Dr. Holger Ruland - Catalytic Technology

Dr. Holger Ruland
Head of Group Catalytic Technology
Department Heterogeneous Reactions

Vita

DiplomaUniversität zu Köln, Dipl.-Chem. (2007)
PhD / PostdocRuhr University Bochum (Laboratory of Industrial chemistry, Prof. M. Muhler) (2007-2016)
PostdocMPI CEC (Heterogeneous Reactions, Prof. R. Schlögl) (2016)
Group LeaderMPI CEC 'Catalytic Technology' (since 2018)

Publications

Download: Publikationsliste (.pdf)

2018

  • J. Schittkowski, H. Ruland, D. Laudenschleger, K. Girod, K. Kähler, S. Kaluza, M. Muhler, R. Schlögl, Methanol Synthesis from Steel Mill Exhaust Gases: Challenges for the Industrial Cu/ZnO/Al2O3 Catalyst, Chemie Ingenieur Technik 90 (2018) 1419-1429.
  • H. Song, C. Watermann, D. Laudenschleger, F. Yang, H. Ruland, M. Muhler, The effect of the thermal pretreatment on the performance of ZnO/Cr2O3 catalysts applied in high-temperature methanol synthesis, Molecular Catalysis 451 (2018) 76-86.

2017

  • H. Song, D. Laudenschleger, J.J. Carey, H. Ruland, M. Nolan, M. Muhler, Spinel-Structured ZnCr2O4 with Excess Zn Is the Active ZnO/Cr2O3 Catalyst for High-Temperature Methanol Synthesis, ACS Catalysis (2017) 7610-7622.
  • P. Kangvansura, L.M. Chew, C. Kongmark, P. Santawaja, H. Ruland, W. Xia, H. Schulz, A. Worayingyong, M. Muhler, Effects of Potassium and Manganese Promoters on Nitrogen-Doped Carbon Nanotube-Supported Iron Catalysts for CO2 Hydrogenation, Engineering 3 (2017) 385-392.

2016

  • J. Anton, J. Nebel, C. Göbel, T. Gabrysch, H. Song, C. Froese, H. Ruland, M. Muhler, S. Kaluza, CO Hydrogenation to Higher Alcohols over Cu-Co-Based Catalysts Derived from Hydrotalcite-Type Precursors, Topics in Catalysis 59 (2016) 1361-1370.
  • W. Dong, P. Chen, W. Xia, P. Weide, H. Ruland, A. Kostka, K. Köhler, M. Muhler, Palladium Nanoparticles Supported on Nitrogen-Doped Carbon Nanotubes as a Release-and-Catch Catalytic System in Aerobic Liquid-Phase Ethanol Oxidation, ChemCatChem 8 (2016) 1269-1273.
  • L.M. Chew, W. Xia, H. Düdder, P. Weide, H. Ruland, M. Muhler, On the role of the stability of functional groups in multi-walled carbon nanotubes applied as support in iron-based high-temperature Fischer–Tropsch synthesis, Catalysis Today 270 (2016) 85-92.
  • J. Anton, J. Nebel, H. Song, C. Froese, P. Weide, H. Ruland, M. Muhler, S. Kaluza, The effect of sodium on the structure–activity relationships of cobalt-modified Cu/ZnO/Al2O3 catalysts applied in the hydrogenation of carbon monoxide to higher alcohols, Journal of Catalysis 335 (2016) 175-186.

2015

  • W. Dong, S. Reichenberger, S. Chu, P. Weide, H. Ruland, S. Barcikowski, P. Wagener, M. Muhler, The effect of the Au loading on the liquid-phase aerobic oxidation of ethanol over Au/TiO2 catalysts prepared by pulsed laser ablation, Journal of Catalysis 330 (2015) 497-506.
  • Bordoloi, J. Anton, H. Ruland, M. Muhler, S. Kaluza, Metal-support interactions in surface-modified Cu-Co catalysts applied in higher alcohol synthesis, Catalysis Science & Technology 5 (2015) 3603-3612.
  • J. Anton, H. Ruland, S. Kaluza, M. Muhler, Fast and Reproducible Testing of Cu-Co-Based Catalysts Applied in the Conversion of Synthesis Gas to Ethanol and Higher Alcohols, Catalysis Letters 145 (2015) 1374-1381.
  • J. Anton, J. Nebel, H. Song, C. Froese, P. Weide, H. Ruland, M. Muhler, S. Kaluza, Structure–activity relationships of Co-modified Cu/ZnO/Al2O3 catalysts applied in the synthesis of higher alcohols from synthesis gas, Applied Catalysis A: General 505 (2015) 326-333.

2014

  • L.M. Chew, H. Ruland, H.J. Schulte, W. Xia, M. Muhler, CO2 hydrogenation to hydrocarbons over iron nanoparticles supported on oxygen-functionalized carbon nanotubes, Journal of Chemical Sciences 126 (2014) 481-486.
  • L.M. Chew, P. Kangvansura, H. Ruland, H.J. Schulte, C. Somsen, W. Xia, G. Eggeler, A. Worayingyong, M. Muhler, Effect of nitrogen doping on the reducibility, activity and selectivity of carbon nanotube-supported iron catalysts applied in CO2 hydrogenation, Applied Catalysis A: General 482 (2014) 163-170.
  • H. Ruland, W. Busser, H. Otto, M. Muhler, Effect of Constant-Rate Reduction on the Performance of a Ternary Cu/ZnO/Al2O3 Catalyst in Methanol Synthesis, Chemie Ingenieur Technik 86 (2014) 1890-1893.

2012

  • M. Peter, M.B. Fichtl, H. Ruland, S. Kaluza, M. Muhler, O. Hinrichsen, Detailed kinetic modeling of methanol synthesis over a ternary copper catalyst, Chemical Engineering Journal 203 (2012) 480-491.

2011

  • M. Behrens, S. Kißner, F. Girsgdies, I. Kasatkin, F. Hermerschmidt, K. Mette, H. Ruland, M. Muhler, R. Schlögl, Knowledge-based development of a nitrate-free synthesis route for Cu/ZnO methanol synthesis catalysts via formate precursors, Chemical Communications 47 (2011) 1701-1703.

Group members

Scientific staff

  • Dr. Jorge Iván Salazar Gómez
  • Dr. Julian Schittkowski

Postdocs

  • Dr. Jiayue He
  • Dr. Oliver Hegen
  • Dr. Simon Ristig
  • Dr. Nuria Sánchez Bastardo
  • Dr. Huiqing Song

PhD students

  • Jan Markus Folke
  • Omar Alberto Mayorga Vielma (Guest)
  • Denise Rein

Lab staff

  • Dennis Ernst
  • Jan Niklas Filipp
  • Janina Jaspert
  • Christian Klucken
  • Martha Sojka
  • Agnes Stoer
  • Johanna Taing

Scientific/technical staff

  • Christina Grünwald

Catalytic technology group

In the catalytictechnology group heterogeneously catalyzed reactions are investigated.Catalysis is of major importance for an energy-effective and sustainableconversion of reactants as it lowers the activation barrier of a chemicalreaction by changing its reaction mechanism. In heterogeneous catalysis,usually, the catalyst is a solid, whereas the reactants exist in thesurrounding fluid phase.  Deeperunderstanding of catalytic processes can help to improve the efficiency ofreactions and, therefore, help to save resources and lower the overall energydemand.

In the catalytictechnology group reactions are focused, which are of interest in the scope ofenergy conversion and storage. Nowadays, solar, wind, and hydro energy areoften regarded as sustainable energy sources and can help to solve the shortageof hydro carbon-based energy sources in an environmentally friendly way.Electro-catalytic hydrogen production is investigated in the institute and isoften discussed as key technology to store the fluctuatingly appearingrenewable energies. Numerous techniques to store the hydrogen have beensuggested including the generation of ammonia and methanol, which areinvestigated in the catalytic technology group. Both substances offer theadvantage of high hydrogen contents and are easy to store as they arecondensable [1].

Analysis of exhaust gases of steel mill plants

Besides the electro-catalytic generated hydrogen different other chemical source materials can play an important role in chemical industry for the future. In the catalytic technology group the capability of the usage of industrial exhaust gases as potential hydrogen, carbon and/or nitrogen sources for methanol and ammonia synthesis is investigated. An extensive analysis of real exhaust gases from steel mill plants is performed for all kind of trace components including metals, sulfur-, nitrogen-, and chlorine-containing compounds, polycyclic aromatic hydrocarbons, as well as benzene, toluene, ethylbenzene, and xylene (BTEX-aromatics), and for many other gaseous components. Off-line exhaust gas analysis from blast furnace gas, coke oven gas, and converter gas were already performed. As the complex composition of the exhaust gases depends on the production conditions as well as the raw materials and is, therefore, time dependent, a detailed continuous analysis over longer time periods is mandatory. That is why in the catalytic technology group two mobile containers (a Lab-container and a Supply-container) were designed and constructed within the Project HügaProp (German: Hüttengasproperties), which was funded by the Federal Ministry of Education and Research (German: Bundesministerium für Bildung und Forschung BMBF, Förderkennzeichen 03EK3546). The Lab-container is a mobile high-end gas analysis laboratory housed in a container to analyze the steel mill gases directly on-site. It is equipped with a new generation PTR-SRI-QiTOF-MS for high performance analysis and reactor set-ups for catalytic testing in methanol. The exhaust gas analysis of the steel mill plants will be performed within the project Carbon2Chem in the subproject L0, which is also funded by the Federal Ministry of Education and Research (German: Bundesministerium für Bildung und Forschung BMBF, Förderkennzeichen 03EK3038C).

Methanol synthesis

Nowadays methanolis produced from feed gas mixtures containing CO, CO2, and H2in a conventional, continuously performed process using a Cu/ZnO/Al2O3catalyst. As the Cu/ZnO/Al2O3 system is also active inthe hydrogenation of pure CO2 without CO in the feed gas, themethanol synthesis starting from CO2/H2 mixtures is apromising candidate to help to stabilize the CO2 level of theatmosphere. Simultaneously, a re-incorporation of the green-house gas CO2into the value added chain of the industrial chemistry can be achieved asmethanol is the most important alcohol with respect to its production volumeand numerous applications. A future sustainable and environmental friendlyproduction route from exhaust gases renders a deeper understanding of the CO2hydrogenation and an expansion of the known parameter space of a Cu-basedcatalyst important. The usage of CO2-rich feed gases, possiblywithout any CO at all, and dynamic operation conditions pose typical challengesfor such a process and are investigated in the catalytic technology group. Theinfluence of parameters such as pressure, temperature and space velocity isinvestigated with respect to the reaction performance to help to establish afundament for the usage of exhaust gases of e.g. steel mill plants [2].

In the catalytictechnology group reactivity studies of the CO2 hydrogenation areperformed within the project Carbon2Chemin the subproject L2 (ProMeOH -Methanolsynthese aus Hüttengasen), which is funded by the Federal Ministryof Education and Research (BMBF, Förderkennzeichen 03EK3039D). The reactorapplied houses sufficient catalyst to determine the productivity by volumetricanalysis of condensate and high-precision GC-MS product analysis. Furthermore,the influence of impurities of the exhaust gases on the catalyst activity andstability is investigated. To find out to which extent gas purification isnecessary, systematic reactivity and stability studies in methanol synthesishave been started. Feed gases consist of COx, hydrogen, andadditionally trace components, which are usually found in the exhaust gases,like benzene as a representative of BTEX-aromatics.

Ammonia synthesis

Ammonia synthesisrepresents an additional way to store hydrogen produced with renewable energysources. It is well known that ammonia synthesis is a structure sensitivereaction [3]. Nevertheless, there is still a large pressure and material gapbetween activity data at industrial relevant conditions and surface scienceapproaches. That is why it was planned to investigate a systematic series ofcatalysts with different surface structures and to correlate their activity totheir structure. For this purpose the catalytic technology group investigatesthe activity and stability of alternative Fe-based catalyst systems in akinetic flow set-up [4].Another key point in the alternativecatalyst preparation routes is the circumvention of the high-temperature meltingprocess of the iron oxide precursor. Such a “green” synthesis allows studyingthe interplay of morphology and promoter chemistry in the formation of theactive iron species.

A special reactorwas constructed allowing the disassembly of the catalyst inside a glove boxwithout contact to the ambient for ex-situ characterization methods. This mayhelp to elucidate whether surface, subsurface, or bulk nitride species aregenerated during the reaction, as the active phase of the Fe-based catalystunder industrially used conditions is still unclear [5]. The very lowconversion in ammonia synthesis at mbar pressure precludes direct in-situanalysis and the extreme air-sensitivity of the activated catalysts representsa major hurdle in getting insight into the chemistry of the active form ofammonia iron.

Oxidative dehydrogenation of ethyl benzene

For the investigations of the oxidative dehydrogenation (ODH) of ethylbenzene forming styrene, a kinetic flow set-up was constructed in the catalytic technology group. ODH is an energy saving candidate for the synthesis of styrene. Additionally, ODH can also be employed for the characterization of carbon materials, which are produced in the “carbon synthesis and application” group in the institute. Carbon materials are active in the ODH reaction and are, therefore, interesting and cost-effective materials [6]. (Di)carbonyl surface functional groups that can be modified by additional dopants such as nitrogen are assigned to be the active sites [7]. An extensive characterization and correlation to activity data can shed light into this assignment. If the structure-activity relation is identified, the ODH of ethyl benzene can outstandingly supplement the existing characterization methods and can be incorporated perfectly in the master plan of the institute.

References

[1] Jensen, J. O.; Vestbø, A. P.; Li, Q.; Bjerrum, N. J., J. Alloys Compd. (2007) 446-447, 723.

[2] Bukhtiyarova, M., Lunkenbein, T., Kähler, K., Schlögl, R., Catal. Lett. (2017) DOI: 10.1007/s10562-016-1960-x.

[3] Schlögl, R., Ammonia Synthesis. In Handbook of Heterogeneous Catalysis, 2 ed.; Ertl, G.; Knözinger, H.; Schüth, F.; Weitkamp, J., Eds. Weinheim (2008).

[4] Ortega, K.F., Rein, D., Lüttmann,, C., Heese, J., Özcan, F., Heidelmann, M., Folke, J., Kähler, K.,  Schlögl, R., Behrens, M., ChemCatChem, DOI: 10.1002/cctc.201601355.

[5] Kandemir, T., Schuster, M.E.,  Senyshyn, A., Behrens, M., Schlögl, R., Angew. Chem. Int. Ed. (2013) 52, 12723.

[6] Delgado, J., Chen, X., Frank, B., Su, D.S. , Schlögl, R., Catal. Today (2012) 186, 93.

[7] Rinaldi, A., Zhang, J., Frank, B., Su, D.S., Hamid, S.B.A., Schlögl, R. ChemSusChem (2010) 3, 254.

Projects