Catalytic conversion of pyrolysis gas in the WoodRoll process for enhanced process reliability Pouya H. Moud1), Dennis Fällén Holm1), Alfred Halvarsson1), Klas Andersson2), Efthymios Kantarelis1), Marko Amovic3), Rolf Ljunggren3), Klas Engvall1) 1) KTH, Dept of Chemical Engineering, Stockholm 2) Haldor Topsoe A/S, Kgs. Lyngby, Denmark 3) Cortus Energy AB, Kista Nyheter och forskningsresultat om energigas 8-9 June 2017, Göteborg

Scope of study The scope of the project was to perform an early evaluation of a technical solution, based on a catalytic conversion, simplifying the conveying of the pyrolysis gas in pipelines and valves, as well as improve combustion properties in the radiant heat tube burners. ”Raw pyrolysis gas with 35-40% oil” Filter Catalytic reactor Burners ”Energy gas with lighter CxHy” Pyrolytic residues

Outline Cortus Energy The WoodRoll® technology Experimental tests and methods Results enhanced process reliability Other potential applications Summary

1. Cortus Energy

Cortus Energy Founded in 2006 to develop and commercialize the patented gasification process WoodRoll®. WoodRoll® is a gasification process for biomass, producing clean energy gas with a high energy value. The purity and high energy value of the energy gas makes it suitable for replacing fossil fuels. Listed on Nasdaq OMX First North since february 2013. The company has 12 employees and 10 consultants.

2. The WoodRoll® technology

The WoodRoll® technology Tar free product gas The WoodRoll® thermal gasification technology is an integrated process for converting wet solid biomass to clean syngas in three steps, drying, pyrolysis and gasification. The process is fully allothermal from wet biomass to clean syngas. Tar and higher hydrocarbons in a pyrolysis gas is incinerated to indirectly generate the heat for the endothermic gasification process. Excess heat is used counter current the biomass processing to syngas. This means that the hot flue gases from the indirect heating of the gasifier is the heat source for the pyrolysis process. Finally, the excess heat from the pyrolysis is enhancing the dryer. In this manner a thermal yield of 80% can be reached for wet biomass to clean syngas.

The WoodRoll® technology Biofuels 20 biofuels verified Drying Controlled dusting and condensate Single percentage humidity in operation Pyrolysis Combustion stable Char yield [T, Xi] 35% ±10% Pyrolysis oil yield 35% ±10% Gasification >99% Conversion rate reached Ash melting only for chemical sludge Clean product gas

3. Experimental setup and methods

Experimental setup and methods Experiments on-site in Köping Wood chips of GROT Real biomass pyrolysis gas including bio-crude Sampling before and after catalytic reactor Tests included Fe-based material and dolomite mineral as catalysts

Experimental setup and methods Pyrolysis gas line Pyrolyser Burner Permanent gases and oil samples

Experimental setup and methods Pyrolysis oil sampling Basic evaluation Permanent gas analysis Bio-crude analyses Gravimetric C/H/O Catalyst characterization Surface area Carbon laydown TPO XRD Mass balance evaluation for C,H,O Extended analysis Bio-crude analyses H-NMR GC/MS Proposed mechanism

4. Results enhanced process reliability

Experimental conditions Experimental conditions using Fe-based catalyst The pyrolysis gas was treated under stable conditons for 8 hours with the iron-based catalyst The dolomite bed collapsed totally after 30 minutes of use

Operational stability catalytic bed T-profile inside the reactor versus time on stream Initial activation Stable operation TC TC TC Successful activation of the catalyst Fluctuation in temperature due to initial activation Stable T-profiles after activation Catalytic effect remained despite surface S and C

Permanent gases Average molar flow rates of permanent gases A significant increase of hydrogen Increase in H2 and CO2 content WGS activity

Mass distribution and bio-crude analysis C/H/O analysis (dry basis), water content, S/C, O/C, and H/C of the raw and treated solvent-free condensate 51% reduction in bio-crude content Decrease in oxygen content Increase in S/C ratio => lower carbon formation on catalyst

Burner performance More rapid combustion of the treated pyrolysis gas, resulting in a more evenly distributed temperature profile. Combustion zone for treated oil is longer than raw oil.

Burner performance Lower NOx implies a more uniform combustion

5. Other potential applications

A step for pre-conditioning The change of pyrolysis oil to lighter hydrocarbons, the lowering of oxygen content and the change in permanent gases implies a possible use of the as a pre-conditioning step. Evaluation point at dehydration/decarbonylation of hydrocarbons followed by a subsequent water-gas shift reaction Paper describing in-depth analysis and mechanism is submitted and under review. Dehydration: R-CH2-OH R=CH + H2O Decarbonylation: R-CHO R-H + CO Water-gas shift: CO + H2O CO2 + H2 Potential catalytic process

6. Summary

Summary The catalytic process was successfully used for 8 hours in real pyrolysis gas converting heavy hydrocarbons to lighter ones. A reduction in the amount of bio-crude of approximately 51 % could be achieved in the tests. The gas volume increased significantly after the conversion. The composition of the pyrolysis oil also changed. For example, the amount of oxygen was dramatically reduced after the conversion. Implying less oxygenated compounds. The combustion of the gas in the radiant tube burner displayed a changed behaviour using the treated pyrolysis gas. The combustion started closer to the burner nozzle, which means a longer flame. The iron-based catalytic process has the potential as a pre-reformer step (pre- reformer concept) for bio-crude rich pyrolysis gas The production of hydrogen from pyrolysis gas without hydrogen/steam addition in atmospheric pressure seems to be a viable pathway for hydrogen- rich gas production Experiments with longer exposure time is necessary to investigate the lifetime of the catalyst

KTH collaborators and funding partners

Questions?