SIMULATION OF PROCESSES FOR EFFICIENT METHANOL PRODUCTION USING CO2 AND SOLAR ENERGY

Sven Kluczka 1, Spiros Alexopoulos 2*, Christiane Vaeen 3, Martina Neises 4 and Martin Roeb 5
1 2

M.Sc., University of Applied Sciences Aachen, Solar-Institut Jlich (SIJ), Jlich, Germany.

Dr.-Ing., University of Applied Sciences Aachen, Solar-Institut Jlich (SIJ), Heinrich-Mumann-Str. 5, 52428 Jlich, Germany; Phone: +49(0)241 6009 53522, E-Mail address: alexopoulos@sij.fh-aachen.de
3

Prof. Dr. rer. nat, University of Applied Sciences Aachen, Solar-Institut Jlich (SIJ), Jlich, Germany.
45

Dr. rer. nat., German Aerospace Center (DLR), Linder Hhe, 51147 Cologne, Germany

Abstract An alternative to the excessive use of fossil fuels and the resulting carbon footprint, due to the release of CO2 to the atmosphere, is to generate a CO2-neutral energy source, by chemically binding the energy, coming from solar irradiation, in form of hydrogen or hydrocarbons like methanol. To enable a CO2-neutral energy supply, it is possible to recycle CO2 from industrial exhaust gases and supply it as a base product to the methanol production process. In cooperation with the German Aerospace Centre, the Solar-Institut Jlich is examining and comparing solar production pathways for the generation of methanol from CO2. Within this project, the processes for CO2 extraction and methanol production will be examined and processed. Keywords: Methanol, CO2, synthesis gas, solar energy, methane reforming 1. Introduction The suitability of technical concepts for solar methanol production is dependant on the state of technology, the plant size, local weather conditions, local infrastructure and supply of resources, as well as fuel costs. To develop suitable concepts for different locations, special requirements and assessment criteria have been devised. Possible assessment criteria are for example investment and operating costs or the efficiency of different technologies. Based on this a preselection of locally adjusted concepts has been developed. For these defined concepts the expected amount of produced methanol will be calculated with a developed simulation model and the operating costs will be estimated. Due to the previously defined assessment criteria and the results from simulation and costeffectiveness calculations, an evaluation of the best suitable concepts for different local conditions are possible. 2. Scenario Development and Simulation The main processes that are analyzed are the generation and supply of CO2, the production of hydrogen or synthesis gas respectively and methanol synthesis. During a literature study, some processes have been determined that show a high efficiency and cost-effectiveness, as well as a high potential to implement solar energy into the process [1]. According to three main process fields, the following sub-processes will be analyzed for the scenario development:

 CO2-Generation

Post-Combustion

Post-Combustion describes a secondary measurement to clean up industrial exhaust gases, where CO2 is extracted in a washing process from the flue gas. As absorbing agent watery amine solutions can be used. The alkaline absorbent binds the CO2 chemically reversible. Mostly ethanolamine derivates are used, due to their physical properties like vapor pressure and viscosity. Absorption takes place at temperatures of around 30C and thermal desorption at around 150C. To optimize the rate of yield and the purity of extracted CO2, an upstream dedusting and desulfurization is necessary. The degree of effectiveness with post-combustion is approximately 90%. The process of post combustion is the most technically established one in the field of carbon capture and storage (CCS) [2-4]. o Atmospheric CO2-extraction

Under certain conditions it is possible to extract CO2 from ambient air by using artificial trees. Those continuously absorb CO2 from the air, while the speed of absorption is not only dependent on the prevailing concentrations on the site of operation, but also on the flow-rate of air and the flow conditions. Due to high CO2 concentrations, free inflow and sufficient free space possible sites of operation are highways and offshore regions. The deposition rate of a unit with the size of a natural tree amounts to about 10 t/day, but structure and size of these plants are variable. Sorbents that have been used in the first pilot plants were NaOH- and Ca(OH)2-solutions. Nowadays energetic more efficient sorbents are available that need only so much energy for regeneration that only 5 % of extracted CO2 will be re-emitted. These sorbents are generally artificial resins, which can bind CO2 and sets it free at contact with water [5].
H2-/synthesis gas production (methane reforming)

One possible process to produce synthesis gas while parallel energetically upgrade fossil fuels, is the reforming of methane. Concerning reforming processes, it is distinguished between steam reforming CH4 + H2O 3 H2 + CO and dry reforming with CO2 CH4 + CO2 2H2 + 2CO. Methane steam reforming is a strongly endothermic process. Therefore, in order to adjust the thermodynamic balance, high temperatures are required. Conventional steam reformers are mainly fixed bed reactors that are operated at temperatures between 850 and 1100 K. During the last years, the process of methane dry reformation gained more importance, because it allows the direct transition of CO2 to synthesis gas and therefore a reduction of CO2 emissions. Due to a water-gas shift reaction the amount of H2 in the product gas can be increased while simultaneously decreasing the amount of CO.
Methanol synthesis

The synthesis of methanol from synthesis gas can be implemented at temperatures below 800C. Different types of reactors, like fixed bed, tubular or falling film reactors can be used for this process.

Part of the necessary reaction energy can be implemented into the process in form of solar energy. After methanol synthesis a purification of the reaction products is necessary. In several distillation steps, side products like ethanol or dimethyl ether are extracted from the raw methanol. These side products can also be used as base products for different processes. From theses processes two concept scenarios have been developed that will be simulated to perform production and cost-effectiveness calculations. These scenarios will be described in the following. Scenario 1: Post-combustion CO2 extraction and methane reforming

Figure 1: Scenario 1:Post-Combustion and steam reforming; (1) desulphurisation; (2) flue gas cooler; (3) compressor; (4) CO2-absorber (MEA); (5) MEA-cooler; (6) heat exchanger; (7) CO2-desorber; (8) reboiler; (9) CO2-cooler; (10) CO2-condenser; (11) storage tank; (12) vaporizer; (13) steam reforming reactor; (14) heat exchanger; (15) condenser; (16) tube reactor; (17) hydrogen stripper; (18) hydrogen condenser; (19) distillation column; (20) distillation column; (21) methanol storage

In the first scenario (Figure 1) the CO2-extraction is implemented in form of a post combustion process. Industrial, CO2-containing flue gas will be dedusted and desulfurized and after that, the CO2 fraction will be extracted in an amine washer and finally condensed. The extracted CO2 is then directed to a reforming reactor, where it will be catalytically converted with methane and steam at a reaction temperature of 700C to synthesis gas. In a different reactor, the synthesis gas will be converted under pressure and at a temperature of 250C to methanol. Excess synthesis gas is separated and recycled. To

purify the produced raw methanol, it is distilled in two steps, to extract by-products like dimethyl ether or ethanol. For the sub-process of desulfurization during post combustion a stationary model has been developed with Matlab/Simulink. For all other processes dynamic models have been developed. As input values for these models the mass flows, temperature, pressure, enthalpie and total mass flow have been used. The calculated product flows will then be assigned to the following relevant model and processed. CO2 extraction in the simulated post combustion process is accomplished by an absorber-/desorbersystem, using monoethanol amine (MEA) as solvent. The reaction temperature in the absorber is 40C and in the desorber 90-100C. The simulation model is mainly based on data from the post combustion system which is implemented in the RWE lignite power plant in Niederaussem, Germany [6]. Besides a separate model for desulfuration, the post combustion process is simulated as one complex model, representing the sub-processes absorption, desorption and heat exchange. The process simulation has been performed with Matlab/Simulink. Input values for the main model are the mass flows of CO2, MEA, H2O, N2 and O2 as in liquid as in gaseous state and the mass flows for MEAH+, MEACOO-, HCO3-, OH- and H3O+ in the liquid phase. Furthermore the temperature for the gaseous and liquid phases and the pressures for the absorber and desorber have been used. The input values used for this model originate from a 400 MW lignite power plant that produces one million tons of CO2 per year. Subsequent to the post combustion model is the model for steam reforming for the production of synthesis gas. The reforming process is simulated with a model of a single-step primary tubular reactor with a fixed catalyst bed. This simulation model is based on industrial standard reforming reactors of the companies Uhde, Lurgi and Topse. In a first step, the model is designed to simulate a standard steam reforming process, using steam and methane as feed. Parallel to the simulation work, field tests in a small lab plant are performed, to gather input values for a dry reformation process. In a tubular reactor, equipped with different fixed bed catalyst mountings (NiO/CaAl12O19, NiO/MgO, Ru/Al2O3) process parameters and long term catalyst behavior during methane dry reforming with CO2 are analyzed (Figure 2). The received results are then used to optimize the existing model for steam reformation to utilize the CO2, extracted during post combustion.

Figure 2: Furnace tube reactor for methane dry reformation

To simulate the standard steam reforming process, a one dimensional pseudohomogenous model of a tubular reactor has been developed. In the developed model only one tube is simulated and the results of this simulation have to be extrapolated. Due to the fact that the reactor model only displays one subprocess of the scenario, it is necessary that the calculations have to be performed in very short amount of time to guarantee a smooth performance of the model and a short simulation time. Therefore the reactor was designed as a one dimensional pseudohomogenous model, which demands less time for calculation. It is possible to perform simulations under non-critical conditions to analyze the performance of the process. The chosen input parameters that have been used to develop the model are shown in Table 1. Tube layout: Educts: CH4, H2O, H2, CO2, N2 Products: CH4, H2O, CO, H2, CO2, N2 Entrance reactor temperature: 793 K Total pressure in the reactor: 29 bar
Table 1: Standard simulation parameters for a tubular reactor for methane steam reformation

Following the results of the previous models, the model for the methanol synthesis reactor was designed. CO2, which was produced in the post combustion process as well as the synthesis gas from steam reforming are used as feed for the methanol reactor. Inside of the reactor following reactions occur: CO2 + 3 H2 CH3OH + H2O CO + 2 H2 CH3OH Based on input data of a small-scale tubular reactor, mounted with a Cu/ZnO/Al2O3 catalyst, the model was developed [7]. To reach an industrial production standard, the calculated results will be extrapolated afterwards. To optimize the purity of the raw methanol produced in the reactor, a three step purification unit is added downstream of the reactor. In a first step the remaining hydrogen in the product will be extracted and recycled. Furthermore, in two distillation steps the remaining traces of ethanol and dimethyl ether will be extracted. Besides scenario 1 a second scenario that displays the opportunities for solar methanol synthesis has been developed. This scenario was developed as a small scale stand alone system, which represents the extraction of CO2 from the atmosphere as well as photocatalytical methanol synthesis. Artificial trees absorb CO2 directly from the air and desorb it in a solvent solution. The extracted CO2 will be compressed and directed to a reactor tube, embedded in a parabolic trough receiver, where, in combination with water and a photocatalyst, methanol will be produced. Scenario 2 is especially designed for small, local applications for example close to highways or off-shore regions. 3. Conclusions and Outlook

All necessary components of the two scenarios have been simulated with Matlab/Simulink. Each single model has to be further optimized in order to enable a smooth simulation and calculation of annual outcomes of the complete scenario. The calculation time has to be reduced and the product mass flows have to be adjusted to connect the single models to one continuous process. Furthermore modules have to be developed, to implement the use of solar energy into the model. One possible solution to use solar energy is to use concentrated solar radiation to generate the necessary reaction temperature for methane reformation. The process temperature of 850C can be generated with a volumetric receiver-reactor, mounted on top of solar tower. With a heliostat field, sunlight will be bundled and focused into the reactor. Additionally, the excess heat, which is generated during this process, can be used for low temperature applications (CO2 resorption, methanol synthesis) in the scenario. To optimize the developed model to use concentrated sunlight as energy source, it is possible to use already existing models (i.e. for heliostat fields or heat exchanger). Acknowledgements SolMethCO2 is a Ziel-2 project of the EU co-funded by the Ministry of Innovation of North RhineWestphalia (NRW). References [1] S. Kluczka, M. Schmitz, M. Roeb, C. Vaeen, Methanol from CO2 and Solar Energy A Literature Study, Journal of Energy and Power Engineering, 6/3 (2012) 361-369 [2] Fischedick, M.; Esken, A.; Pastowski, A.; Schwer, D.; Supersberger, N.; Viebahn, P.; Bandi, A.; Zuberbhler, U.; Edenhofer, O.; RECCS Strukturell-konomisch-kologischer Vergleich regenerativer Energietechnologien (RE) mit Carbon Capture and Storage (CCS). Final report (2007), Federal Ministry of Environment, Nature Conservation and Nuclear Safety [3] Mller, D.; CCS Eine Technologie fr den Klimaschutz, Vattenfall Europe AG,
http://www.vattenfall.de/www/vf/vf_de/225583xberx/228407klima/228587co2f/index.jsp

[4] Jockenhoevel, T.; Schneider, R.; Rode, H.; Development of an Economic Post-Combustion Carbon Capture Process. Energy Procedia 1/1 (2009) 1043-1050 [5] Wright, A.; Lackner, K.; Peters, E.; Removal of Carbon Dioxide from Air; United States Patent (2010) Patent No. US 7,655,069 B2 [6] Moser, P.; Schmidt, S.; Sieder, G.; Garcia, H.; Ciattaglia, I.; Klein, H.; Enabling Post Combustion Capture Optimization The Pilot Plant Project in Niederaussem; Energy Procedia 1 (2009) 807-814 [7] K.M Vanden Bussche, G.F. Froment, A Steady-State Kinetic Model for Methanol Synthesis and the Water Gas Shift Reaction on a Commercial Cu/ZnO/Al2O3 Catalyst, Journal of Catalysis 161 (1996) 1-10