Industrial Catalysis

Research Areas

Industrial Catalysis

Low temperature selective hydrogenation using noble metal catalysts

In collaboration with GE, SINTEF Industry

Master student 2019/20: Ingvill Andrea Røed

Supervisors: prof. Magnus Rønning, Senior Researcher Rune Lødeng (SINTEF)

Carbon formation and catalysis in the conversion of methyl chloride and silicon into dimethyldichlorosilane

In collaboration with Elkem – Bluestar

Master student 2019/20: Hammad Farooq

Researcher: Mehdi Mahmoodinia

Supervisors: prof. Hilde J. Venvik, prof. Edd Blekkan

Promoter Effects on Ethylene oxychlorination reaction for CuCl2/gamma-Al2O3 based catalysts

PhD student: Endre Fenes; Supervisor: prof. De Chen

Co-supervisor: Industry Researcher Terje Fuglerud, INOVYN

The ethylene oxychlorination process produces ethylene dichloride (EDC). EDC is a precursor in the production of poly-vinyl chloride; one of the most commonly used polymers throughout the world. The process is catalyzed by CuCl2/γ-Al2O3 based catalysts and consists of three distinct reaction steps in which copper cycles between Cu2+ and Cu1+ oxidation states: catalyst reduction by ethylene, consuming chlorine from the catalyst, catalyst oxidation and at last, catalyst hydrochlorination.
In this project, the effect of promotors, i.e., mostly alkali, alkali earth and lanthanide elements on turnover frequency, catalytic activity, selectivity and stability is investigated with an operando study, combining mass- and UV-Vis-NIR spectrometry during both transient and steady state experiments.


Impact of promoters on ethylene oxychlorination catalyst

PhD student: Hongfei Ma; Supervisor: prof. De Chen

Master student 2019/20: Jithin Gopakumar

Vinyl chloride monomer (VCM) is the monomer from which poly vinyl chloride (PVC) is made. PVC is one of the most commonly used plastics and has a wide range of applications in our daily life, for example in construction materials, clothe, electronics. This is largely due to the ability to modify the properties of the substance using dopants, for example to alter its rigidity. As a result, there is a high demand for the plastic, with over 40 million tons of PVC produced every year, leading to VCM being a very valuable chemical. VCM is produced from ethylene and chlorine in a process involving several conversion steps. Oxychlorination of ethylene, where ethylene dichloride (EDC) is formed from ethylene, HCl and oxygen in a catalytic gas phase reactor, is used to recycle the HCl formed in EDC cracking. In addition, the selective chlorination and hydrogenation are used actively to control the composition of process streams with the aim of improving process efficiency and reduce fouling process equipment.

Investigations of the methanol to formaldehyde (MTF) reaction over silver

PhD student: Stine Lervold; Supervisor: prof. Hilde J. Venvik

Master student 2019/20: Susanne Klungland Stokkevåg

Formaldehyde is the essential component of wood adhesives for a wide range of applications and an important intermediate in the production of several fine chemicals. Formaldehyde is produced via selective catalytic oxidation of methanol to formaldehyde. Industrially, production of formaldehyde from methanol is performed via two main processes: either partial oxidation over a silver catalyst or oxidation in excess air over base metal oxides. Dynea owns both technologies and recognizes an economic potential for the silver-based process with the main objective to improve the yield and lifetime of the silver catalyst. The PhD project focuses on kinetic experiments that can be linked to the surface structure and composition of the Ag catalyst. Initial activities have concerned the development of experimental protocols that allow extraction of kinetic data in the experimental setup, including specific reactor designs.

Biofuels


Biofuels

Bio-Ethanol steam reforming for on board hydrogen generation system

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

Researcher: Nikolaos Tsakoumis

Master student 2019/20: Eirik Søreide Hansen 

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.

 

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

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

Master student 2019/20: Julie Christine Claussen

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.

Biomass to Liquid Fuels - Steam Reforming of Tar and Methane from Biomass Gasification

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

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

 

Bio Fischer-Tropsch (BioFT)-Staging and Multiple Hydrogen Feed of Biomass to Fischer-Tropsch Fuel Synthesis

Postdoc: Ljubisa Gavrilovic; Senior: prof. Edd Blekkan

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

Fischer-Tropsch kinetic study where effects of H2-CO ratio, Temperature, CO conversion and water on activity and selectivity of the cobalt based catalyst are investigated. Catalyst deactivation is studient and described. Effect of staging and subsequent H2 addition on Hydrocabon selectivity of the Cobalt FTS catalyst is investigated. The experimental data re-fitted in the updated model covering all the aspects. 

 

Conversion of lignocellulosic waste into biofuels and bioplastics

Postdoc: Zhenping Cai; Senior: prof. De Chen

Master students 2019/20: Petter Tingelstad, Kishore Rajendran

The dwindling of petroleum resources and global environment problem have forced a rethink on the continued use of fossil fuels and focus on renewable resources valorization such as lignocellulosic biomass, which is expected to be the most promising feedstock owing that it does not increase the level of CO2 in the atmosphere and wide abundance. To date, bench-scale depolymerization technologies such as pyrolysis, gasification, liquefaction, and hydrogenolysis have been shown to convert biomass into bio-oil and value-added chemicals.
Lactic acid, an industrially important chemical widely used in food, pharmaceutical, and bioplastics, can be catalytically produced from several feedstocks, such as biomass, cellulose and sugars. Both heterogeneous and homogeneous catalysts have been employed to catalyze the reactions. For example, metal ions have been used to produce directly from lignocellulosic biomass under subcritical water. And several types of heterogeneous catalysts such as zeolites, sulfonated carbon, sulfated zirconia, tungstated alumina, and heteropolyacids was also investigated. However, the low yield and selectivity with harsh reaction conditions limit the commercialization of this chemical route. As a result, development of novel efficient catalysts for selective conversion biomass and cellulose into lactic acid should be paid much attention. In this project, we focus on the direct production of lactic acid as the feedstock of bioplastics. Global consumption of bioplastics for packaging is projected to grow to just over 2 million tons by 2020, with a market value of almost $5 billion. In particular, polylactic acid (PLA) is a transparent plastic and biodegradable polymer which is used in the plastic processing industry for the production of films, fibers, plastic containers, cups and bottles. Moreover, the use of low cost biomass as feedstock for PLA generation makes our process economically viable. Here, we proposed a series of novel single-site tungsten oxide supported catalysts for conversion of cellulose into lactic acid directly.

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, Kumar Ranjan Rout

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


Environmental Catalysis

Kinetic Studies of aqueous phase reforming

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.

Production of olefins from waste plastics

Master student 2019/20: Vilde Vinnes Jacobsen; Supervisor: prof. De Chen

There is an increasing demanding of plastics in many sectors and the global plastic production is expected to increase over years. However, it has caused the plastic wastes accumulation in the landfill consumed a lot of spaces that contributed to the environmental problem. This project is concerning the conversion of waste plastic to base chemicals such as olefins. There will be performed a pyrolysis of the plastics and a catalytic upgrading of the pyrolysis vapors with the Zeolite ZSM-5 as catalyst.

Catalysts for NOx-reduction in maritime transportation

PhD student: Ole Håvik Bjørkedal; Supervisor: prof. Magnus Rønning

In most chemical processes, from internal combustion engines to industrial process plants, we have to account for environmental pollutants generated in the process, and hinder these from reaching the atmosphere. Examples of such compounds are nitrogen oxides (NOx), sulphur oxides (SOx), hydrocarbons, volatile organic compounds (VOCs) and particulates. Catalytic abatement technology seeks to prevent or reduce the emission of such compounds by converting them to inert molecules that can be released into the air.

Chemical processes, engines and other technological solutions are continuosly being developed and introduced in our society, often close to densely populated urban areas where environmental pollution has severe impact. Relevant, reliable and efficient emission abatement technology is therefore required, and have to be developed to satisfy a wide range of standards and operating conditions.

x-conversion and Methane oxidation catalysts to prevent methane emissions. These catalysts are, and will still be a cornerstone for a sustainable industry and society in the future.

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 (NOx) 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


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.

Insights into the kinetics and mechanism of selected industrial catalyzed reactions

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

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). 

Fundamental study of CuCl2/g-alumina catalyzed ethylene oxychlorination and methanol oxidation

Postdoc: Yanying Qi; Senior: prof. De Chen

Ethylene oxychlorination is an important step in the industrial production of vinyl chloride monomer (VCM), which is needed for polyvinyl chloride (PVC) production. CuCl2/ γ-Al2O3 based catalysts are effective to catalyze ethylene, HCl and oxygen to produce 1,2-dichloroethane (EDC) in this process. In this project, we performed DFT calculations to investigate the nature of active phase and to understand the promoter effect.
We built a new model to present CuCl2 supported on γ-Al2O3. The new model involves the contribution of support, which is more close to the real catalyst compared with the previous model (i.e, CuCl2 surface). Based on the new model, the adsorption behaviors of ethylene at different loadings were investigated. Distinct adsorption modes at high loadings and low loadings were observed and the underlying reason was discovered by the analysis of the electron properties, such as Bader charge analysis.

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, Marie Døvre Strømsheim; 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 CxHy 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.

Advanced characterization of Pd-based membrane model systems

Researcher: Marie Døvre Strømsheim

The postdoctoral work is part of the H2MemX-project, a joint effort between NTNU and SINTEF, and in cooperation with Lund University/the MAXIV Laboratory, to advance the understanding of Pd-based membranes for hydrogen separation from gas mixtures. Further knowledge of these membranes is desirable as they may enable the production of high purity hydrogen regardless of the feedstock (biomass, natural gas). The specific focus of the postdoctoral project is the investigation of the surface chemistry and segregation phenomena of the Pd-alloy membranes/model systems (i.e. single crystals), under conditions as near as possible to application. The overall aim is to apply the insight of segregation phenomena and changes in surface chemistry and composition under these conditions towards tuning membrane performance and stability. The Pd/Pd-alloy membranes are manufactured by SINTEF through a two-step sputtering method of the desired Pd and alloy material on to a Si substrate. This method allows for easy separation of the membrane from the substrate and application to a wide range of support configurations, as well as control of the thickness and composition of the resulting membranes.

Microstructured Reactors and Membrane Reactors


Microstructured Reactors and Membrane Reactors

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).

Material degradation by metal dusting corrosion in compact reformer concepts

PhD student: Xiaoyang Guo; Supervisor: prof. Hilde J. Venvik

Metal dusting is a corrosive degradation phenomenon on metals and alloys that proceeds by a gradual breakdown of the material into fine particles. It constitutes a problem in the chemical industries, where metals and alloys are extensively exposed to carbon-supersaturated gaseous with low partial pressures of oxygen and/or steam in a critical temperature range of 300–850 ˚C. Metal dusting carries significant cost, since certain precautions are needed to avoid catastrophic events. Micro-structured reactors are being developed for process intensification in order to enable safer, more cost-effective and sustainable conversion of natural gas in the small-to-medium scale. Due to the large inner surface area of the reaction volumes and highly integrated heat exchange between reactant and product streams metal dusting becomes a more severe issue than in conventional reactor vessels.

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.

 

Production and Application of Carbon Nanomaterials


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

Carbon Nanomaterial-Ionic Liquid Hybrid for Ultrahigh Energy Supercapacitor

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

Researcher: Suresh Kannan Balasingam

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

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

Master student 2019/20: Maren Wassås Kveinå

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.

Carbon spheres - Supercapacitor

Researcher: Navaneethan Muthuswamy; Senior: prof. De Chen

Gas Cleaning


Gas Cleaning

Chemical Looping Desulfurization

PhD student: Jianyu Ma; Supervisor: prof. Edd Blekkan

Researcher: Mehdi Mahmoodinia; Exchange Master Student: Rodrigo Ortiz Sanchez-Ramos

Bioenergy is a significant contributor to the renewable energy supply in Norway, today mainly used for heating. Syngas from biomass gasification can be used for electricity production or chemical synthesis to produce synthetic fuels. The gas is a complex mixture including H2, CO, H2O, as well as S- containing species, which lead to the formation of H2S or other sulfides that can cause corrosion of downstream equipment and poison catalysts used for fuel synthesis. Hence, removal of sulphur is important for utilizing biomass on energy producing.
The Chemical Looping Desulphurization project (CLD), focuses on using Mn-based high temperature solid sorbent (HTSS) for desulphurization in a novel reactor system. Sulfur removal from the syngas from biomass gasification by HTSS represents a promising and energy efficient method for gas cleaning. Mn-based solid sorbents are promising HTSS for sulfur removal due to their unique chemical properties, and their abundant occurrence and low cost. The aim of the project is to solve key technological issues and placing this technology within the portfolio of cost-effective S capture technologies.
The research topics include development of chemically- and mechanically stable Mn-based HTSS spherical pellets, and developing a kinetic model for sulfurization/de-sulfurization based on a non-catalytic gas-solid reaction mechanism. The work is part of a larger project (collaboration with SINTEF), where the results will be used in developing a new reactor and process for gas cleaning.

Low Temperature CO2 capture

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

Master students 2019/20: Yun Liu, Jørgen Lausund Grinna

Catalytic Methane abatement for natural gas engines

Master student 2019/20: Jon Arve Selnes; Supervisor: prof. Hilde J. Venvik

Moving Bed Carbonate Looping (MBCL), Phase I and II

In collaboration with Fjell Technology Group

Participants: Oscar Ivanez, Ainara Moral, Yuanwei Zhang, Li He, De Chen (NTNU); Kumar R. Rout (SINTEF); 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


Photocatalysis

Gold-Bismutite Hybrid Catalysts for Photosynthesis of Ammonia

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

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 CO32- 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.

 

Enhanced visible light adsorption TiO2 based catalysts for photocatalytic H2 production

PhD student: Muhammad Zubair; Supervisors: Associate prof. Jia Yang, prof. Magnus Rønning

Accelerated environmental pollution on a global scale has drawn attention to the need for totally new environmentally friendly and clean chemical technologies. The application of photocatalysis to reduce toxic agents in air and water by developing catalysts that can utilise clean and abundant solar energy and convert it into useful chemical energy is a promising challenge. Photocatalysts that can operate at ambient temperature without producing harmful by-products are ideal as environmentally sound catalysts. For such systems to be considered in large-scale applications, photocatalytic systems that are able to operate effectively and efficiently using sunlight must be established.

Solar energy, water and N2 from air can be used to produce ammonia. Photocatalytic ammonia synthesis is performed using semiconducting photocatalytic nanomaterials. The photocatalysts can operate at ambient temperature which is ideal for environmentally sound processes.

Hydrogen can be produced by photoinduced reforming of organic compounds, including methane and alcohols. Furthermore, the photoreduction of carbon dioxide into useful chemicals is a desirable prospect. It is essential to convert CO2 into useful substances that are common feedstocks for the production of other chemicals (C2-C3+, alcohols, etc.).

The picture represents flower-structured bismutite particles (Bi2O2CO3) synthesized through a hydrothermal synthesis approach, where bismutite disks have self-assembled to form the desired flower particles. The materials are used for photocatalytic nitrogen fixatio

 

Refinery Operations


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


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

 

Materials Development

 


 

Materials Development

Low Cost Drill Bit for Geothermal Applications

In collaboration and funded by Lyng Drilling, Schlumberger, Norwegian Research Council and the Department of Chemical Engineering, NTNU

Researcher: Xiaoyang Guo with associate prof. Jia Yang, and prof. De Chen

The underlying idea of the project is to reduce the cost of polycristalline diamond compact, PDC, (fixed cutter) drill bits, currently used extensively in the oil and gas industry, to a cost-level that makes them competitive in geothermal applications. The current preferred drill bit types in geothermal applications are roller cone drill bits. These drill bits have a low cost and can drill just about any rock type. The major drawbacks associated with roller cone bits are low drilling speeds (inefficient), low durability (due to moving parts) and low temperature tolerance (due to use of seals).

 

Exchange Students 2020


Exchange Students 2020

Ethanol fuel cells and also the ORR catalysts for fuel cells

PhD student: Nianjun Hou

Oxidation of Propene to Propene oxide over gold catalysts

PhD Student: Gang Wang

Redox catalytic cycle of VOC oxidation and ethylene epoxidation

PhD Student: Wenzhao Fu

XAS study of nanoclusters in electrochemical reaction

PhD Student: Hao Zhang