomass (1.04 Euro/L) via fast hydropyrolysis. The key here is to increase the carbon retention with reduced oxygen content in the final bio-oil through ex-situ tandem configuration of carbon-carbon coupling and hydro-deoxygenation catalyst after fast hydropyrolysis of biomass.

Chemical transformation of enzymatic hydrolysis Lignin (EHL) with catalytic solvolysis to fuel commodities under mild conditions, EHLCATHOL, EU Project

Researcher: Hongfei Ma; Advisor: prof. De Chen

Senior Researcher: Kumar R. Rout

Stabilize the virgin Enzymatic hydrolysis lignin catalytic solvolysis oil to facilitate separation and upgrade the bio-oil from the solvolysis reaction to increase the C6+ yield; regulate and optimize fuel properties through product engineering by tuning the catalyst selectivity.

Bio-Ethanol steam reforming for on board hydrogen generation system

PhD student: Mario Ernesto Casalegno; Supervisor: prof. De Chen

The transition towards more sustainable means of energy production, distribution and use is a key issue. Slowing down, or even reversing the negative climatic effects from the utilization of fossil fuels is the ultimate goal. Utilization of hydrogen (H₂) as an energy carrier can be a sustainable solution that will reduce the impact of human activities on the environment. Provided that H₂ is produced in a sustainable way from renewable sources, such as water (using renewable energy) or from biomass it has the potential, through its use in fuel cells with favorable efficiencies, to cover energy needs with a significant reduction in greenhouse gas emissions. H₂ production through steam reforming of hydrocarbons is a mature technology that can be extended to use ethanol as a feedstock. Bioethanol formed by fermentation processes has significant advantages and appears to be a strong candidate as an energy vector suitable for H2 production.
Our efforts in this project are focusing on the creation of a prototype that integrates steam reforming of bioethanol for hydrogen production with hydrogen combustion into a compact multichannel reactor that can be used on board vehicles. Optimization of catalytic materials for both reaction applications will be assisted by kinetic experiments and theoretical calculations that will be used for building a microkinetic model. The optimal process conditions to run que experiments will be calculated using Aspen Plus simulator.

Biomass to Liquid Fuels - Steam Reforming of Tar and Methane from Biomass Gasification, Bio4Fuels, NFR project

PhD student: Ask Lysne; Supervisor: prof. Edd Blekkan

Senior Researcher: Kumar R. Rout

The project is part of the Centre for Environment-frienly Energy Research (FME) Bio4Fuels

The growing world population and increasing awareness of the effects of greenhouse gas emissions on the global environment has made the provision of renewable energy sources evident as a major challenge for future sustainable development [1-3]. The world population is expected to exceed 9 billion people by 2050 and the International Energy Agency (IEA) have estimated a 42-50% increase in the global energy demand by 2035 compared to the 2009 consumption [3]. Renewable energy sources including hydroelectric, wind and solar power can provide vital low-emission electricity, but the electrification of some industrial and transportation niches is limited by the considerably lower energy density and recharging efficiency compared to liquid fuels [3]. The transportation sector accounts for around 25% of the global CO2 emission, where 90% utilizes petroleum based fuels [4-6]. The substitution of currently applied fossil fuels by liquid fuels produced from renewable resources can hereby provide an efficient reduction of the global net CO2 emission including the considerable advantage of the continued utilization of currently operating combustion engine technology [6]. The annual growth of terrestrial plants store more than 3 times the global energy demand, and biomass is in practice the only viable feedstock regarding production of renewable carbon-based liquid fuels [7]. The successful adaptation of the Fischer-Tropsch (FT) hydrocarbon synthesis from the original coal to liquid (CTL) technology to the natural gas to liquid (GTL) process has presented the development of biomass to liquid (BTL) and organic waste to liquid (WTL) technology integrating thermal gasification and FT synthesis as a highly attractive option for high-quality second-generation feedstock liquid biofuel production [8]. The approach includes the considerable advantage of the utilization of already available gasification and FT technology [9]. The successful integration of gasification and FT technology is however limited by technical difficulties regarding the intermediate gas conditioning of the synthesis gas (syngas) requiring the removal of inorganic, organic and particulate contaminants [10]. The elimination of tar has herein been put forth as the most cumbersome challenge of the commercialization of such processes [11]. The PhD project will address catalytic steam of tar and methane as part of this key gas conditioning step. The effects of operating parameters like temperature and steam to carbon (S/C) ratio on catalyst activity as well as deactivation effects regarding coke formation and poisoning from inorganic contaminants are within the scope of the experimental approach.

[1] Dincer, I. Renewable energy and sustainable development: a crucial review, Renew. Sustain. Energy Rev., 2000, 157-175. [2] Panwar, N. L.; Kaushik, S. C.; Kothari, S. Role of renewable energy sources in environmental protection: A review. Renew. Sustain. Energy Rev. 2011, 15, 1513-1524. [3] Chu, S.; Majumdar, A. Opportunities and challenges for a sustainable energy future. Nature 2012, 488, 294-303. [4] Simionescu, M.; Albu, L.-L.; Szeles, M. R.; Bilan, Y. The Impact of Biofuels Utilisation in Transport on the Sustainable Development in the European Union. Technol. Econ. Dev. Eco. 2017, 23, 667-686. [5] Chapman, L. Transport and climate change: a review. J. Transp. Geogr. 2007, 15, 354-367. [6] Butterman, H. C.; Castaldi, M. J. CO2 as a Carbon Neutral Fuel Source via Enhanced Biomass Gasification. Environ. Sci. Technol. 2009, 43, 9030-9037. [7] Guo, M.; Song, W.; Buhain, J. Bioenergy and biofuels: History, status and perspective. Renew. Sustain. Energy Rev. 2015, 42, 712-725. [8] Zennaro, R.; Ricci, M.; Bua, L.; Querci, C.; Carnelli, L.; d'Arminio Monforte, A. In Greener Fischer-Tropsch Processes for Fuels and Feedstocks, Maitlis, P. M., de Klerk, A., Eds.; Wiley-VCH: Weinheim, 2013; Chapter 2, pp 19-49. [9] Ail, S. S.; Dasappa, S. Biomass to liquid transportation fuels via Fischer-Tropsch synthesis - Technology review and current scenario. Renew. Sustain. Energy Rev. 2016, 58, 267-286. [10] Rauch, R.; Kiennemann, A.; Sauciuc, A. In The Role of Catalysis for the Sustainable Production of Bio-fuels and Bio-chemicals, Triantafyllidis, K. S., Lappas, A. A., Stöcker, M., Eds.; Elsevier B.V.: Oxford, 2013; Chapter 12, pp 397-443. [11] Huber, G. W.; Iborra, S.; Corma, A. Synthesis of Transportation Fuels from Biomass: Chemistry, Catalysts, and Engineering. Chem. Rev. 2006, 106, 4044-4098

Novel Fe catalysts for the Fischer Tropsch synthesis based on renewable feedstocks

PhD student: Joakim Tafjord; Supervisor: Associate prof. Jia Yang

The depletion of oil reserves has increased the interest in developing and improving processes that can replace the use of crude oil. An alternative is the Fischer Tropsch synthesis (FTS), a catalytic process where syngas (CO+H₂) reacts to form a range of hydrocarbons, such as light olefins, gasoline, diesel and waxes. The lower olefins (C2-C4) and their derivatives are important building blocks in the chemical industry, used to produce many high performance materials and chemical products, i.e. plastic and engineering resins, lubricants, coatings and paints. To increase the renewability of the process, the syngas feedstock should derive from biomass. However, syngas from biomass is lean in hydrogen, and can be rich in CO₂ if extensively removed. This makes iron an attractive catalyst, as it can manage a relatively wide range of syngas feed ratios (H₂/CO = 0.5-2.5), due to the water-gas-shift activity, additionally it can work at higher temperatures with low methane production. However, iron catalyst are prone to deactivation by sintering, catalyst attrition, phase-transformations and carbon deposition.

Gasification and FT-synthesis of lignocellulosic feedstocks (GAFT) - SINTEF Industry

Staff: Research Scientist Rune Myrstad, Senior Research Scientist Bjørn Christian Enger

Project Category: KPN-project in ENERGIX. Project Responsible: SINTEF Energy Research

The overall objective of the GAFT project is to contribute to accelerated implementation of liquid biofuels production in Norway. Particular attention is paid to feedstock mixing and torrefaction of challenging biomass enabling entrained flow (EF) gasification, EF gasification technology development and medium scale Fischer-Tropsch synthesis (FTS) development based on synthetic gas from the EF gasifier.

Pulp and Paper Industry Wastes to Fuel - SINTEF Industry

Staff: Senior Research Scientist Bjørn Christian Enger, Research Scientists Rune Myrstad, Håkon Bergem, Julian Richard Tolchard

Project Category: EU Horizon 2020. Project Coordinator: CEA Liten

The Pulp&Fuel concept is to develop a simple and robust fuel synthesis process taking advantage of the synergy between super critical water gasification (wet gasification) and fixed bed gasification (dry gasification). 

Biofuels from waste to road transport - SINTEF Industry

Staff: Senior Research Scientist Rune Lødeng, Research Scientists Håkon Bergem and Roman Tschenscher, Anette Mathiesen

Project Category: EU Horizon 2020, "Development of next generation biofuel and alternative renewable fuel technologies for read transport", Project Coordinator: SINTEF Industry 

The main objectives of Water2Road are to develop a representative and cost-effective waste supply and management system to reduce and optimize the supply costs while diversifying the biomass feedstock basis and to develop new biofuels production technilogy while increasing understanding and control of the whole value chain. 

Upgraded scenarios for integration of biofuel value chains into refinery processes - SINTEF Industry

Staff: Senior Research Scientist Rune Lødeng, Research Scientists Håkon Bergem and Roman Tschenscher

Project Category: EU Horizon 2020, "Development of next generation biofuel technologies", Project Coordinator: SINTEF Industry

The main objectives of 4REFINERY are to develop new biofuels production technology while at the same time increase understanding and control of the entire value chain, to scale up materials and testing procedures to define scenarios for the best further implementation in existing refineries, to develop solutions to answer key societal and environmental challenges.

Environmental Catalysis - 3 on-going projects

Design of low-cost and carbon-resistant Ni-based mesoporous silicas for chemical CO₂ utilization through tri-reforming of methane, Marie Skłodowska Curie - Individual Fellowship, Horizon 2020, EU project

Researcher: Katarzyna Swirk; Supervisor: prof. Magnus Rønning. 

The process of carbon capture and utilization has been gaining attention as a potential strategy to significantly reduce greenhouse gas emissions from major industrial emitters. Tri-reforming of methane is viewed as a part of these technologies. Not only does the process produce synthesis gas with the desired ratios of hydrogen–carbon monoxide, but it also eliminates carbon formation – a serious concern in methane reforming. Furthermore, the process allows direct CO₂ conversion from flue gases when applied in natural gas-fired power plants. Lack of efficient catalysts has prevented the tri-reforming of methane from making a bigger impact. The EU-funded MesoSi-CO₂ project (Marie Skłodowska Curie - Individual Fellowship, Horizon 2020) plans to design efficient nickel-based catalysts supported on mesoporous silica. For their synthesis, the project will take advantage of renewable bio-sources, zero-cost industrial waste, and microwave technology.

Kinetic Studies of aqueous phase reforming, BIKE, EU project

PhD student: Monica Pazos Urrea; Supervisor: prof. Magnus Rønning. 

The project is part of the BIKE EU-project. BIKE - Bimetallic Catalysts knowledge-based development for energy applications - is a MSCA-ITA project involving 17 European partners. The main objective is to train young scientists to master and combine various state-of-the-art methodologies for rational development of bimetallic catalysts to improve the current processes of renewable raw materials conversion to Hydrogen and to implement them in an industrial context. Aqueous phase reforming (APR) is an alternative to the traditional steam reforming since it can be used to convert streams of low-value mixed to H₂/CO₂.

An R&D base for reduced exhaust emissions in the Norwegian maritime transportation sector - SINTEF Industry

Staff: Senior Research Scientist Rune Lødeng

Project Category: Research council of Norway, Project Leader: Prof. Hilde J. Venvik

The proposed project targets new knowledge and innovation for emissions abatement, more speficially nitrogen oxides (NO_x) and methane (CH₄) in the marine sector. It is a collaboration project between NTNU and SINTEF. NTNU is focused on selective catalytic reduction (see above) and SINTEF is focusing on methane abatement for natural gas engines in the marine sector.

Fundamental Studies of Heterogeneous Catalysis

Several experimental techniques are used to study the details of solid catalysts. We are working together with Department of Physics on the use of Transmission Electron Microscopy and Scanning Tunnelling Microscopy. We focus on characterisation of catalysts at working conditions (in situ characterisation) and for this purpose we are using the European Synchrotron Radiation Facility in Grenoble. We have in-house facilities for in situ IR and Raman spectroscopy. Steady State Isotopic Transient Kinetic Analysis (SSITKA) and the Tapered Element Oscillating Microbalance (TEOM) are powerful techniques for studying important phenomena such as reaction kinetics, mechanisms, catalyst deactivation, diffusion in porous materials and adsorption, absorption and desorption.

In-situ analysis of industrial catalytic reactions using a novel ISMA - iCSI Center, NFR project

PhD student: Björn Baumgarten

Master student 2021/22: Muhammad Arslan Aslam

Supervisors: associate prof. Jia Yang, Senior Researcher Rune Lødeng (SINTEF Industry)

An ISMA is a fixed-bed reactor, but with the added ability to measure the weight of the catalyst bed during reaction. The reactor tube is oscillating, and the frequency is depending on the mass. Thus, the mass of the catalyst can be recorded in real time during the reaction. For many industrial reactions, the formation of coke (or other deposits) is a relevant side reaction which leads to deactivation of the catalyst. With the ISMA, deposition kinetics (i.e., the weight change of the catalyst) and deactivation kinetics (decrease of yield) can be investigated simultaneously. In addition, sorption processes can be investigated. To evaluate the ISMA, CO₂ hydrogenation to Methanol, coupled with Methanol to Olefins, will be tested. CO₂ hydrogenation currently receives much attention, as it is an opportunity to reduce the requirement of fossil fuel by converting it into green fuel, or to store CO₂ e.g. when turned into green plastics.

Transmission electron microscopy characterisation of catalysts - iCSI Center, NFR project

Researcher: Tina Bergh 

Advisor: prof. Hilde J. Venvik

Tina characterises materials from micrometre to atomic scale, using electron microscopy, primarily transmission electron microscopy (TEM). TEM techniques include various imaging, diffraction, and spectroscopy techniques, which enable studying the morphologies, crystal structures and chemical compositions of thin specimens. Tina is partly employed within the centre iCSI, where she contributes to better understanding of various catalyst materials. For instance, she is currently studying silver used as a catalyst in the methanol to formaldehyde reaction.

Insights into the kinetics and mechanism of selected industrial catalyzed reactions - iCSI Center, NFR project

PhD student: Moses Mawanga; Supervisors: prof. Edd Blekkan, associate prof. Jia Yang

The goal of the proejct is to conduct mechanistic and kinetic studies in the transient regimes to provide fundamental experimental data for some selected industrial catalyzed reactions. This approach will guarantee the qualitative and quantitative determination of the composition of adsorbed surface species during the reaction and provide information on the sequanece of elementary steps that govern the global reaction kinetic rate. The project is comprised of two parts:

Part I entails the investigation of intrinsic kinetics of the oxidation reaction of nitric oxide; a reaction that is fundamental to the Ostwald process. Supported platinum manganese-based catalysts as well as peroskites will be tested to understand the structure-activity dependence of the catalytic system to understand the mechanism (Mars van Krevelen/Eley-Rideal/ Langmuir-Hinshelwood type) by which the catalyst functions in converting nitric oxide to dioxide. More so, the combined SSITKA-FTIR setup will also help to discriminate between the reactant species as well as spectator species on the catalyst surface. 

Part II involves using the adsorption microcalorimetry to measure the heats of adsorption for catalytic activation and functionalization o light alkanes, e.g. using zeolites or copper-based catalysts. Heats of adsorption are indicative of the adsorption energetics and bonding strength of surface species to probe the nature of active sites of the catalyst. With these fundamental experimental data, it will be possible to have a better understanding of the catalytic reactions and thereby use the data for better catalyst design.

Advanced in situ characterization of heterogeneous catalysts for sustainable process industries - iCSI Center, NFR project

PhD student: Samuel K. Regli; Supervisor: prof. Magnus Rønning

This PhD project is part of the industrial Catalysis Science and Innovation (iCSI) Center. We are investigation heterogeneous catalysts during operation at industrially relevant conditions and develop the necessary data analysis tools as neede. In order to link structural properties of the material with catalytic activity during reaction, we apply spectroscopy (Infrared, X-ray, UV-Vis) in-house and at synchrotrons. We have synergies with four out of the six work packages within iCSI and collaboration within KinCat (Fe-based Fischer-Tropsch synthesis to olefins from renewable feedstocks and selective catalytic reduction of No by ammonia over Cu-based catalysts), but also with SUNCAT in Stanford (Hydrogenation of CO and CO2 to Methanol). 

Nanoscale Investigation of Co(0001), Co(10-12) and Co(11-20) Single Crystals as Catalyst Model Systems: Insights from Experiment and Theory

Researchers: Mehdi Mahmoodinia; Senior: prof. Hilde J. Venvik

Single crystals provide model systems that can further the understanding of phenomena occuring at the surface of a catalyst e.g. adsorption/desorption, reaction, surface segregation, reconstruction, promotion and poisoning. Understanding the dynamic surface of a cobalt (Co)-based Fischer Tropsch (FT) catalyst motivated the work with the Co single crystals.
In the Co-based Fischer-Tropsch synthesis (FTS) reaction, the carbon and oxygen atoms of the CO precursor molecule react with surface hydrogen atoms to form C_xH_y and H₂O. The idea is to increase the selectivity of this reaction in order to produce long chain aliphatic hydrocarbons at relatively low temperature, around or below 500 K. The active phase of industrially applied cobalt catalysts consists of metallic nanoparticles, which expose a heterogeneous surface with a large variety of active sites (corners, edges, steps, kinks, reconstruction). Therefore, a fundamental understanding of the adsorbates on different Co surfaces and the elementary reaction steps involved is an essential tool for catalyst design and optimization in the FT synthesis. Three different single crystal surfaces of cobalt were used to address this question: Co(0001), Co(10-12) and Co(11-20). A combination of density functional theory (DFT) study, temperature programmed desorption (TPD) and low electron energy diffraction experiments in collaboration with SynCat@DIFFER research lab in Eindhoven, the Netherlands, have been used to gain insight into the structure of cobalt surfaces upon adsorption of H₂ and CO and to study the adsorption strength of hydrogen atoms or CO as a function of surface structure and surface coverage.

Microstructured Reactors and Membrane Reactors

Hydrogen Membrane Technology

PhD student: Junbo Yu; Supervisor: prof. Hilde J. Venvik

This PhD project is a part of H2MemX project. H2MemX targets unprecedented insight into surface phenomena critical to the performance of Pd based membranes for hydrogen separation as a basis for developing sustainablem environmentally friendly and cost effective H₂ production. In the PhD project, the surface chemistry of sputtered Pd-alloy membranes of relevant binary and/or ternary mixtures under different conditions (Temperautre and Pressure) will be focused on. The long-term stability and durability of the membrane under industrially relevant conditions during cycling will also be studied. Moreover the effect of heat treatment in air (HTA) procedure on hydrgene permeation and CO inhibition will be investigated.

Kinetic Study of Bimetallic Catalysts for Compact Steam Reformer

PhD student: Shirley Liland; Supervisor: prof. De Chen

Today the preferred route to chemicals and liquid fuels are through synthesis gas, where synthesis gas production accounts for at least 60% of the total plant investment. The production is most commonly performed by the steam reforming (SR) process. A possibility for reducing the costs will be to achieve a small scale GTL (gas to liquid) process using a microchannel reactor.
The goal for this project is to develop a new microchannel reactor to achieve the maximum volumetric productivity. This will be accomplished through optimization of the integration of combustion and steam reforming processes, including development of advanced catalysts for both processes. Reactor modeling and analysis will be utilized to analyze how to achieve the maximum heat flux between the two adjunct channels, which will limit the maximum reaction rate of steam reforming. An advantage of the microchannel reactor is that it can be further integrated into compact Fischer-Tropsch reactors. In the microchannel reactor the SR reaction (endothermic, outer channel) will get energy supplied as heat from a combustion reaction (exothermic, inner channel).

Production and Application of Carbon Nanomaterials, Carbon Nanofibers, Nanotubes and Graphene

Cobalt Catalyzed Fischer-Tropsch Synthesis: Systematic Studies on Carbon Support Effects on Catalyst Activity and Deactivation, BIKE, EU Project

One of the most fundamental problems of Cobalt based catalysts for Fischer-Tropsch synthesis (FTS) is their rapid deactivation, owing to re-oxidation of Co⁰ and sintering, e. g., the reduction of the active surface area of Co nanoparticles. In terms of deactivation-resistant Co catalysts, the catalyst support is a key component: In addition to increasing the active Co surface area by dispersion, it promotes reducibility while stabilizing the active nanoparticles against deactivation by sintering. In this context, carbon represents an attractive support, as carbon materials are characterized by high surface areas, chemical inertness, and almost unlimited possibilities for the targeted manipulation of structure and surface chemistry. However, due to the large number of influencing factors, the impact of individual support properties (e. g. crystallinity, texture, surface chemistry) on catalytic performance and deactivation behavior of Co based FTS catalysts remains opaque. Against this background, we work on a systematic approach to disentangle carbon support effects on catalyst performance and catalyst deactivation. In this context, the influence of carbon structure, surface oxides, and heteroatom doping will be studied in isolation and without interference from Co-particle size effects.

Carbon Nanomaterial-Ionic Liquid Hybrid for Ultrahigh Energy Supercapacitor

PhD student: Daniel Skodvin; Supervisor: prof. De Chen

The desire to use more renewable energy has made energy storage and conversion one of the greatest challenges in today’s society. Energy needs to be stored more efficiently, thus improvements in the energy density of supercapacitors (SCs) should be achieved in order to meet today’s requirements. In this research, mesoporous carbon nanospheres are synthesized and used as electrode material in SCs using ionic liquids. The main objective is to develop SCs with high energy density (> 80 Wh/kg) and specific power (> 10 kW/kg). In addition, a high specific capacitance of 600 F/g should be realized using an operating voltage window of 4 V. This could be achieved by maximizing the ion packing density in the nanopores. In addition, the amount of mesopores in the carbon materials should be maximized, since mesopores provide low resistance during ion transport. Mesoporous carbon materials should have high specific surface areas (> 3000 m²/g) and pore volumes (> 2 cm³/g), which will provide a high ion packing ability. This could be realized by a careful study of the activation procedure, where several activating agents, including CO₂, ammonia and steam, will be used in order to optimize the pore size distribution of the carbon material.
To date, a maximum specific capacitance of 300 F/g using an operating voltage window of 4 V has been achieved in this work. Addition of TMABF4, TEABF4 or smaller cations like Li⁺, Na⁺, Mg²⁺ or Zn²⁺ to the ionic liquid, could be a promising method to further enhance the capacitance. Achieving these goals would enable a wide application range in the energy sector and improve renewable energy storage and conversion. This project could promote the use of renewable energy in the public transportation sector.

Development of stable Cu/C catalysts for selective hydrogenation of hydroxyacetone to 1.2-propanediol, Bio4Fuels Centre, NFR Project

PhD student: Martina Cazzolaro; Supervisor: prof. De Chen

Various biomass-based processes lead to the production of hydroxyacetone (HA), i.e. biomass pyrolysis, sugar hydrogenolysis, glycerol dehydration. Via selective hydrogenation of HA, a major commodity chemical as 1,2-propanediol (PD) can be produced. Cu-based catalysts showed good activity in hydro-deoxygenation of bio-oil from biomass pyrolysis, but coke formation resulted in shortened catalyst lifetime. High activity was also observed in hydrogenolysis of glycerol to PD, having HA as dehydration intermediate: Cu particle size, dispersion and active area were reported to be of great importance for high activity and stability; particles agglomeration and formation of irregularly shaped clusters were suggested as deactivation causes. Carbon nanofibers (CNF) are attractive catalyst supports having high surface area and large number of edges, exploitable as metals anchoring sites. Moreover, surface oxidation, foreign-ion doping or confinement effect can be used to adjust CNF surface properties. This project aims to develop a stable Cu-based catalyst for selective gas-phase hydrogenation of HA to PD, by tuning the carbon support properties.

Gas Cleaning

Synthesis of Low Temperature Carbon Dioxide Adsorbents, CLIMIT program, NFR project

PhD student: Dumitrita Spinu; Supervisor: prof. De Chen

Co-supervisor: Adjunct Prof. Kumar Ranjan Rout

It is well-known that the largest amount of CO₂ emissions comes from fossil fuel power plants, and because of its destructive effect on the global climate, urgent actions must be considered. One of it is CO₂ capture and storage (CCS) which is an intensively researched area aimed at mitigating the CO₂ release into atmosphere. Due to the increase of total natural gas/coal generated electrical power ratio, the project scope is focused on designing CO₂ sorbents for post-combustion natural gas combined cycle (NGCC) power plants. In addition, a cost-effective retrofit can be implemented for the existing power plants.

Various technologies and materials have been developed and investigated, especially the aqueous alkanolamines scrubbing of CO₂. However, the large water content used in this process rises the energy consumption amount, and the direct contact of the amine solution with the equipment requires anti-corrosive materials which are very expensive. Accordingly, amine functionalized solid sorbents are proposed for this project. By anchoring the amine containing material on the pore surface of the support, the amine-equipment contact is avoided. Furthermore, less energy is consumed because no water is involved in the chemisorption process. If comparing with the monoethanolamine NGCC integrated process, a cost saving of 25-30% is estimated by using solid sorbents.

Nevertheless, the amine functionalized solid adsorbents have also some drawbacks like reduced capacity at low CO₂ partial pressure and low chemical and thermal stability. Herein, polyethyleneimine (PEI) and penthaethylenehexamine (PEHA) are planned to be used as the active material for chemisorption. They are described by a very high amine density, an important property required to achieve a high CO₂ adsorption capacity. Moreover, their large molecular weight, especially the one of PEI, increases their resistance to high adsorption-desorption temperatures. However, a very high molecular weight is unwanted because it is difficult to impregnate into the pores. Furthermore, a highly viscous material also involves a very hydrogen bonded environment which minimizes the CO₂ diffusion to the amine sites. The diffusion is also decreased by the high amine loadings. In order to develop large loadings, supports with enough pore volume and pore size are required. In this work, silica supports are used due to their thermal and mechanical stability. The crosslinking and support bonding of amines concepts are also considered in order to avoid amine loss.

The kinetical and performance investigations are already in progress. This year, two master students, Yun Liu and Jørgen Grinna, joined our project. Yun studies the silica supports synthesis method and their physical properties effect on the PEI loading and performance. Jørgen works on the kinetic model of CO₂ adsorption on PEI.

In order to store pure CO₂, the adsorption process should be very selective, and the desorption step should be realized in pure CO₂. As the process is designed based on temperature swing adsorption, a desorption step in pure CO₂ and high temperature deactivate very fast the amines because of the ureas formation. Secondary amines manifest a quite high resistance towards this type of deactivation, thus a process of converting of primary amines into secondary will be considered. Moreover, the deactivation mechanism will be developed.

The major problem of amine containing materials is their high sensitivity to oxygen. As these materials contain also carbon, the formation of C-O radicals will easily imply the amine group deactivation, especially if the materials or the adsorption environment contain metals like iron or copper, which speed up the radicals’ formation. This problem will be tackled in different ways, considering different antioxidants and amine’s modifications. Furthermore, the adsorption conditions will be optimized in order to slow down the radicals’ formation process.

Moving Bed Carbonate Looping (MBCL), in collaboration with Fjell Technology Group (FTG)

Researcher: Ainara Moral

Advisors: Prof. De Chen Kumar R. Rout; Torleif Madsen, Asbjørn Strand (FTG)

An innovative moving bed reactor (MBR) is proposed in the MBCL project Phase I: one or more mass transfer regions are arranged such that the solid reactant is retained within the one of more mass transfer regions as the solid reactant flows through the mass transfer system and the mass transfer between the gas and the solid reactant occurs in the one or more mass transfer regions. Extensive research has been done before in order to produce a cost efficient chemically and mechniacally stable solid sorbent including our effort to our previous patent (NTNU). For the 420MW power plant we need 80ton of solid inventory to capture 85% of CO2. The reported solid sorbent cost varies from 2800-4600 USB/ton, which is not feasible for the CCS scenario at an industrial scale. Therefore, effort is made in the MBCL phase I to produce chemically stable doped dolomite solid sorbent by utilizing our doped dolomite cost around 750 USD/ton.

Further advanced characterization of developed doped dolomite solid sorbent pellets is needed and proposed in the MBCL Phase II. Apart from this, a proper kinetic study needs to be done in order to develop kinetic model, which will be implemented in MBCL hot (numeric) reactor model that will be developed in the Phase II. Cold flow MBCL reactor consists of multi-channel carbonator, calciner MBR and riser will be build in the proposed MBCL phase II, equil to the hot rig design.

In parallel to the technilogical process, the project will start a process for commercialization. There will be identified and selected potential partners, increasing ressources for the next phases.

Photocatalysis

Gold-Bismutite Hybrid Catalysts for Photosynthesis of Ammonia

PhD student: Jibin Antony; Supervisor: prof. Magnus Rønning

Master student 2021/22: Leo Gräber

Co-supervisor: Dr. Sulalit Bandyupadhyay and Ass. Prof. Jia Yang

Ammonia is one of the most important chemicals for the industrial production of fertilizers, pharmaceuticals, and many other nitrogenous compounds [1]. The industrial production of ammonia takes place via the Haber-Bosch process, which requires high temperature and pressure (typically 400-500°C and 200 atm), thereby making it an energy intensive process. This accounts for 1-2% of the world’s energy consumption and approximately 5% of the world’s natural gas production [1]. The current global production of ammonia is estimated to be around 200 million tons per annum, which accounts for more than 1.6% of global CO2 emissions [2]. This calls for a pressing need for an alternative greener synthesis route for NH₃ production.

The conversion of N₂ to NH₃ in nature at ambient conditions by the nitrogenase enzyme motivates the search for similar sustainable technologies for industrial scale NH₃ production. Photocatalytic ammonia production is one such field gaining popularity owing to the mild reaction conditions at which it allows the reduction of N₂ to NH₃. Bismutite (Bi₂O₂CO₃) nanoparticles (NPs) have recently emerged as an important candidate in photocatalysis owing to the alternative (Bi₂O₂)²⁺ and CO₃^2- layered anisotropic crystal structure, which leads to an internal static electric field thereby facilitating photoinduced charge separation and transfer [1]. However, these NPs have a relatively wide bandgap (~ 3.15 eV) which limits its performance in the visible region of the solar spectrum. Furthermore, the high stability of the N₂ molecule with a bond strength of 941 kJ.mol^-1, makes the activation step of N₂ quite challenging at these conditions [3]. Hence, the development of highly efficient photocatalytic materials with improved light harnessing properties have garnered significant research interest.

Au NPs, owing to their excellent optical properties and localized surface plasmon resonance (LSPR) effect, have emerged as attractive candidates for catalysis and other applications. As a result of the LSPR effect, enhanced field strength of the electromagnetic fields near the surface of Au NPs can be over 500 times larger than the applied field for structures with sharp edges [4]. This may cause heating of the NPs by just absorbing sunlight, which could in turn activate the molecules bonded to the surface. Hence plasmon enhanced photocatalysis would improve the solar energy collection efficiency of semiconductors and is expected to give better yields of ammonia. Recent work by Xiao et al. reported chemical bath deposition of Au NPs on bismutite and studied the same for photocatalytic ammonia synthesis [1]. However, controlling the morphologies of Au NPs is an area that has not yet been explored, and is expected to have a significant effect on the photocatalytic performance.

This project aims at synthesizing hybrid NPs of Au with bismutite and to study their performance in photocatalytic ammonia production. Various shapes of bismutite NPs such as disks and 3D stacked structures will be synthesized using a facile hydrothermal method. Au NPs will be deposited on the bismutite NPs via different approaches such as photodeposition, ultrasonication and seed-mediated growth in the presence of cetrimonium bromide (CTAB) as surfactant. The photocatalytic performance of the hybrid catalysts will be studied in the presence of methanol as sacrificial agent under simulated solar light. A 300W Xenon arc lamp equipped with AM1.5 filter will be used to irradiate the reactor under N2 purging with 1 sun radiation. Careful optimization of the synthesis route for these Au-bismutite hybrids is anticipated to pave way for a greener and energy efficient photosynthesis of ammonia.

[1] C. Xiao, H. Hu, X. Zhang and D. R. MacFarlane, ACS Sustainable Chemistry Engineering, 2017, 5,10858-10863.

[2] S. Zhang, Y. Zhao, R. Shi, G. I. Waterhouse and T. Zhang, EnergyChem, 2019, 100013.

[3] D. Kumar, S. Pal and S. Krishnamurty, Physical Chemistry Chemical Physics, 2016, 18, 27721-27727.

[4] X. Chen, H. Y. Zhu, J. C. Zhao, Z. F. Zheng and X. P. Gao, Angewandte Chemie International Edition, 2008, 47, 5353-5356.

Refinery Operations

Hydrotreating - SINTEF Industry

Staff: Research Scientist Håkon Bergem, Senior Engineer Camilla Otterlei, Professor Edd A. Blekkan

The project aims to improve the performance of the client's commercial hydrotreating units. The staff is involved in research in aiming at developing new and better catalysts but also process optimization and modeling based on insight into the detailed mechanisms of the actual reactions.

Octane Processes - SINTEF Industry

Staff: Research Scientist Hilde Bjørkan, Senior Engineer Camilla Otterlei, Senior Scientist Torbjørn Gjervan

Client: Equinor ASA

The project aims to improve the performance of the client's commercial catalytic reforming and isomerisation units. The heart of the proejct is a small-scale pilot unit, but additional chemical or physical characterization tools are used as well.

Natural Gas Conversion

Benchmarking low temperature shift catalysts - SINTEF Industry

Staff: Senior Scientist Bjørn Christian Enger, Research Scientist Rune Myrstad

Client: Borealis

The goal of this project is to support the client's efforts in selecting catalysts for gas conditioning. This involves testing of commercial catalysts using the client's conditions and analysis of gaseous and liquid products.

Natural gas is an abundant hydrocarbon fuel and chemical feedstock, and utilizing this resource with minimum environmental impact is a major challenge to catalysis. It is the main goal of the present programme to study catalytic processes for conversion of natural gas to chemicals and fuels including hydrogen. The programme includes production of synthesis gas, Fischer-Tropsch synthesis, and dehydrogenation of C₂-C₄ alkanes. The work is carried out in close collaboration with international industry and SIN

Exchange Students 2021

PhD Student: Yurou Li - 1 year from September 2021

PhD Student: Aldo Lanza - 2 months from June 2021

PhD Student: Consolato Rosmini - 2 months from February 2021