Background of the ingap Centre of Research-based Innovation within Innovative Natural gas Processes and Products

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1 ANNUAL REPORT 2011

2 Background of the ingap Centre of Research-based Innovation within Innovative Natural gas Processes and Products ingap is one of 14 National Centres of Research-based Innovation, appointed by the Research Council of Norway for a period of 5-8 years, starting in ingap comprises the leading research institutions within catalysis research in Norway; the University of Oslo (UiO), the Norwegian University of Science and Technology (NTNU) and SINTEF. Our industry partners, Borealis, Haldor Topsøe, INEOS and Statoil, are global players within energy and petrochemicals production, a field in which catalysis plays a major role. Catalysis is thus the focal point in our research. ingap s strategy is to establish a cross-disciplinary centre that integrates experiments, theory and technology within the field of catalytic processes related to chemical conversion of natural gas. Each industry partner has defined a process of particular interest to them, and identified technical challenges in these processes which are addressed on a fundamental level in joint industry-institute-academia projects. To support the projects that directly address each of these processes, several fundamental projects have been defined; addressing topics such as synthesis of model materials and methods development. Further, investments are made in instruments and equipment of particular importance for the study of each of the processes. ingap s approach to research-based innovation: Large-scale technical challenges are addressed at the fundamental level, where the insight gained will be used to design improved catalysts and processes. 2 Cover by Senior researcher Børge Holme (SINTEF Materials and Chemistry) AFM (Atomic Force Microscopy) surface of a SAPO-34-crystal. The picture is in phase which gives a shadow effect.

3 Centre vision The ingap Centre vision is: Value creation in natural-gas processes through rational design of processes and products based on atomistic and mechanistic insight in catalyst and reactor parameters under operative conditions Main challenges To combine and further develop our cross-disciplinary resources into research in the international fore-front, thereby improving the visibility and competitive position of all partners To attract highly qualified scientists and students to work in the centre Centre goals The following Centre goals have been defined: To provide advanced methodology and fundamental insight into catalyst technology to industry partners, thereby promoting higher productivity in existing plants, a systematic approach to development of improved catalysts and processes and the basis for creating new natural gas processes and products. Funding and research training of at least 18 PhD students and temporary researchers. At least 80 publications in high-ranked journals, and 80 oral and poster presentations at conferences. Hosting 3 (biannual) International Schools of Catalysis. Personnel exchange (8 man-years) between industry and academia. 3-5 patent applications, of which at least one should be subjected to commercialisation measures. 3

4 Director s report Research plan / strategy Natural gas is Norway s most important natural resource, today and in the foreseeable future. ingap s main goal is to contribute to the competitiveness of chemical conversion processes for natural gas, economically as well as environmentally. This target is achieved by close interaction between industrial companies which are international leaders in segments of petrochemical processes, and research organisations which are specialised in the various aspects of catalysis; the workhorse of petrochemical industry. Fundamental insight in catalyst reaction correlations rely on studies of catalytically active materials under working conditions. In , the main scientific focus of ingap was to construct and further develop equipment and methods for such studies. In , the methods were implemented in the studies of target processes, and in , the first reports came from industry telling that knowledge gained in ingap had helped them improve process performance. Thus, the ultimate goal of the CRI scheme; research-based innovation; was accomplished. Education of candidates with state-of-the-art knowledge of the catalysis field is an important sub-target of ingap. In 2011, the first two ingap doctors were created, one at NTNU, the other at UiO. Both candidates continue to work in ingap-associated projects and coloborate with their former industrial partner with whom they had their ingap traineeships. Two new PhD students started in The mid-term evaluation in 2010 gave ingap excellent score: «ingap has very successfully developed research on natural gas processing in the international frontline and maintains excellent contacts and technology transfer with partner industries. The Centre is led by a dynamic managing director in a way that resulted in excellent cooperation between those involved in ingap research. The evaluation team concludes that it is highly likely that this excellent development will continue during coming years. However, and luckily, the evaluators also pointed to potential improvements, which were mainly in line with our self-assessment: - that the Centre endeavour to expand the facilities for in-situ spectroscopic investigations - that the issue of novel chemistry for catalytic upgrading of natural gas be dealt with at an increased intensity - that the possibilities of PhD students to discuss their research with senior scientists be increased - that the Centre as soon as possible starts planning of how to ensure preservation of cooperation, skills and resources after In 2011, the spectroscopy issue was pursued by the employment of a leading spectroscopist, Prof. Silvia Bordiga, Univiversity of Torino, in a 20 % position at UiO. Furthermore, in-situ cells for FTIR DRIFTS/ATR were installed at NTNU and a strategic project was dedicated to IR spectroscopy at SINTEF. 4

5 The novel chemistry issue was targeted by organising a novel chemistry competition in 2011, and by hiring one PhD students and having two MSc students work on metal-organic framework compounds, and another PhD student to work on metal particle synthesis. The student supervision issue was addressed by the decision to reduce the number of processes under study when Borealis would leave the centre by the end of Furthermore, the host institution (UiO) made a huge contribution by hiring two new, permanent ingap-associated professors; Prof. Anja Olafsen Sjåstad (Materials synthesis) and Assoc. Prof. Stian Svelle (Catalysis). The final issue, planning of the post-ingap period, was undertaken by a catalysis SFF application in 2011, as well as initiating discussions to make a new CRI application in years into the 8 years CRI scheme, ingap is still dynamic, and hungry for more success! Oslo, March 20, 2012 Letter from the Head of the Board Industry impact of ingap One of the main ingap centre goals is: To provide advanced methodology and fundamental insight into catalyst technology to industry partners, thereby promoting higher productivity in existing plants, a systematic approach to development of improved catalysts and processes and the basis for creating new natural gas processes and products. ingap has now been in operation since 2007 and this is a good time for checking status against this important centre goal. The industry partners have quite different types of projects in ingap. Some projects are related to technologies that are in the development phase, some are related to technologies that are in an early phase of commercialization, while other projects are related to technologies that are used in commercial plants today. An evaluation of ingap s industrial contribution needs to be based on this background. A general statement on industrial relevance is found in the report from the mid-term evaluation late 2010: In their presentations the industrial partners indicated that they were very satisfied with the progress made to date and rated interactions and contributions to their organizations very highly. Managing Director 5

6 More specific comments from the industrial parties are summarized in the following. For Statoil, ingap has been an important contribution to fundamental competence development within Gas to Liquids (GTL) technology. This includes improved understanding of both Fischer-Tropsch catalyst technology and material corrosion connected to production of synthesis gas. GTL could be a technology option for future gas fields world-wide, and technology know-how is crucial for developing GTL industry. In addition, the material corrosion competence has been utilized in connection with optimal operation of the methanol plant at Tjeldbergodden. For Haldor Topsøe, the work performed within the ingap framework, has greatly improved the fundamental understanding of the zeolite mediated methanol to hydrocarbons conversion. In particular, the generation of kinetic models has provided the necessary tools to evaluate the performance of catalysts, which is a prerequisite for industrial catalyst development. Exploring the shape selectivity of zeolites in collaboration with the groups at UiO gives Haldor Topsøe the unique opportunity to look beyond the horizon of classical industrial research and the insight gained from this project will help Topsøe to continue offering our clients the optimum solution. INEOS has two projects. In the MTO project important results have been achieved which increase the understanding of catalyst stability. This is important as the technology is about to be commercialized in China through a license sold by INEOS technology partner UOP. The other INEOS project is focused on improved understanding of catalyst properties and performance in the Oxychlorination step in production of Vinyl Chloride Monomer (for PVC production). INEOS operates several VCM plants and results from ingap on catalyst properties have been used in selecting better catalysts in commercial plants and also contributed to improved performance of the plants and thereby reduced production costs. Borealis decided to leave ingap in 2011, but emphasized that the reasons for leaving ingap were strategic, not the quality and relevance of the results. On the contrary, Borealis expressed great satisfaction with the results that were achieved in their project on new technology for light olefins production. 6

7 Table of contents Organisation... 8 Scientific Activities and Results Natural Gas to Syngas Natural Gas to Fuels Natural Gas to Petrochemicals New Chemistry Methods International Collaboration Recruitment Communication Supplements Fiancancing Publications, Presentations and Patent Applications

8 ORGANISATION Organisation Structure The ingap centre is organized through a project based matrix. Each project has been allocated to an Innovation Area, with an Innovation Area Manager. The Areas are: NG (Natural Gas) to syngas NG to fuels NG to petrochemicals New chemistry Methods The Innovation Area Managers are part of ingap s management team, together with the Managing Director and the Administrative Leader. The Innovation Area Managers report to the Managing Director. There are two types of projects within ingap: 1) Each industry partner has defined a Restricted Technology Area (RTA) project, for which they are given priority to intellectual property rights (IPR). 2) Non-RTA projects, which are of global interest to the Centre partners, mainly focusing on method development as well as preparation, characterization and testing of model materials. Steering Board Board leader: Steinar Kvisle Management team Managing Director: Unni Olsbye Administrator: Gloria Bostick International Advisory Board NG to syngas Leader: Bjørnar Arstad NG to fuels Leader: Øyvind Borg & Torhild H. Skarseth NG to petrochemicals Leader: Stian Svelle New chemistry Leader: Torbjørn Gjervan Methods Leader: Magnus Rønning 8

9 The Steering Board has members from each of the consortium partners and has the overall responsibility for all ingap s activities. The Head of the Board is appointed for 2 years at a time and for the years the Head of the board is Steinar Kvisle (INEOS). In addition, Tronn Øystein Hansen is The Research Council of Norway s observer to the Board. Partner Representative Deputy Borealis Klaus-Joachim Jens Eberhard Dreher Haldor Topsøe Jesper Nerlov Pablo Beato INEOS Steinar Kvisle Terje Fuglerud NTNU Anders Holmen Edd Blekkan SINTEF Duncan Akporiaye Aage Stori Statoil Morten Rønnekleiv Erling Rytter UiO Helmer Fjellvåg Anders Elverhøi An International Advisory Board (IAB) has been appointed from 01/2008, for a period of 2+2 years. Each Advisor covers a research area closely related to ingaps main activities. The IAB consists of the following persons during (in alphabetical order): Prof. Ferdi Schüth, Max-Planck institute für Kohlenforschung (Nanomaterials) Prof. Gabor Somorjai, University of California at Berkeley (Surface characterization) Prof. Bert Weckhuysen, University of Utrecht (In-situ characterization) The IAB assists the Steering Board in evaluating activities and recommending long-term strategies and priorities. 9

10 Partners ingap is a consortium between the following partners: Host institution: University of Oslo (UiO) Industry: Borealis Haldor Topsøe INEOS Statoil Non-industry: Norges Tekniske- Naturvitenskapelige Universitet (NTNU) SINTEF The ingap family gathered for the annual seminar in Trondheim in December Partner Collaboration Collaboration in ingap is ensured by three elements: Project collaboration. One very important goal for ingap is to combine the partners expertise and knowledge to advance understanding on selected processes. To achieve this goal all innovation areas and most projects involve several partners. In this way the transfer of competence between partners is assured and, hence, a united centre accomplished. Personnel exchange. All Ph.D. students employed within the centre will spend 6 months in one of the industry partners research facilities. Since the exchange takes place in the last part of the Ph.D. program, the industry partner gets a highly skilled chemist/chemical engineer in the laboratory and one that has been working on problems related to that partner s processes. At the same time this gives the student a chance to experience the challenges in high scale production chemistry and boost motivation even further. In 2011, Ph.D. students have had internships at INEOS, Haldor Topsøe AS and Statoil. Internal seminars. An internal seminar is organized each year. In 2011, the ingap seminar was organized as a 2-day meeting, where each project was introduced by the project leader, while detailed scientific presentations were given by the personnel carrying out the research. A main purpose of the seminar was exchange of skills and knowledge between the various projects and partners. The members of the International Scientific Board participated actively in the poster sessions, giving advice on project goals and methods. 10

11 SCIENTIFIC ACTIVITIES AND RESULTS SCIENTIFIC ACTIVITIES AND RESULTS ingap s vision can be shortened to: Innovation through fundamental insight. Catalysis is the workhorse of petrochemical industry, and fundamental insight is primarily obtained by studying catalysts under working conditions (Operando/insitu), in combination with mechanistic and kinetic reaction studies as well as quantumchemical modeling. Innovation is achieved whenever our findings are implemented as process improvements in industry. In the following, main challenges to natural gas conversion, as well as our approach to solving them, are presented, grouped by product and process areas. Insight at the fundamental level enables industrial scale improvements - ingap reasearch improves processes economically and environmentally. 11

12 NATURAL GAS TO SYNGAS NATURAL GAS TO SYNGAS Synthesis gas (Syngas, a mix of CO and H 2 ) is the common first step from natural gas, biomass or coal to a host of hydrocarbon products and others, via methanol, ammonia, or Fisher-Tropsch products. The processes for making synthesis gas are therefore highly relevant to any type of natural gas utilization that does not involve complete combustion. With synthesis gas as intermediate step, any organic product can be made from natural gas. NATURAL GAS TO SYNGAS Projects Metal Dusting Circulating Fluid Bed 12

13 NATURAL GAS TO SYNGAS Metal Dusting New approach to Metal Dusting studies Metal dusting corrosion can occur when steels and Nialloys are exposed to a strongly carburizing gas, such as synthesis gas, at temperatures between 400 C and 800 C. The corrosion product may include carbides, oxides, and graphitic carbon. Coke deposition is a key component of the process and is encouraged by the presence of metallic nanoparticles in the corrosion product. Low chromium steels are understood to corrode by a process that involves the initial formation of a layer of the metastable carbide, Fe 3 C, at the alloy surface. Alloys with a higher Cr content are initially protected by a surface Cr 2 O 3 -rich oxide. However, defects in the oxide can allow ingress of carbon. This leads to carburization of the alloy under the corroding surface and localized pitting corrosion. Important techniques for studying the MD phenomenon are electron microscopy techniques like Scanning Electron Microscopy (SEM) and Transmission Electron Microscopy (TEM). TEM is a powerful tool, but sample preparation for the study of alloy surfaces is demanding. MD-corroded surfaces are inhomogeneous in terms of precipitation and morphology and the most important, near-surface, regions have proven extremely difficult to prepare during earlier TEM studies. The Focused Ion Beam (FIB) technique provides the possibility to prepare samples from specific positions in a material microstructure. A Focused Ion Beam (FIB) technique has been used to cut out samples for analysis by Transition Electron Microscopy (TEM) and together with elemental analysis we have been able to identify new Metal-Carbon phases. The goal of this project is to understand the corrosion mechanism so that measures can be taken to avoid this material degradation. SEM images of a metallographically prepared cross section sample. The whole surface is corroded and pits are present underneath the coke deposit and corrosion product, as indicated by arrows. Around 300 μm of the original alloy thickness has been lost due to corrosion. After exposure, the thickness of the coke and corrosion product layer was 100 μm [1]. [1]: The evolution and oxidation of carbides in an Alloy 601 exposed to long term high temperature corrosion conditions J.C. Walmsley, J.Z. Albertsen, J. Friis and R.H. Mathiesen. Corrosion Science 52 (2010) NATURAL GAS TO SYNGAS 13

14 NATURAL GAS TO SYNGAS Circulating Fluidized Bed Reactor Circulating Fluidized Bed Reactor for sorption enhanced steam methane reforming H 2 production with simultaneous capture of CO 2 to reduce greenhouse gas emissions may be obtained by Sorption Enhanced Steam Methane Reforming (SE-SMR). The resulting product is a clean source of H 2 that may be used in power generation without greenhouse gas emissions or in fuel cells after an additional purification step. ingap collaborators have developed a new reactor system for this process, currently demonstrated on lab-scale. The Circulating Fluidized Bed Reactor enables continuous SE-SMR operation, which is highly advantageous to industry because it removes the otherwise necessary step of plant shut-down to regenerate the catalyst. There are three fundamental reactions in the SE-SMR unit. 1) CH 4 (g) + H 2 O (g) CO (g) + 3 H 2 (g) [Reforming] 2) CO (g) + H 2 O (g) CO 2 (g) + H 2 (g) [Water-gas shift] 3) MO (s) + CO 2 (g) MCO 3 (s) [Sorption] Where MO is a metal oxide that captures CO 2. The overall reaction is CH 4 (g) + 2 H 2 O (g) + MO (s) MCO 3 (s) + 4 H 2 (g), and this shows that by applying a suitable sorbent (MO) the hydrogen yield will be very high. By using CaO as sorbent the yield will be around 98%. A schematic drawing of the process is given below together with an experiment s hydrogen yield and CO 2 capture efficiency [1]. In this particular work the maximum thermodynamic CO 2 separation efficiency was 84% and that was almost reached in this experiment. NATURAL GAS TO SYNGAS [1] Continuous hydrogen production by sorption enhanced steam methane reforming (SE-SMR) in a circulating fluidized bed reactor Sorbent to catalyst ratio dependencies B. Arstad, J. Prostak, R. Blom, Chem. Eng. J. 2012, 14

15 NATURAL GAS TO FUELS NATURAL GAS TO FUELS High quality liquid fuels can be produced from any carbon-containing feedstock, including natural gas, biomass and coal. The Fischer-Tropsch and Methanolto-Gasoline processes are viable processes for such production. The catalyst and reaction conditions have a large impact on the product spectrum. With extensive knowledge within this area, ingap contributes to development of alternative routes for production of transportation fuels. The methanol-to-gasoline (MTG) process converts methanol directly to high octane gasoline. Projects Fischer-Tropsch technology Methanol-to-Gasoline (MTG) NATURAL GAS TO FUELS 15

16 NATURAL GAS TO FUELS Fischer-Tropsch technology and deactivation mechanisms Fischer-Tropsch technology and deactivation mechanisms Synthesis gas derived from carbon sources such as natural gas, coal or biomass, can be converted by the Fischer-Tropsch process into liquid hydrocarbons that can be upgraded further to products like synthetic diesel fuel, jet fuel, petrochemical naphtha and base lubricant oils. The Fischer-Tropsch (FT) process has been known for nearly 100 years and has been applied in several situations when crude oil was a limited or very expensive resource. Now the world oil resources are diminishing and alternative routes to produce fuels and petrochemical derivatives are receiving increased attention. The FT technology provides a route for comparatively cheap natural gas resources to enter the existing high value transportation fuel market. Several metals may be used as catalysts in the FT process and Co has many advantages compared to Fe, but the relatively high price of Co requires careful design and optimization of the catalyst in order to gain commercial advantages. We have therefore chosen to study deactivation processes in detail, a task that is particularly challenging because the particles are encapsulated by long hydrocarbons (wax) during the process. It is especially demanding to study deactivation in an operating environment. Two doctor theses are focusing on this task. A major difference between laboratory scale experiments and industrially run reactors is the presence and amount of impurities. Whenever catalysts or reactants are prepared in large batches, impurities are easily introduced to the system. An ingap project therefore focuses on the effect of various impurities on the FT reaction. Even small (ppm) level of an impurity may have effect on the reaction, and indeed we have seen that the presence of alkali and alkaline earth metals decreases the activity of the reaction. NATURAL GAS TO FUELS Graphical presentation of some of the suggested causes of catalyst deactivation in cobalt based Fischer-Tropsch synthesis. Cobalt (blue, oxygen (red), hydrogen (white) carbon (grey), sulphur (yellow) and aluminium (purple) 16

17 NATURAL GAS TO FUELS Methanol-to-Gasoline (MTG) Methanol-to-Gasoline (MTG) Methanol is a small and versatile molecule which can be converted to a myriad of different hydrocarbons by means of the MTG process. Under optimal conditions a high octane clean gasoline is produced. Since methanol is easily produced from natural gas, biomass or coal, the MTG process offers an important alternative route for fuel supply to the existing transportation market. At present, the world is dependent on oil for production of both fuels and raw materials for plastics. Gasoline production by the MTG process was started at industrial scale during the oil crisis in the 1980s, but the subsequent drop in oil price led to shut down of the Gasoline production part of the plants. Today s economy, however, shows renewed interest and boost in the industrial sector for this process. The catalysts: Zeolites Zeolites are the catalysts used in the MTG-process. Zeolites are microporous crystalline structures. These solid particles look like powders or pellets to our eyes, but at the molecular level they can be considered 3-dimensional labyrinths. Each crystal contains cavities and channels which the reactant methanol can diffuse into, and inside these channels the reaction occurs. The resulting product mixture depends on the type of zeolite we use as well as reaction conditions. For gasoline production the product molecules must be allowed to diffuse trough channels consisting of at least 10 T-atoms. Mechanism studies At ingap we study the mechanisms of the MTG reaction down to the molecular level in order to understand how to tune processes into producing only the products we desire. As the reaction mechanisms involved are highly complex, a range of advanced techniques have to be utilized in combination with each other. This requires a research group mastering a wide range of disciplines within chemistry. The diversity of experience and specialties found within the ingap center ensures that the group remains world-leading in studies of this highly complex and important reaction. Detailed insight gives new possibilities Our researchers have been able to determine the presence of two different mechanisms in the MTG process: an aromatic based cycle and an alkene based cycle. The aromatic cycle requires more space for the reaction to proceed than the alkene based cycle. This insight enabled the prediction that low-aromatic gasoline may be produced in a zeolite with just enough space for branched alkene production, but small enough to repress the aromatic cycle. Our detailed insight provided us the opportunity for rational design of a new process making the desired low-aromatic gasoline product. Different intermediates fit into the different zeolites, thereby determining the product distribution. NATURAL GAS TO FUELS 17

18 NATURAL GAS TO PETROCHEMICALS NATURAL GAS TO PETROCHEMICALS The main component in natural gas is methane, CH4, while petrochemicals consist of many carbon (C) atoms connected in various conformations. ingap has chosen a few areas in which we focus on the production of building blocks for petrochemicals. For instance ethene and functionalised ethenes are molecules required for making various plastic products. NATURAL GAS TO PETROCHEMICALS ingap focuses on developing new and improving existing technologies for making monomers for polymer production. Projects Methanol-to-Olefins (MTO) Olefin Technology Oxychlorination 18

19 NATURAL GAS TO PETROCHEMICALS What are petrochemicals? As the name implies, petrochemicals are chemical products manufactured from petroleum. The large majority of chemical products are produced from petroleum (oil) or natural gas. Sometimes, coal or biomass is employed. Among the petrochemical products, we find plastics, such as polyvinylchloride (PVC), polyethene, polypropylene; synthetic fibers such as polyesters, nylons; elastomers which are rubber-type materials; fertilizers; pharmaceuticals; paints; detergents; insecticides; vitamins; etc. Most of these products are made from surprisingly few chemical intermediates, referred to as base chemicals: Light alkenes - ethene, propene, and butadiene. Aromatic compounds - benzene, toluene, and xylenes. Synthesis gas (carbon monoxide and hydrogen and products made from syngas - ammonia and methanol. Petrochemicals from natural gas Several of these base chemicals may be made more readily from natural gas rather than petroleum. Synthesis gas is an obvious candidate, due to the high hydrogen content of natural gas. Moreover, the light alkenes may be made from wet natural gas (NGL) in a process known as steam cracking. Within ingap, we carry out research in order to understand how ethene and ethene derivatives are formed in several chemical processes. These compounds are used to produce plastic polymers. How chemistry resembles LEGO Plastic products are composed of small chemical compounds connected in rows and networks so that they become large molecules. These small chemical compounds can be considered the lego-blocks of the petrochemical industry. By making small alterations to these building blocks, an incredible variety of plastics can be produced. For instance, everyday use articles such as plastic spectacles (you might not know that most glasses today are made of plastic and not glass), your computer keyboard, the car dashboard, and your shopping bag are all made of plastic. It is easy to note that plastics cover a wide range from soft and pliable to hard and seemingly unbreakable. Plastics may be transparent or opaque. ingap s building blocks for plastic In ingap, we focus on processes that are particularly relevant for our industrial partners. One example is production of the Vinyl Chloride Monomer (VCM or H 2 C=CHCl). This is the building block used for making PVC, which is a very common type of hard plastic. Based on new knowledge achieved within the ingap collaboration, our industrial partner INEOS changed the catalyst in a running VCM plant in 2010, thus drastically improving the competitiveness of their process. Another research activity in ingap is directed towards a process for the formation of ethene (H 2 C=CH 2 ) and propene (H 2 C=CHCH 3 ) from natural gas. In the Methanol-to-Olefins (MTO) process, methanol is converted to these light alkenes. This process is similar to the Methanol-to-Gasoline process, also studied within ingap. The main difference is the choice of catalyst and operating conditions. We have developed extremely advanced equipment that allows us to monitor in real time the reactions that occur on the actual surface of the catalyst using high energy radiation only available at synchrotrons. NATURAL GAS TO PETROCHEMICALS 19

20 NATURAL GAS TO PETROCHEMICALS Methanol-to-Olefins (MTO) Methanol-to-Olefins (MTO) Zeolites are solids with tiny holes and channels which allow molecules in and out according to their size and shape. This property is used in methanol-to-olefins technology: methanol diffuses into the zeolite and is converted into ethene and propene which are small enough to escape. These products are the basis for a whole range of chemical products, particularly plastics. Olefins (a common name for light alkenes) are currently produced from oil, which is becoming increasingly expensive and scarce. MTO technology offers a flexible and specific route from raw materials like gas and biomass to the high value alkenes. Researchers at UiO, SINTEF, NTNU and Ineos have played a major role in the development of the process, using the SAPO-34 catalyst, which is currently being commercialized in China. Research at ingap is focused on extending the lifetime of the catalyst under industrial conditions. We have used state of the art techniques including multi-technique in situ studies of the reaction, computational studies and isotope substitution to reveal expansion in the catalyst driven by the buildup of reaction intermediates inside the zeolite channels, the precise molecules which cause expansion, the structure of the methanol-sapo-34 complex, migration of the active silicon atoms and variations in catalyst behavior in different parts of a reactor bed. Future research will focus on structural defects in the catalyst which are often the most important sites for catalysis. With in-situ XRD at the synchrotron in Grenoble we are able to see how pores inside the solid framework (solid balls and lines) fill with products (white cloud ) during reaction. NATURAL GAS TO PETROCHEMICALS 20

21 NATURAL GAS TO PETROCHEMICALS Olefin technology Olefin technology Ethene may be produced from dehydrogenation (=removing hydrogen) of ethane. Oxygen may be added to the feed to produce heat for the reaction. However, oxidative dehydrogenation of ethane (ODE) is a complex process involving extremely fast reactions at high temperature. Heat and reaction modelling in interplay with experiment are our tools to select the best reactor and conditions for the process. The reactions involved in the oxidative dehydrogenation of ethane (ODE) are extremely fast and occur at high temperature. Special challenges are then connected to the mixing of reagents, heating, cooling and stabilization of reaction conditions, and there is therefore a need to develop special reactors for this application. Heat and reaction modeling of these reactors is necessary to choose the best reactor and the best conditions for the process. A better understanding of the reaction kinetics for dehydrogenation of ethane, in the presence and absence of oxygen containing species, is important in optimizing the process conditions and the reactor model. The high reaction temperatures (up to C) involved leads to considerations regarding the choice of analytical method, sample and sample environment. In the current project we have developed an analytical technique based on infrared emission spectroscopy which makes it possible to quantitatively study the components involved at high temperatures. The technique has been demonstrated to be applicable within wide concentration ranges in small volume flowing reactor cells (4 mm I.D.). A kinetic model has been developed to describe the kinetics of oxidative dehydrogenation of ethane in gas phase, which has been employed to optimize the reaction towards the highest ethene yield. A detailed reaction routine was performed to understand the key radices and reaction steps leading to the secondary reaction of ethene and thus lower ethene selectivity. The results were compared to the reported kinetic data of catalytic oxidative dehydrogenation. It is interesting to note that the ethene yield obtained by the gas phase is higher than the most of reported values by catalytic ODE. The gas phase ODE provides a promises route to produce ethene from ethane. The 1-D and 2-D reactor models were developed to design and optimize the reactor with a multiple oxygen injection to achieve the theoretic maximum yield. Infrared emission spectroscopy (IRES) makes it possible to directly monitor the conversion of ethane to ethene in the reactor. NATURAL GAS TO PETROCHEMICALS 21

22 NATURAL GAS TO PETROCHEMICALS Oxychlorination Oxychlorination NATURAL GAS TO PETROCHEMICALS Oxychlorination of ethene is a key process step in the production of PVC (polyvinyl chloride) a thermoplastic produced by polymerisation of VCM (vinyl chloride monomer). INEOS ChlorVinyls, one of ingap s industrial partners, is the leading producer of PVC in Europe, and has production facilities at Rafnes, Norway, which is almost entirely based on LPG from the Norwegian continental shelf, representing a significant value creation for Norwegian natural gas resources. PVC is a thermoplastic (it can be melted and frozen into desired shapes repeatedly), its versatility ranging from building and aerospace products to pharmaceuticals. This makes PVC the second largest commodity plastic after polyethene, and the PVC world production is expected to exceed 40 million tonnes per year by Oxychlorination of ethene is a catalytic process performed over a copper based heterogeneous catalyst in either a fluidized bed or a multitubular fixed bed reactor. The catalyst typically contains cupric chloride (CuCl 2 ) as the primary active ingredient, impregnated on a porous support such as alumina, and may also contain numerous additives. Since the oxychlorination reaction is a highly exothermic reaction (releases energy as heat), the temperature rise and high volatility of active species are the main concerns. Deactivation of catalyst and production of unwanted chlorinated by-products causing high handling costs to the overall economy of the process. Despite of its commercial usage for more than 40 years, the deep understanding of the catalyst and its mechanism is still under investigation. ingap has taken up this challenge and the aim of the activities within ingap is to; Develop reaction kinetics based on fundamental understanding of the reaction mechanism. Gain understanding, at the atomic level, of the working catalytic system, particularly the role played by the additives and the carrier. The work is carried out in collaboration between University of Oslo, NTNU, University of Turin and INEOS. The approach is to study the catalyst under working conditions by in-situ and in-operando techniques. Our aim is to understand, at the atomic level, the role played by additives in the industrial catalyst. Our approach is to use a multi technique approach combined with expertise from industrial and academic partnerships. FTIR, UV-vis, XRD, EXAFS, XANES, CO-chemisoprtion ex-situ and in-situ, as well as traditional catalytic testing are our methods of choice. Several reports have already been published in international journals. Our studies so far show that a main challenge is to maintain the catalyst surface in an optimal state of chlorination, vital to achieve high activities and selectivities. Understanding the catalytic system under realistic conditions using combined characterisation techniques and systematic kinetic studies gives an insight into the mechanism of the process and thereby provides ways of tuning the catalyst as desired. The results are utilised in INEOS continuous efforts to improve the performance of the oxychlorination reactors and thereby the company s competitiveness. 22

23 New Chemistry New Chemistry Much of ingaps resources are focused on developing and improving existing processes in close collaboration with industrial partners. However, we are also dedicating ourselves to new chemistry, with the aim of developing completely novel catalytic systems. The innovation area New Chemistry aims to identify new catalysts, new processes and new chemical conversion routes for natural gas to products based on generic insight gained in the center. In addition, promising new (radical) ideas reported in the literature are evaluated. New Chemistry can include new methods, new characterization techniques, new materials and synthesis routes, and radically new technology/new routes to products. The innovation area pursues ideas and concepts not natural for the other innovation areas to follow up. So far, the innovation area has focused on new materials and catalysts, which includes catalytic MOFs (Metal Organic Frameworks), cobalt nano-particles for Fischer- Tropsch catalysts, and hydrothermal-electrothermal synthesis of porous systems. Projects Catalytic MOFs Cobalt Nanoparticles New Chemistry 23

24 New Chemistry Catalytic MOFs Catalytic MOFs Metal-Organic Frameworks (MOFs) can be considered to be molecular sponges. In the same way that the pores in a bathing sponge absorb lots of water, these materials use their much tinier pores to absorb vast amounts of gas phase molecules into a relatively small amount of material. The pores are simply empty space within the MOF structure. A metal organic framework is made of linkers (or spacers) which are carbon (organic) based and cornerstones which are metal based. In the figure shown, the spacers are represented by blue cylinders and the cornerstones by red cubes. The spacers link between the cornerstones in three dimensions but the arrangement leaves a high volume of empty space for the adsorption of gases, observable in the figure. New Chemistry A schematic model of a MOF. The ease in which the spacer and cornerstone of the material can be changed makes the total amount of different compounds with different properties nearly infinite. For example, simply increasing the length of the spacer would result in more empty space for the uptake of gas molecules. The connectivity of the linker may be changed e.g. a trigonal linker will connect 3 cornerstones while a linear linker connects only 2. The metal on the cornerstone may also be changed which may result in the cornerstone changing its shape. Using the figure as an example, the cube may become a tetrahedron or indeed any other polyhedron. It is also easy to adjust the chemical groups on the linker so that they interact more strongly with a particular gas, the purple balls on a stick are a representation of a functional chemical group on a linker. It is for this reason that these materials have attracted a lot of attention for their potential application as gas adsorbants to store environmentally or energetically strategic gases. Examples may include the adsorption of carbon dioxide (carbon capture) as a measure to combat global warming and the adsorption and storage of hydrogen for use as an ideal clean energy source. 24

25 New Chemistry Catalytic MOFs Our interest lies in the use of MOFs as catalysts. MOFs are commonly referred to for their potential in this application, however the science is young and the number of studies is relatively low. The main problem with MOFs in this application is that their stability under the harsh conditions of catalytic reactions is insufficient. We have made a milestone to overcome this by synthesising one of the most stable MOFs which we named UiO-66. Represented in a similar simple figure as the one shown, UiO-66 would have a dodecahedral (12 sided) cornerstone. One of our main goals is to make this material into an active catalyst by introducing chemical groups which are known to be catalytically active on to the linkers. We are also making a similar approach in order to make UiO-66 efficient in absorbing light for use in photocatalysis. The linkers may be modified in such a way that they act as antennae for the harvesting of light. When light is absorbed by a photocatalyst, electrons and holes are formed which are available to react with adsorbed molecules. One possible application is in the decomposition of environmental pollutants in the incidence of a chemical spill, for example. Representations of the UIO-66 framework, shown in different projections. New Chemistry 25

26 New Chemistry Cobalt Nanoparticles Synthesis and characterization of cobalt nanoparticles, and development of well defined metal on support model catalyst systems Nanotechnology is a term used when working with components in the range nanometer (nm). One nanometer corresponds to m. Nanomaterials attract huge attention due to their often unexpected physical and chemical properties relative to the same materials when composed of larger components. This makes also nanomaterials commercially important and scientifically very interesting. For example, in the oil industry metal-on-support catalysts are frequently used for converting natural gas (via synthesis gas) to valuable oil products. Fischer-Tropsch (FT) synthesis is one such process, and this process is controlled by a metal-on-support catalyst fabricated by nanometer sized metal particles deposited onto a porous support. The metal component of the FT-catalyst is often cobalt (Co). In order to optimize the industrial process to give high reaction rates and no undesired by-products we need to understand how the small catalytic particles must be designed with respect to size, shape and atomic arrangement. Figure 1 shows some possible shapes of such metal nanoparticles. In cobalt metal and in cobalt nanoparticles, the cobalt atoms can be arranged in different ways giving rise to slightly different atomic arrangements, or polytypes. The two most common polytypes are face centered cubic (fcc) and hexagonal closed packed (hcp), see Figure 2. For large particles the hcp type is stable below 420 o C, whereas the fcc-type exists at higher temperatures. However, when the cobalt particle size become smaller than approximately 20 nm, the fcc-type will also be the favoured polytype below 420 o C, which in turn may affect the catalytic properties in a cobalt based metalon-support catalyst. Several efforts have been done to correlate cobalt particle size, shape, atomic arrangement and controlled addition of an extra element to the cobalt particle with respect to catalyst performance. Most studies are hampered by not being carried out in a systematic manner, varying just one or a minimum materials parameters. Also the preparation route may be a factor affecting the atomic arrangement and composition of the particles, in particular when more elements are added to cobalt. In this project we target on developing synthetic routes that yield particles with narrow size distribution, welldefined atomic arrangement and chemical composition. These carefully designed particles will in a next step be applied for preparation of well defined model metalon-support catalysts. Finally, systematic studies will be undertaken to search for significant correlations between particle properties and catalyst performance. New Chemistry 26

27 New Chemistry Cobalt Nanoparticles Figure 1 Some possible shapes of cobalt nanoparticles. Figure 2 Structural representation of fcc Co presented in a pseudo hexagonal cell (left panel) and hcp Co (right panel). New Chemistry 27

28 METHODS Methods METHODS A main challenge in today s catalysis research is to study the processes at molecular level while running at realistic conditions. Method development is an ingap focus area targeted towards state-of-theart in situ techniques. In addition, new methods for making and studying model systems receive high priority. ESRF in Grenoble, where ingap has been a leading contributor to the building of in situ equipment. Projects In-situ techniques TEM ALD NMR Scientists are trying to find out in detail which reactions take place during industrial processes and with this knowledge we want to design more active and stable catalyst materials. Common industrial processes such as the Fischer-Tropsch synthesis and the methanol to olefins process operate at demanding pressures and temperatures. Not long ago, the only way to study these catalyst systems was restricted to ex situ characterisation methods. These are not necessarily reliable since their behaviour and chemical state is highly dependant on the reaction environment. For example, cobalt metal particles can be re-oxidised when exposed to air. In situ methods offer the possibility to work with sample environments where the reaction conditions can be reproduced (i.e. high temperature, reaction gas mixture and also high pressures). InGAP has invested in advanced equipment for further development and refinement of a wide range of techniques which allow scientists to get information on different aspects of catalyst structure, such as the nature of crystalline phases, sizes of metal and oxide nanoparticles, and the oxidation state of the atoms in the catalysts. Synchrotron-based X-ray techniques are directly combined with more conventional methods, such as Raman and infrared spectroscopy. The main characterisation methods used by ingap are XRD (X-ray diffraction), XAS (X-ray absorption spectroscopy), diffuse reflectance infrared Fourier-transform spectroscopy (DRIFTS), Nuclear magnetic resonance (NMR) transmission electron microscopy (TEM) and microcalorimetry. The centre has also a strong emphasis on advanced synthesis methods such as atomic layer chemical vapour deposition (ALCVD). ingap has been a leading contributor to the building of in situ equipment at the Swiss-Norwegian Beam Line (SNBL) at ESRF in Grenoble. It is now possible to study the surface reactions on the catalyst at high temperature, high pressure and with a reactant gas flow. 28

29 METHODS ALD Atomic layer deposition - building surfaces by atom by atom Imagine being able to build surfaces with atomic precision. The atomic layer deposition (ALD) technique can provide such control by depositing monolayers of compounds in a sequential manner. The ALD technique builds new surfaces by exploiting self-limiting reactions between highly reactive gas molecules and active sites on surfaces. The self-limiting nature of the process ensures conformal and pin-hole free film on surfaces with complex geometries such as porous supports. The technique is currently used in large scale for deposition of high-k materials for transistors, enabling the ever shrinking size of such microelectronics. It is also used in corrosion protection - from exposed process equipment to delicate silver jewelry. We exploit the technique in deposition of model materials for studies of catalytic processes since it can provide even distribution of catalytic materials on porous supports, even in the very tiniest pores. The principle behind the technique is to split a chemical reaction between two compounds into a sequential process, where each compound is allowed to saturate a substrate or support in an alternating manner. This strategy provides a digital control of the deposited material in terms of both thickness and composition. We have demonstrated its suitability to deposit materials such as metals, oxides, nitrides, phosphates, organic- inorganic hybrids, and also purely organic compounds. Its potential is huge, both in terms of types of materials, applications, and also possibilities for studying chemical reactions in a detailed manner. METHODS 29

30 METHODS NMR NMR During 2009 SINTEF, together with the University of Oslo, established a new Nuclear Magnetic Resonance (NMR) spectroscopy lab. The lab was financed by SINTEF, the Norwegian Research Council program NANOMAT and by ingap. The new lab is located in SINTEF s laboratories in Oslo. The NMR lab has been established as a national research tool platform and includes two state-of-theart Bruker Avance III NMR instruments - a 400 MHz instrument for liquid samples and a 500 MHz wide bore instrument for solid samples, high temperature experiments and gas flow (catalytic) experiments. The 500 MHz instrument is equipped with four different solid-state sample holders (probes): Two different MAS probes (3.2 mm triple resonance and 4 mm extended tuning range and high T) for solid-state NMR and two other special probes; a HR-MAS probe suitable for solidliquid samples, such as tissues and gels and a MASCAT flow probe allowing NMR studies of a sample under flowing gas. This latter probe has a working temperature up to about 400 C and allows studies of gas-solid interactions relevant for catalysis. This probe has the required gas feeding systems and online analysis based on GC. The new NMR laboratory is a major upgrade of the national NMR infrastructure in Norway and has a special focus on studies within material science. The NMR laboratory is available for basic research in addition to providing services for companies. METHODS The NMR lab at SINTEF is available for basic research in addition to providing services for companies 30

31 INTERNATIONAL COLLABORATION INTERNATIONAL COLLABORATION ingap is international in nature, with 3 out of 4 industry partners being based outside Norway. Statoil has a partnership with Lurgi (Germany) and PetroSA (South-Africa) on the F-T process and Johnson Matthey (England) on catalyst manufacture, while INEOS has partnership with UOP (USA) on the MTO process. ingap benefits from the wide and active international network of its partners. The Centre partners have a long tradition of sending Ph.D. students abroad for a 6 month traineeship, and this tradition is continued within ingap. The receiving institution for such stays is selected based on the priorities and needs of the project. As such, the University of Utrecht (in-situ spectroscopy), the University of Berkeley (metal nano-particles) and the University of Versailles (in-situ solid-state NMR) are new collaboration partners during the Centre period. ingap has further extended the partner institutions collaboration with the European Synchrothron Research facilities in Grenoble, France (ESRF), by the investment of a stateof-the-art system for in-situ catalyst studies under industrial working conditions (20 bars, 1000 o C). In 2011, ingap has received 7 visiting students and 7 visiting researchers, from Europe and Asia. Centre partners are involved in 8 EU projects under the 7 th research programme, and one of them (OCMOL) is a direct result of the ingap centre collaboration. ingap recruits internationally, and strong post-doctoral researchers are coming from e.g. University of Aveiro, Portugal; University of St. Andrews, Scotland; IRCE-Lyon, France. ingap s Advisory board consists of three internationally leading scientist in core fields for ingap: Prof. Gabor Somorjai, Univ. Berkeley; Prof. Bert Weckhuysen, Univ. Utrecht, Prof. Ferdi Schüth, Max Planck Institute für Kohlenforschung. The internationally leading scientist within ethene oxychlorination materials (one of our target processes), Prof. Carlo Lamberti, Univ. Torino, Italy, is an associated member of ingap and co-supervises one of the Ph.D. students. 31

32 RECRUITMENT RECRUITMENT ingap has a goal of educating 18 Ph.D. students and Postdoc fellows or researchers during the expected 8 year lifespan of the Centre. By the end of 2011, 2 PhD students had completed their degree, while 11 PhD students and 2 Postdoc fellows were working in the Centre. The female share of PhD students and postdocs are 36 % and 25%, respectively. COMMUNICATION COMMUNICATION Scientific communication within ingap is mainly achieved through project meetings within each subproject, about 4-6 per year per project. Knowledge exchange between projects and research areas is secured through an annual ingap seminar, where all ingap personnel is gathered for scientific lectures and strategic discussions. Dissemination of project results to a wider audience is secured through oral and poster contributions at national and international workshops and symposia, and through scientific articles in peer-reviewed journals. After 5 years of operation, the annual production of scientific papers and conference contributions from ingap has stabilised at a high level; the scientific publication number from ingap was 17, plus 80 associated publications, in

33 SUPPLEMENTS Ph.D. students with financial support from the Centre budget Name Nationality From To M/F Topic Partner Daham Sanjaya G. P Vidana Indian M Metal Dusting NTNU Nikolaos Tsakoumis Greek M Fischer-Tropsch Technology NTNU Eleni Patanou Greek F Microkinetics/microcalorimetry NTNU Alexey Voronov Russian M Study of deactivation mechanisms NTNU Hassan Jamil Dar Pakistani M Olefin technology NTNU Madeleine Diskus French F Model compounds M/support UiO Miroslav Surma Czech M VCM technology NTNU Mahsa Zokaie Iranian F Model compounds-microporous UiO Naresh Muddada Indian M Oxychlorination UiO Wegard Skistad Norwegian M Methanol to gasoline UiO Shewangizaw Teketel Ethiopian M Methanol to gasoline UiO Marius Westgård Erichsen Norwegian M Mechanistic studies, acid catalysis UiO Greig Shearer Scottish M Catalytic MOFs UiO Eirini Zacharaki Greek F Cobalt Nanoparticles UiO 33

34 SUPPLEMENTS Postdoctoral researchers with financial support from the Centre budget and other sources Name Nationality From To M/F Topic Partner David Wragg British M In-situ@UiO UiO Erwan Rauwel French M Fischer-Tropsch Technology UiO Merete Hellner Nilsen Norwegian F VISTA: functionalization and UiO applications of zirconium-containing metal organic framework Linn Edda Sommer German F Nonoxidative methane activation UiO Sandrine Benard French F EU/OCMOL UiO Sami Malola Finnish M Quantum modelling studies UiO Marian Palcut Solvakian M Perovskite partial oxidation catalysis UiO Radostina Palcheva Bulgarian F Catalysis, metal oxide UiO Torstein Fjermestad Norwegian M Quantum modelling studies UiO Haiyan Song Chinese F Novel Catalysts UiO Karima Benyahia Moroccan F Periodic calculations of MgO-surface SINTEF with Ni-metal Sara Boullosa-Eiras Spanish F NTNU Nina Hammer Norwegian M NFR/SYNKROTRON NTNU Fan Huang Chinese M NTNU Javier Fermoso Dominguez Spanish NTNU M Bjørn Christian Enger Norwegian M VISTA NTNU Ingeborg-Helene Svenum Norwegian F NFR/KOSK NTNU Espen Wangen Norwegian M EU-FP7 NTNU Jun Zhu Chinese M NFR7/KOSK NTNU 34

35 SUPPLEMENTS Ph.D. students working on projects in the Centre with financial support from other sources Name Nationality Funding M/F Partner Federica Mudu Italian NFR/Petromaks F UiO Bjørn Tore L. Bleken Norwegian NFR/Gassmaks M UiO Einar Andre Eilertsen Norwegian NFR/KOSK M UiO Søren Jakobsen Danish UiO/KD M UiO Christoph Sprung German NFR/Renergi M UiO Francesca L. Bleken Norwegian NFR/Frinat F UiO Nelli Pfaff German F UiO Asmira Delic Norwegian NTNU F NTNU Charitha Udani Sri Lankan NTNU F NTNU Ingvild Tronstad Norwegian NFR F NTNU Fan Huang Chinese NFR/Gassmaks M NTNU Saima Sultana Kazi Bangladeshi NFR/Renergi F NTNU Tayyaba Noor Pakistani NFR/KOSK F NTNU Ilya Gorelkin Russian NFR/Gassmaks M NTNU Georg Voss German NFR/KOSK M NTNU Andrey Volynkin Russian NTNU M NTNU Fengliu Lou Chinese Vista M NTNU Andreas Helland Lillebø Norwegian Statoil/NFR M NTNU Navaneethan Muthuswamy Indian NF/Nanomat M NTNU Paul Radstake Dutch NFR/Gassmaks M NTNU Nicla Vicinanxa Italian NFR F NTNU Farbod Dadgar Iranian NFR M NTNU 35

36 SUPPLEMENTS Master students in the Centre 2011 Name F/M Topic Partner Tone Colbjørnsen F Zirconium-containing metal organic framework: Study of UiO fundamental properties of UiO-66 Kjetil Gurholt Evensen M Comparative investigations of zeolite catalyst deactivation using UiO UV-Visible spectroscopy and catalyst dissolution/coke extraction Sigurd Øien M Synthesis and characterization of modified UiO-67 MOF UiO Geard Ayuso Virgili M NTNU Aina-Elin Karlsen F Synthesis and Characterisation of Co-based Fischer-Tropsch Catalysts and Supports, using hydrothermal and chemical attrition Method STATOIL Visting Researchers Name Nationality F/M Partner Guangming Zeng Chinese M UiO Silvia Bordiga Italian F UiO Carlo Lamberti Italian M UiO Javier Ruiz-Martinez Spanish M UiO Saepurahman Saepurahman Indonesian M UiO Corrales Aramburo Spanish M UiO Filippo Giordanino Italian M UiO Jeroen Van der Mynsbrugge Belgian M UiO Kristof De Wispelaere Belgian M UiO Norbert Stock German M UiO 36

37 SUPPLEMENTS Senior personnel Partner Name Main research area Haldor Topsøe A/S Pablo Beato Catalyst synthesis, testing and characterisation (spectroscopy) Ton Janssens Catalyst testing Finn Joensen Catalyst testing Jesper Nerlov Catalyst characterisation INEOS Terje Fuglerud Catalyst testing and characterisation Arne Grønvold Catalyst testing and characterisation Tone Kleivane Catalyst testing and characterisation Lola Irene Sanna Catalyst testing and characterisation NTNU Edd Blekkan Catalyst testing and characterisation De Chen Catalyst testing and characterisation Anders Holmen Catalyst testing and characterisation Magnus Rønning Catalyst testing and characterisation Hilde Venvik Catalyst testing and characterisation SINTEF Duncan Akporaiye Catalyst testing and characterisation Bjørnar Arstad Catalyst testing and characterisation Jasmina H. Cavka Catalyst synthesis and characterisation Torbjørn Gjervan Catalyst testing Odd Asbjørn Lindvåg Catalytst testing Rune Lødeng Catalyst testing and characterisation Rune Myrstad Catalyst testing Knut Thorshaug Catalytst characterisation John C. Walmsley Catalyst characterisation Statoil Øyvind Borg Catalyst testing and characterisation Morten Brustad Material characterisation Emil Edwin Material characterisation Sigrid Eri Catalyst testing and characterisation Iver Espen Pedersen Material characterisation Erling Rytter Catalyst testing and characterisation Torild H. Skarseth Catalyst testing and characterisation UiO Sharmala Aravinthan Catalyst testing and characterisation Gloria Bostick Administration Helmer Fjellvåg Catalyst synthesis and characterisation Karl Petter Lillerud Catalyst synthesis and characterisation Ola Nilsen Catalyst synthesis and characterisation Unni Olsbye Catalyst testing and characterisation Anja Sjåstad Catalyst synthesis and characterisation Stian Svelle Catalyst testing and characterisation and modeling Ole Swang Quantum-chemical modeling 37

38 FINANCING - COST ingap Funding Total Item RCN Grant Host: UiO NTNU SINTEF Borealis Ineos HTAS Statoil public financing Total financing Type of partner P P R Large Ent. Large Ent. Large Ent. Large Ent. 1. NG to syngas NG to fuels NG to petrochemicals New chemistry Methods/equipment Administration Total budget Cost Thematic -area/activity Host: UiO NTNU SINTEF Borealis Ineos HTAS Statoil Total 1. NG to syngas NG to fuels NG to petrochemicals New chemistry Methods/equipment Administration Total budget

39 Publications, presentations and patent applications Publications by ingap PhD theses N. Tsakoumis «Deactivation of cobalt based Fischer- Tropsch synthesis catalysts». NTNU, Trondheim: Institutt for kjemisk prosessteknologi, NTNU 2011 (ISBN ) 212 s. M. Diskus On model materials designed by atomic layer deposition for catalysis purposes, UiO. ingap Publications A. M. Beale, M. G. O Brien, M. Kasunic, A. Golobic, M. Sanchez-Sanchez, A. J. W. Lobo, D. W. Lewis, D. S. Wragg,S. Nikitenko, W. Bras, B. M. Weckhuysen Probing ZnAPO-34 Self-Assembly Using Simultaneous Multiple in Situ Techniques. Journal of Physical Chemistry C, 115(14) (2011) F. Bleken, W. Skistad, K. Barbera, M. Kustova, S. Bordiga, P. Beato, K. P. Lillerud, S. Svelle, U. Olsbye Conversion of Methanol over 10-Ring Zeolites with Differing Volumes at Channel Intersections: Comparison of TNU-9, IM-5, ZSM-11 amd ZSM-5 Physical Chemistry Chemical Physics, 13(7) (2011) Ø. Borg, N. Hammer, B. C. Enger, R. Myrstad, O. A. Lindvåg, S. Eri, T. H. Skagseth, E. Rytter, Effect of biomass-derived synthesis gas impurity elements on cobalt Fischer-Tropsch catalyst performance including in situ sulphur and nitrogen addition, Journal of Catalysis, 279 (2011) R. Dehghan-Niri, T. W. Hansen, J. B. Wagner, A. Holmen, E. Rytter, Ø. Borg, J. C. Walmsley In situ Reduction of Promoted Cobalt Oxide Supported on Alumina by Environmental Transmission Electron Microscopy, Catalysis Letters, 141 (2011) M. Diskus, O. Nilsen, S. Diplas, P. Beato, C. Harvey, E. van Schrojenstein Lantman, B. M. Weckhuysen and H. Fjellvåg Combination of characterization techniques for ALD MoO3 coatings: from the amorphous to the orthorhombic alpha-moo3 crystalline phase, Journal of Vacuum Science & Technology A, 30 (2012) doi: / M. Diskus, O. Nilsen, H. Fjellvåg Growth of thin films of molybdenum oxide by atomic layer deposition, Journal of Materials Chemistry, 21(3) (2011) M. Diskus, O. Nilsen, H. Fjellvåg, Thin Films of Cobalt Oxide Deposited on High Aspect Ratio Supports by Atomic Layer Deposition, Chemical Vapor Deposition, 17(4-6) (2011) D. Gianolio, N.B. Muddada, U. Olsbye, C. Lamberti Doped- CuCl 2 /Al 2 O 3 catalysts for ethylene oxychlorination: influence of additives on the nature of active phase and reducibility Nuclear Instruments and Methods in Physics Research B, (2011) doi: /j. nimb N.B. Muddada, U. Olsbye, T. Fuglerud, S. Vidotto, A. Marsella, S. Bordiga, D. Gianolio, G. Leofanti, C. Lamberti The role of chlorine and additives on the density and strength of Lewis and Brønsted acidic sites of gamma-al 2 O 3 support used in oxychlorination catalysis: a FTIR study Journal of Catalysis, 284(2) (2011) U. Olsbye, O.V. Saure, N. B. Muddada, S. Bordiga, C. Lamberti, M. H. Nilsen, K.P. Lillerud, S. Svelle Methane conversion to light olefins-how does the methyl halide route differ from the methanol to olefins (MTO) route? Catalysis Today, 171(1) (2011)

40 E. Rauwel, O. Nilsen, A. Galeckas, J. Walmsley, E. Rytter, H. Fjellvåg ALD Applied to Conformal Coating of Nanoporous γ-alumina: Spinel Formation and Luminescence Induced by Europium Doping ECS Transactions, 41(2) (2011) S. Svelle, L. E. Sommer, K. Barbera, P. N. R. Vennestrøm, U. Olsbye, K. P. Lillerud, S. Bordiga, Y.-H. Pan, P. Beato How defects and crystal morphology control the effects of desilication Catalysis Today, 168(1) (2011) S. Svelle, M. Visur, U. Olsbye, Saepurahman, M. Bjørgen Mechanistic Aspects of the Zeolite Catalyzed Methylation of Alkenes and Aromatics with Methanol: A Review. Topics in Catalysis, 54(13-15) (2011) S. Svelle, M. Bjørgen Selective catalysts for petrochemical industry - shape selectivity in microporous materials in: A. Zecchina, S. Bordiga, E. Groppo (Eds.), Selective nanocatalysts and nanoscience: Concepts for hetereogeneous and homogeneous catalysis, Wiley-VCH, Weinheim, Germany, (2011), pp S. Teketel, W. Skistad, S. Benard, U. Olsbye, K. P. Lillerud, P. Beato, S. Svelle Shape selectivity in the conversion of methanol to hydrocarbons: the catalytic performance of one dimensional 10-ring zeolites: ZSM-22, ZSM-23, ZSM-48 and EU-1 ACS Catalysis, (2011) doi: /cs200517u. D. S. Wragg, G. M. Fullerton, P. J. Byrne, A. M. Z. Slawin, J. E. Warren, S. J. Teat, R. E. Morris Solvothermal aluminophosphate zeotype synthesis with ionic liquid precursors. Dalton Transactions, 40 (2011) D. S. Wragg, D. Akporiaye, H. Fjellvåg Direct observation of catalyst behaviour under real working conditions with X-ray diffraction: Comparing SAPO-18 and SAPO-34 methanol to olefin catalysts. Journal of Catalysis, 279(2) (2011) ingap Invited Lectures at International Conferences R. H. Heyn Incorporation of CO2 into Fine Chemicals The CO2Chem Network Meeting, Newcastle (UK) September 21, U. Olsbye Conversion of methanol to hydrocarbons how the zeolite host structure affects product selectivity XV. International symposium on relations between homogeneous and heterogeneous catalysis, Berlin (Germany), September 11-16, U. Olsbye Oxygenate and chlorocarbon conversion to olefins on the correlation between zeolite topology and product selectivity. 22nd North American Catalysis Society Meeting, Detroit (USA), June 5-10, U.Olsbye 34 years of MTO and MTG research What is still new? The 12 th Netherlands Catalysis and Chemistry Symposium, Noordwijkerhout (The Netherlands) February 28 March 2, S. Svelle Kinetic studies of zeolite catalyzed methylation reactions 2nd International NAPEN 2011 Workshop, Rhodes (Greece) June 9-13, ingap Associated Publications M. A. K. Ahmed, H. Fjellvåg, A. Kjekshus, D. S. Wragg, N. S. Gupta Synthesis and Crystal Structure of [Cr(thd) 2 (OEt)] 2 Zeitschrift für anorganische und allgemeine Chemie, 637(1) (2011) M. A.K. Ahmed, H. Fjellvåg, A. Kjekshus, P. D. C. Dietzel, D. S. Wragg, «The Mixed-Valence, Mixed-Ligand Complex Co3(thd)3(EtO)4(tert-BuCOO).» Zeitschrift für Anorganische und Allgemeines Chemie 2011; Volum 637. s

41 E. Bakken, P. D. Cobden, P. P. Henriksen, S. F. Håkonsen, A. I. Spjelkavik, M. Stange, R. E. Stensrød, Ø. Vistad, R. Blom Development of CO2 sorbents for the SEWGS process using high throughput techniques Energy Procedia, 4 (2011) V. Bakken, E. Rytter, O. Swang Chemisorption on Cobalt Surfaces: The Effect of Subsurface Rhenium Atoms from Quantum Chemical Cluster Model Calculations Surface Science, 605(6-5) (2011) M. Bjørgen, A. H. Grave, Saepurahman, A. Volynkin, K. Mathisen, K. P. Lillerud, U. Olsbye, S. Svelle Spectroscopic and catalytic characterization of extra large pore zeotype H-ITQ-33 Microporous and Mesoporous Materials, (2011) doi: /j. micromeso F. L. Bleken, W. Skistad, K. Barbera, M. Kustova, S. Bordiga, P. Beato, K. P. Lillerud, S. Svelle, U. Olbye, «Conversion of methanol over 10-ring zeolites with differing volumes at channel intersections: comparison of TNU-9, IM-5, ZSM- 11 and ZSM-5.» Physical Chemistry, Chemical Physics - PCCP 2011; Volume 13.(7) s E. A. Blekkan, D. Chen, M. Rønning, H. J. Venvik Preface. Topics in catalysis, 54 (2011) S. Braovac, H. Kutzke, S. Jørgensen, A. Bouzga, B. Arstad, E. W. Hansen Alum-treated wood: characterization using infrared spectroscopy and solid state 1h and 13C NMR. Shiprecks 2011; J. M. G Carballo, J. Yang, A. Holmen, S. Garcia-Rodriguez, S. Rojas, Sergio; M. Ojeda, J. L. G. Fierro «Catalytic effects of ruthenium particle size on the Fischer- Tropsch Synthesis». Journal of Catalysis 2011; Volum 284.(1) s D. Chen, C- J Liu «A Current Perspective on Catalysis for New Energy Technologies». ChemCatChem 2011;Volum 3.(3) s D. Chen, J. Moljord, A. Holmen Methanol to Olefins: Coke Formation and Deactivation. I: Deactivation and Regeneration of Zeolite Catalysts. Imperial College Press 2011 ISBN s D. Chen, R. Lødeng, H. Svendsen, A. Holmen Hierarchical multi-scale modeling of methane steam reforming reactions Industrial Engineering Chemistry Research, 50(5) (2011) X. Duan, G. Qian, X. Zhou, Z. Sui, D. Chen, W. Yuan Tuning the size and shape of Fe nanoparticles on carbon nanofibers for catalytic ammonia decomposition. Applied Catalysis B: Environmental, 101(3-4) (2011) J. C. den Breejen, A. M. Frey, J. Yang, A. Holmen, M. M. van Schooneveld, F. M. R. de Groot, O. Stephan, J. H. Bitter, K. P. de Jong A Highly Active and Selective Manganese Oxide Promoted Cobalt-on-Silica Fischer-Tropsch Catalyst. Topics in catalysis 2011; Volum 54. s E. A. Eilertsen, F. Giordanino, C. Lamberti, S. Bordiga, A. Damin, F. Bonino, U. Olsbye, K. P. Lillerud Ti-STT: a new zeotype shape selective oxidation catalyst. Chemical Communications, 47 (2011) E. A. Eilertsen, S. Bordiga, C. Lamberti, A. Damin, F. Bonino, B. Arstad, S. Svelle, U. Olsbye, K. P. Lillerud Synthesis of Titanium Chabazite: A New Shape Selective Oxidation Catalyst with Small Pore Openings and Application in the Production of Methyl Formate from Methanol. ChemCatChem, (2011) Volum 3.(12) s D. Chen, L. He «Towards an Efficient Hydrogen Production from Biomass: A Review of Processes and Materials.» ChemCatChem 2011;olum 3.(3) s

42 E. A. Eilertsen, I. Ogino, S.-J. Hwang, T. Rea, S. Yeh, S. I. Zones, A. Katz Nonaqueous Fluoride/Chloride Anion-Promoted Delamination of 2 Layered Zeolite Precursors: Synthesis and Characterization of UCB- 2 Chemistry Materials, (2011) volum 23.(24)s E.A. Eilertsen, B. Arstad, S. Svelle, K. P. Lillerud, Karl Petter, «Single Parameter Synthesis of High Silica CHA Zeolites from Fluoride Media.» Microporous and Mesoporous Materials 2011; Volume 53. s E. A. Eilertsen, M. Haouas, K. P. Lillerud, F. Taulelle Connectivity analysis of aluminum and silicon in the clear sol precursor of SSZ-13 chabazitetype zeolite. FEZA 2011; S. B. Eiras, E. M. M. Vanhaecke, T. Zhao, D. Chen, A. Holmen Raman spectroscopy and X-ray diffraction study of the phase transformation of ZrO2 Al2O3 and CeO2 Al2O3 nanocomposites. Catalysis Today, 166(1) (2011) S. B. Eiras, T. Zhao, D. Chen, A. Holmen Effect of the preparation methods and alumina nanoparticles on the catalytic performance of Rh/ZrxCe1-xO2-Al2O3 in methane partial oxidation. Catalysis Today, 171(1) (2011) S. B. Eiras, T. Zhao, E. M. M. Vanhaecke, D. Chen, A. Holmen Partial oxidation of methane to synthesis gas on Rh/ZrxCe1-xO2-Al2O3. Catalysis Today 2011;Volum 178. s B. C. Enger, Å.-L. Fossan, Ø. Borg, E. Rytter, A. Holmen Modified alumina as catalyst support for cobalt in the Fischer-Tropsch synthesis. Journal of Catalysis, 184(1) (2011) C. Fan, X.-G. Zhou, D. Chen, H.Y. Cheng, Y.-A. Zhu Toward CH4 dissociation and C diffusion during Ni/Fe-catalyzed carbon nanofiber growth: A density functional theory study. Journal of Chemical Physics, 134(13) (2011) doi: / H. Grove, O. M. Løvvik, W. Huang, S. M. Opalka, R. H. Heyn, B. Hauback Decomposition of Lithium Magnesium Aluminum Hydride International Journal of Hydrogen Energy, 36(13) (2011) N. S. Gupta, D. S. Wragg, M. Tilset, J. P. Omtvedt 4,7,13,18-Tetraoxa-1,10-diazoniabicyclo[8.5.5] icosane bis(hexafluoridophosphate) Acta Crystallographica Section E Structure Reports Online, 67 (2011) O1929-U2047. N. S. Gupta, D. S. Wragg, M. Tilset, J. P. Omtvedt, 4, 7, 13, 18-Tetraoxa-1, 10-diazoniabicyclo [8.5.5] icosane hexafluoridosilicate Acta Crystallographica Section E Structure Reports Online, 67 (2011) O1958-U2293. N. Hammer, T. Zscherpe, D. Chen, M. Rønning Selective oxidation of CO on Au/TiO 2 catalysts on a structured carbon support Topics in Catalysis, 54 (2011), E. W. Hansen, J. Paul, S. Jørgensen, B. Arstad, A. Bouzga Quantitative determination of comonomer content in ethene-1-hexene copolymers by solid state 1H-MAS NMR (ethene-α-hexene) International Journal of Research and Reviews in Applied Sciences, 6(4) (2011) X.-X. He, C. Fan, X.-Y. Gu, D. Chen, Y.-A. Zhu Role of CO2 in ethylbenzene dehydrogenation over Fe2O3(0001) from first principles. Journal of Molecular Catalysis A: Chemical, 344(1-2) (2011) E. Hodúlová, M. Palcut, E. Lechovič, B. Šimeková, K. Ulrich Kinetics of intermetallic phase formation at the interface of Sn Ag Cu X (X = Bi, In) solders with Cu substrate Journal of Alloys and Compounds, 509(25) (2011) S. F. Håkonsen, R. Blom Chemical Looping Combustion in a Rotating Bed Reactor Finding Optimal Process Conditions for Prototype Reactor Environmental Science & Technology, 45(22) (2011)

43 S. S. Kazi, D. Chen Enhanced hydrogen production by in situ CO2 removal on CaCeZrOx nanocrystals. Catalysis Today, 171(1) (2011) M. Kandiah, D. S. Wragg, M. Tilset, K. P. Lillerud Poly[tris( -2-aminobenzene-1,4-dicarboxylato) tetrakis(n,n-dimethylformamide)diyttrium(iii)] Acta Crystallographica Section E Structure Reports Online, 67 (2011) M44-U550. S. Kolboe A Computational Study of tert-butylbenzenium Ions Journal of Physical Chemistry A, 115(14) (2011) Q. Li, Z. Sui, X. Zhou, D. Chen Kinetic study of propane dehdyrogenation over Pt-Sn/Al2O3 catalyst. Applied Catalysis A: General 2011; 398.(1-2), S. Lögdberg, M. Boutonnet, J. Walmsley, S. Järås, A. Holmen, E. A. Blekkan «Effect of water on the spacetime yield of different supported cobalt catalysts during Fischer-Tropsch synthesis.» Applied Catalysis A : General 2011; 393(1-2), M. Lualdi, S. Lögdberg, G. Di Carlo, S. Järås, M. Boutonnet, A. M. Venezia, E. A. Blekkan, A. Holmen, Evidence for Diffusion-Controlled Hydrocarbon Selectivities in the Fischer-Tropsch Synthesis Over Cobalt Supported on Ordered Mesoporous Silica. Topics in catalysis 2011; 54, F. Lundvall, D. S. Wragg, M. Tilset (5,5 -Dimethyl-2,2 -bipyridine)iodidotrimethylplatinum(iv) Acta Crystallographica Section E Structure Reports Online, 67 (2011) M617-U1037. R. Lødeng, E. Bjørgum, B. C. Enger, J. L. Eilertsen, A. Holmen, B. Krogh, I. Aartun, M. Rønnekleiv, E. Rytter A fixed-bed reactor study of CH 4 -CPO over Rh/Al 2 O 3 ; An indication of a direct pathway to CO. Topics in Catalysis, 54 (2011) O. Mihai, D. Chen, A. Holmen, Catalytic Consequence of Oxygen of Lanthanum Ferrite Perovskite in Chemical Looping Reforming of Methane. Industrial & Engineering Chemistry Research, 50(5) (2011) D. Mores, J. Kornatowski, U. Olsbye, B. M. Weckhuysen Coke Formation during the Methanol-to-Olefin Conversion: In Situ Microspectroscopy on Individual H-ZSM-5 Crystals with Different Bronsted Acidity Chemistry A European Journal, 17(10) (2011) F. Mudu, B. Arstad, H. Fjellvåg, U. Olsbye Thermodynamic Control of Product Formation During the Reaction Between CH 4 and Pt Promoted Ceria-zirconia Solid Solutions. Catalysis Letters, 141(1) (2011) A. Nanoti, S. Dasgupta, V. Agnihotri, P. Gupta, A. N. Goswami, M. O. Garg, E. Tangstad, M. Stöcker, A. Karlsson, Ø. B. Vistad A zeolite based vapor phase adsorptive desulfurization process for naphtha Microporous and Mesoporous Materials, 146 (2011) O. Mihai, D. Chen, A. Holmen Catalytic Consequence of Oxygen of Lanthanum Ferrite Perovskite in Chemical Looping Reforming of Methane. Industrial & Engineering Chemistry Research 2011; Volum 50.(5) s U. Olsbye, O. V. Saure, N. B. Muddada, S. Bordiga, C. Lamberti, M. H. Nilsen, K. P. Lillerud, S. Svelle, «Methane conversion to light olefins-how does the methyl halide route differ from the methanol to olefins (MTO) route?» Catalysis Today 2011; Volume 171.(1) s Q. Li, Z. Sui, Z. Zhou, Z. Xinggui; Y. Zhu, J. Zhou, D. Chen Coke Formation on Pt-Sn/Al2O3 Catalyst in Propane Dehydrogenation: Coke Characterization and Kinetic Study. Topics in catalysis 2011;Volum 54.(13-15) s

44 44 M. Palcut, R. Knibbe, K. Wiik, T. Grande Cation interdiffusion between LaMnO3 and LaCoO3 materials. Solid State Ionics, 202(1) (2011) E. Rauwel, P. Rauwel, F. Ducroquet, I. Matko, A. C. Lourenço Metallic oxygen barrier diffusion applied to high-κ deposition Journal of Vacuum Science & Technology B, 29 (2011) doi: / P. Rauwel, O. M. Løvvik, E. Rauwel, J. Taftø Nanovoids in thermoelectric β-zn4sb3: A possibility for nanoengineering via Zn diffusion Acta Materialia, 59(13) (2011) P. Rauwel, O. M. Løvvik, E. Rauwel, E. S. Toberer, G. J. Snyder, J. Taftø Nanostructuring in β-zn4sb3 with variable starting Zn compositions Physica Status Solidi A Applications and Materials Science, 208(7) (2011) M. L. Rosenberg, K. Vlas aná, N. S. Gupta, D. Wragg, M. Tilset Highly cis-selective Rh(I)-Catalyzed Cyclopropanation Reactions. Journal of Organic Chemistry, 76(8) (2011) E. Rytter, S. Eri, D. Schanke, H. Wigum, T. H. Skagseth, Ø. Borg, E. Bergene, Development of an Attrition Resistant Fischer-Tropsch Catalyst for Slurry Operation, Top. Catal. 54 (2011) 801. Saepurahman, M. Visur, U. Olsbye, M. Bjørgen, S. Svelle In Situ FT-IR Mechanistic Investigations of the Zeolite Catalyzed Methylation of Benzene with Methanol: H-ZSM-5 versus H-beta Topics in Catalysis, 54(16-18) (2011) A. P. Shaw, M. Tilset, R. H. Heyn, S. Jakobsen Microwave methods for the synthesis of gold(iii) complexes Journal of Coordination Chemistry, 64(1) (2011) R. Skorpa, S. Bordiga, F. Bleken, U. Olsbye, B. Arstad, J. R. Tolchard, K. Mathisen, S. Svelle, M. Bjørgen Assessing the surface sites of the large pore 3-dimensional microporous material H-ITQ-7 using FT-IR spectroscopy and molecular probes Microporous and Mesoporous Materials, 141(1-3) (2011) R. Skorpa, S. Forselv, K. Mathisen, S. Bordiga, M. Bjørgen, S. Svelle Infrared Spectroscopic Investigation of the Acidity and Availability of the Surface Hydroxyls of Three-Dimensional 12-Ring Zeotype H-ITQ-7 Journal of Physical Chemistry C, 115(24) (2011) L. Sommer, A. Krivokapic, S. Svelle, K. P. Lillerud, M. Stöcker, U. Olsbye Enhanced Catalyst Performance of Zeolite SSZ-13 in the Methanol to Olefin Reaction after Neutron Irradiation Journal of Physical Chemistry C, 115 (2011) H. Song, A. O. Sjåstad, H. Fjellvåg, H. Okamoto, Ø. B. Vistad, B. Arstad, P. Norby Exfoliation and thermal transformations of Nb-substituted layered titanates Journal of Solid State Chemistry, 184(12) (2011) C. Sprung, B. Arstad, U. Olsbye Methane Steam Reforming Over Ni/NiAl 2 O 4 Catalyst: The Effect of Steam-to-Methane Ratio Catalysis Today 54(16-18) (2011) M. Tagliabue, C. Rizzo, R. Millini, P. D. C. Dietzel, R. Blom, S. Zanardi Methane storage on CPO-27-Ni pellets Journal of Porous Materials, 18 (2011) L. Valenzano, B. Civalleri, S. Chavan, S. Bordiga, M. H. Nilsen, S. Jakobsen, K. P. Lillerud, C. Lamberti Disclosing the Complex Structure of UiO-66 Metal Organic Framework: A Synergic Combination of Experiment and Theory Chemistry Materials, 37(7) (2011) A. van Miltenburg, L. - C. de Ménorval and M.Stöcker Characterization of the pore architecture created by alkaline treatment of H-MCM-22 using 129Xe NMR Spectroscopy Catalysis Today, 168 (2011) E. Vanhaecke, F. Huang, Y. Yu, M. Rønning, A. Holmen, D. Chen. Catalytic consequence of the interface between iron catalysts and foils in synthesis of aligned nanocarbons on foils. Topics in Catalysis, 54 (2011),

45 A. Venugopal, A. B. Shaw, K. W. Törnroos, R. H. Heyn, M. Tilset Synthesis of a Coordinatively Labile Gold(III) Methyl Complex Organometallics, 30(12) (2011) Y. Wang, Z. Chao, D. Chen, H. A. Jakobsen SE-SMR process performance in CFB reactors: Simulation of the CO2 adsorption/desorption processes with CaO based sorbents. International Journal of Greenhouse Gas Control, 5(3) (2011) E. S. Wangen, A. Osatiashtiani, E. A. Blekkan Reforming of Syngas from Biomass Gasification: Deactivation by Tar and Potassium Species. Topics in Catalysis, 54 (2011) D. S. Wragg, M. A. K. Ahmed, O. Nilsen, H. Fjellvåg E)-1-(2-Iodophenyl)-2-phenyldiazene. Acta Crystallographica Section E Structure Reports Online, 67 (2011) O2326-U174. L-M. Yang, P. Vajeeston, P. Ravindran, H. Fjellvåg, M. Tilset, Revisiting isoreticular MOFs of alkaline earth metals: a comprehensive study on phase stability, electronic structure, chemical bonding, and optical properties of A-IRMOF-1 (A = Be, Mg, Ca, Sr, Ba). Physical Chemistry, Chemical Physics - PCCP 2011;Volum 13.(21) s L-M. Yang, Y.-A. Zhu, C. Fan, Z.-J Sui, D. Chen, X.-G. Zhou DFT study of propane dehydrogenation on Pt catalyst: effects of step sites. Physical Chemistry Chemical Physics, 13(8) (2011) S. Zarubova, S. P. Rane, J. Yang, Y. Yu, Y. Zhu, D. Chen, A. Holmen Fischer-Tropsch Synthesis onhierarchically Structured Cobalt Nanoparticle/ Carbon Nanofiber/Carbon Felt Composites. ChemSusChem, 4(7) (2011) Q. Zhou, P. Li, X.-L. Wang, X.-G. Zhou, D. Yang, D. Chen Preparation of CNF-supported Pt catalysts for hydrogen evolution from decalin. Materials Chemistry and Physics, 126(1-2) (2011) InGAP Oral presentations at international and national conferences from ingap and ingap-associated projects E. Blekkan «Anders Holmen: Highlights.» Seminar Katalyse: Anders Holmen; E. Blekkan «GTL - Gas to liquids Biomass-to-liquids (BTL).» Gasskonferansen; E. Blekkan «Hydrogen adsorption on supported cobalt catalysts for the Fischer-Tropsch synthesis studied by microcalorimetry.» Norwegian Catalysis Symposium 2011; D. Chen «Nanomaterials for energy storage.» Nanolab Seminar»; D. Chen «Towards an efficient hydrogen production from biomass. 1st international symposium on chemistry for energy conversion and storage; D. Chen «3D engineering design of nano-structured composites for energy storage». The 3rd Global Chemical Engineers Seminar; S. Chytil, A. M. Lind, A. H. Lillebø, B.C. Enger, A. Holmen E. A. Blekkan, «Biomass to liquid fuels BTL». 2nd Trondheim Gas Technology Conference; NTNU SINTEF H. J. Dar, S. U. Nanot, K.J. Jens, E. Tangstad, D. Chen «Kinetic analysis of gas phase oxidative dehydrogenaton for ethane to ethylene at atmospheric pressure.» InGap-seminar; M. Diskus, O. Nilsen, H. Fjellvåg, S. Diplas, B. Weckhuysen Innovative characterization techniques for MoO 3 ALD coatings 11 th International Conference on Atomic Layer Deposition, Boston (USA) June 26-29,

46 M. Diskus, O. Nilsen, H. Fjellvåg, B. Weckhuysen Influence of the precursors chemistry on the ALD growth of cobalt-molybdenum oxide films 11 th International Conference on Atomic Layer Deposition, Boston (USA) June 26-29, E. A. Eilertsen Nonaqueous Fluoride/Chloride Anion- Promoted Delamination of Layered Zeolite Precursors: Exfoliation of PREFER Norwegian Catalysis Symposium, Lillestrøm (Norway) September 28-29, E.A. Eilertsen, M. Haouas, K.P. Lillerud, F. Taulelle, Francis, «Connectivity analysis of aluminum and silicon in the clear sol precursor of SSZ-13 chabazite-type zeolite.» FEZA 2011; B. C. Enger, V. Frøseth, E. Rytter, A. Holmen, «Effects of Zn during SSITKA studies of Co-Re/γ-Al2O3 catalysts in the Fischer-Tropsch synthesis». EuropaCat X; M. W. Erichsen, Marius Westgård, «H-SAPO-5 as model catalyst for methanol conversion: Does a lower acid strength shift the alkene formation mechanism?» ingap seminar 2011; J. M. Gonzalez-Carballo, J. Yang, S. Garcia, M. Ojeda, A. Holmen, J. L. G. Fierro, S. Rojas, «Ruthenium particle size effect on the Fischer-Tropsch synthesis». EuropaCat X; L. Gorelkin, E. A. Blekkan Concepts and Models of the Catalytic Dehydrogenation of Propane. 22nd North American Catalysis Society Meeting (NACSM 2011); R. H. Heyn Chemistry for the Conversion of CO2 Norwegian Catalysis Symposium, Lillestrøm (Norway) September 28-29, R. H. Heyn Utilization of CO 2 via Catalysis with Ionic Liquids. 11 th International Conference on Carbon Dioxide Utilization (ICCDU-XI), Dijon (France) June 27-30, A. Holmen «Alumina Supported Co Calysts for Fischer- Tropsch Synthesis. Effect of Particle Size and Alumina Modifications on Activity and Selectivity.» Norwegian Catalysis Symposium 2011; A. Holmen, H. Venvik, «Microstructured reactors for production and conversion of synthesis gas.» Colloquium on Chemical Reaction Engineering 2011 on Methane Valorization (CCRE-2011); Q. Li, Z. Sui, X. Zhou, D. Chen Kinetic study of propane dehdyrogenation. 6th Asia Pacific Chemical Reaction Engineering Symposium; A. H. Lillebø, C. M. Balonek, S. P. Rane, E. Rytter, E. A. Blekkan, A. Holmen, «Fischer-Tropsch biomass to liquids, effect of Li, Na, K and Ca on Cobalt catalysts.» 1st International Congress on Catalysis for Biorefineries(CATBIOR 2011); A. H. Lillebø, C. M. Balonek, E. Rytter, E. A. Blekkan, A. Holmen «Effects of Li, Na, K and Ca on Co-based Fischer-Troopsch Catalysts». EuropaCat X; S. N.B. Muddada, U. Olsbye, T. Fuglerud, C. Lamberti Ethylene Oxychlorination catalysis- Insight through combined spectroscopy and kinetic tests EuropaCat X, Glasgow (Scotland) August 28 September 2, N.B. Muddada, U. Olsbye, T. Fuglerud, C. Lamberti Ethylene oxychlorination catalysis: role of metal promoters on activity and selectivity of the process 2 nd Trondheim Gas Technology conference, Trondheim (Norway) November 2-3, N.B. Muddada, U. Olsbye, T. Fuglerud, C. Lamberti EXAFS, FTIR and Kinetic studies on CuCl 2 based catalysts for Oxychlorination of Ethylene Norwegian Catalysis Symposium, Lillestrøm (Norway) September 28-29,

47 I. Ogino, E.A. Eilertsen, M. Nigra, S. Hwang, J. M. Ha, T. Rea, S. Zones, A. Katz, «Delamination of Layered Zeolite Precursors under Mild Conditions.» FEZA 2011; U. Olsbye, «Back to basics: Kinetic significance of catalyst supports in methane to syngas processes.» Anders Holmen Symposium; R. Palcheva, M. Palcut Partial oxidation of methane to synthesis gas over Rh promoted perovskite based catalysts Norwegian Catalysis Symposium, Lillestrøm (Norway) September 28-29, E. Patanou, D. Chen, E. A. Blekkan «Microcalometric Studies on Cobalt Supported Catalysts for Fischer- Tropsch Synthesis.» EuropaCat 2011; D. S. G. Panditha Vidana, J. Walmsley, T. T. M. Nguyen, Thoa Thi Minh; E. Edwin, A. Holmen, D. Chen, H. J. Venvik, «Metal dusting corrosion initiation in conversion of natural gas to synthesis gas» 2nd Trondheim Gas Technology Conference; D. S. G. Panditha Vidana, J. Walmsley, H. J. Venvik. Investigation of the initiation of metal dusting corrosion. ingap Seminar; E. Rauwel, O. Nilsen, A. Galeckas, J. Walmsley, E. Rytter, H. Fjellvåg, ALD Applied to Conformal Coating of Nanoporous γ-alumina: Spinel Formation and Luminescence Induced by Europium Doping 220th ECS Meeting and Electrochemical Energy Summit, Boston (USA)October 9-14, E. Rauwel, O. Nilsen, J. Walmsley, E. Rytter, H. Fjellvåg, Oxide coating of nanoporous alumina using ALD to produce highly porous spinel ALD 2011, 11th International Conference on Atomic Layer Deposition, Cambridge (USA) June 26-29, E. Rauwel, O. Nilsen, A. Galeckas, P. Rauwel, Protima, J. Walmsley, E. Rytter, H. Fjellvåg, «ALD applied to conformal coating of nanoporous γ-alumina: Spinel formation and luminescence induced by europium doping.» 12 Trends in Nanotechnology International Conference (TNT2011); E. Rauwel, O. Nilsen, J. Walmsley, E. Rytter, H. Fjellvåg, «ALD system combined with glass powder cell applied to oxide coating of nanoporous γ-alumina.» ingap seminar; E. Rauwel, O. Nilsen, H. Fjellvåg, J. Walmsley, E. Rytter, «ALD applied to ZnO coating of nanoporous γ-alumina particles: Conformal coating and spinel formation.» ingap seminar; M. Surma, T. Fuglerud, C. Lamberti, D. Chen «Transient kinetic investigation of Ethylene Oxychlorination». EuropaCat 2011; S. F. Teketel, W. Skistad, S. Benard, U. Olsbye, K.P. Lillerud, P. Beato, S. Svelle, «Shape Selectivity in the Conversion of Methanol to Hydrocarbon: the Catalytic Performance of 1D 10-ring Zeolite: ZSM- 22, ZSM-23, ZSM-48 and EU-1.» Norwegian Catalysis Symposium; N. Tsakoumis, A. S. Voronov, M. Rønning, Ø. Borg, E. Rytter, A. Holmen An operando study of Co-based Fischer-Tropsch synthesis catalysts. EuropaCat X; H. Venvik, F. Hayer, D. H. Bakhtiary, A. Holmen, P. Pfeifer, R. Dittmeyer, R. Myrstad, Direct synthesis of dimethyl ether in microstructured reactors. EuropaCat X; G. J. B. Voss, V. Evenrud, A.S. Voronov, N. Tsakoumis, M. Rønning «The State of Promotors in Fischer-Tropsch Catalysts» European Summer School Energy and Materials of the Sun 2011,

48 D. S. Wragg Observing Catalyst Behaviour Under Working Conditions With X-ray Diffraction Norwegian Solid State Meeting, Trondheim (Norway) May 20, D. S. Wragg, «Modelling Stacking Faults in Real MTO Catalysts.» ingap Annual Meeting; D. S. Wragg, «Silicon Mobility and Defect Formation in SAPO-34.» ingap Annual Meeting; J. Yang, Ø. Borg, D. Chen, A. Holmen, A study of chain termination and propagation on 20% Co/CNT Fischer-Tropsch Catalyst. EuropaCat X; J. Yang, Ø. Borg, D. Chen, A. Holmen, «A study of chain propagation and termination on a 20% cobalt supported on carbon nanotube (CNT) Fischer- Tropsch catalyst». EuropaCat 2011; J. Yang, D. Chen, A. Holmen A study of chain propagation and termination on a Fischer-Tropsch catalyst. Norwegian Symposium on catalysis; X. Zhou, D. Chen, W. Yuan Structure-Directing Manipulation of Catalyst Surface for Better Kinetic Behaviors. 6th Asia Pacific Chemical Reaction Engineering Symposium; J. Zhu, D. Chen, A. Holmen «Carbon Nanofiber/Graphite Felt (CNF/GF) Composite for Waster Water and Crude Oil Purification.» Carbon conference; J. Zhu, D. Chen, A. Holmen «Selective C-H and C-C bond activation of propane on platinum nanoparticles with different sizes and shapes.» EuropaCat 2011; ingap Poster presentations at international and national conferences from ingap and ingap-associated projects F. Bleken, W. Skistad, K. Barbera, M. Kustova, S. Bordiga, P. Beato, K. P. Lillerud, S. Svelle, U. Olsbye Conversion of Methanol over Novel 3-Dimensional 10-Ring Zeolites 5 th International FEZA conference, Valencia (Spain) July 3-7, F. Bleken, W. Skistad, K. Barbera, M. Kustova, S. Bordiga, P. Beato, K. P. Lillerud, S. Svelle, U. Olsbye Conversion of Methanol over Novel 3-Dimensional 10-Ring Zeolites The 12 th Netherlands Catalysis and Chemistry Symposium, Noordwijkerhout (The Netherlands) February 28 March 2, C. Svatopluk, A. M. Lind, A. H. Lillebø, B. C. Enger, A. Holmen, E. Blekkan Biomass to liquid fuels - BTL. 2nd Trondheim Gas Technology Conference; H. J. Dar, Kinetic analysis of gas phase oxidative dehydrogenation for ethane to ethylene at atmospheric pressure R. Dehghan, A. Voronov, N. Tsakoumis, T. Kasama, R. Holmestad, A. Holmen, E. Rytter, Ø. Borg, J.Walmsley Nano structural analysis of promoted cobalt phase supported on gamma alumina by Transmission Electron Microscopy ingap Seminar, Trondheim, December 1-2, M. W. Erichsen, M. H. Nilsen, S. Svelle, K. P. Lillerud, U. Olsbye Mechanisms of olefin formation in H-SAPO-5 during methanol-to-hydrocarbons (MTH) catalysis The 12 th Netherlands Catalysis and Chemistry Symposium, Noordwijkerhout (The Netherlands) February 28 March 2, M. W. Erichsen H-SAPO-5 as model catalyst in methanol-to-hydrocarbons (MTH) research: Does lower acid strength cause a shift in olefin formation mechanisms? Norwegian Catalysis Symposium, Lillestrøm (Norway) September 28-29,

49 M. W. Erichsen Determination of acidity in zeotype materials - How to obtain dependable measurements of amount and strength of acid sites in H-SAPO-5? ingap Seminar, Trondheim, December 1-2, I. Gorelkin, E. A. Blekkan Concepts and models of the catalytic dehydrogenation of propane. Europacat X; A. H. Lillebø, C. Balonek, E. Rytter, E. A. Blekkan, A. Holmen Effects of Li, Na, K and Ca on Co-based Fischer-Troopsch Catalysts. EuropaCat X; S. Malola, F. Bleken, S. Svelle, O. Swang Computational study of zeolite dealumination and formation of silanol nests 5 th International FEZA conference, Valencia (Spain) July 3-7, M. Palcut, H. Fjellvåg, Oxygen intercallation capacity of delafossite oxides for catalytic applications. 7th Petite Workshop on the Defect Chemical Nature of Energy Materials; E. Patanou, Microcalorimetric studies of H2 and CO on cobalt supported catalysts for Fischer Tropsch synthesis ingap Seminar, Trondheim, December 1-2, N. Pfaff, Zeolite membranes for selective CO 2 - separation Norwegian Catalysis Symposium, Lillestrøm (Norway) September 28-29, E. Rauwel ALD applied to ZnO coating of nanoporous γ-aluminaparticles: conformal coating and spinel formation ingap Seminar, Trondheim, December 1-2, G. Shearer Potential of Metal Organic Frameworks as Photocatalysts ingap Seminar, Trondheim, December 1-2, M. Surma, T. Fuglerud, C. Lamberti, D. Chen Transient kinetic investigation of Ethylene Oxychlorination. EuropaCat X, Glasgow (Scotland) August 28 September 2, S. Svelle Computational study of zeolite dealumination and formation of silanol nests. Norwegian Catalysis Symposium, Lillestrøm (Norway) September 28-29, S. Teketel, Production of Non-aromatic Gasoline from Methanol over Unidirectional 10-ring Zeolite Catalysts ingap Seminar, Trondheim, December 1-2, S. Teketel, W. Skistad, S. Benard, U. Olsbye, K.-P. Lillerud, P. Beato, S. Svelle Production of non-aromatic gasoline from methanol over unidirectional 10-ring zeolite catalysts EuropaCat X, Glasgow (Scotland) August 28 September 2, N. E. Tsakoumis, A. Voronov, M. Rønning, Ø. Borg, E. Rytter, A. Holmen An Operando study of Co-based Fischer-Tropsch synthesis catalysts EuropaCat X, Glasgow (Scotland) August 28 September 2, D. S. G. P Vidana, Investigation of the initiation of metal dusting corrosion, ingap Seminar, Trondheim, December 1-2, A. Voronov, N. E. Tsakoumis, Ø. Borg, E. Rytter, A. Holmen, M. Rønning Deactivation studies of Co-based Fischer-Tropsch catalysts by in-situ spectroscopies at realistic working conditions New Developments in the Field of Synchrotron Radiation, Campinas (Brazil) January 17-25, A. Voronov, Study of surface changes in Co-based Fischer-Tropsch catalysts under realistic working conditions ingap Seminar, Trondheim, December 1-2,

50 G. Voss, J. B. Fløystad, A. Voronov, N. Tsakoumis, M. Rønning, The state of promotors in Fischer- Tropsch catalysts, Poster presentation, EuropaCAT X Congress 2011, Glasgow, Scotland, 28 August - 2 September G. Voss, V. Evenrud, A. Voronov, N. Tsakoumis, M. Rønning, The state of promotors in Fischer- Tropsch catalysts, Poster presentation, European Summer School Energy and Materials from the Sun, Kerkrade, Netherland, June D. S. Wragg, Silicon Mobility and Defect Formation in SAPO-34, ingap Seminar, Trondheim, December 1-2, D. S. Wragg, M. G. O Brien, F. Bleken, M. Di Micheli, U. Olsbye, B. M. Weckhuysen, H. Fjellvåg Watching The Methanol to Olefin Process with Time and Space Resolved X-ray Diffraction 5 th International FEZA conference, Valencia (Spain) July 3-7, E. Zacharaki, Synthesis and Characterization of Metal Nanoparticles (NP)- Development of well defined NP/support Model Catalysts ingap Seminar, Trondheim, December 1-2, ingap and InGAP associated Contributions to Popularization of Science (Presentations and Publications) R. H. Heyn CO2 mer enn avfall for deponering?, Article, Teknisk Ukeblad, 158(14) (2011) 83. R. Lødeng Energikilder i endring, Article, Teknisk Ukeblad, 15 (2011) 67. U. Olsbye Hvordan lage drivstoff og plast uten olje, Invited lecture, Det internasjonale kjemiåret, Bergen (Norway) November 4, U. Olsbye Centres for Research-based Innovation - expected versus real impact on industry and university partners OECD workshop on new incentive funding, Paris (France) November 29, U. Olsbye Kjemikerne løser verdensproblemer Forskningsdagene annonsebilag utgitt av Norges Forskningsråd [Avis] M. Zokaie, M. H. Nilsen, U. Olsbye, K. P. Lillerud, O. Swang Proton Redistribution in Silicon Island of SAPO Material 5 th International FEZA conference, Valencia (Spain) July 3-7, M. Zokaie Silicon island in SAPO materials: Thermodynamic consideration from atomistic modeling Norwegian Catalysis Symposium, Lillestrøm (Norway) September 28-29, S. Øien Synthesis and characterization of platinumcontaining UiO-67 Zr-based metal organic framework Norwegian Catalysis Symposium, Lillestrøm (Norway) September 28-29,

51 AFM (Atomic Force Microscopy) surface of a SAPO-34-crystal. The top picture is in phase which gives a shadow effect and the bottom picture shows the topography. 51

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