Christian Wieckert

Solar-driven gasification of carbonaceous feedstock—a review

Given the future importance of solid carbonaceous feedstocks such as coal, coke, biomass, bitumen, and carbon-containing wastes for the power and chemical industries, gasification technologies for their thermochemical conversion into fluid fuels are developing rapidly. Solar-driven gasification, in which concentrated solar radiation is supplied as the energy source of high-temperature process heat to the endothermic reactions, offers an attractive alternative to conventional autothermal processes. It has the potential to produce high-quality synthesis gas with higher output per unit of feedstock and lower specific CO2 emissions, as the calorific value of the feedstock is upgraded through the solar energy input by an amount equal to the enthalpy change of the reaction. The elimination of an air separation unit further facilitates economic competitiveness. Ultimately, solar-driven gasification is an efficient means of storing intermittent solar energy in a transportable and dispatchable chemical form. This review article develops some of the underlying science, examines the thermodynamics and kinetics of the pertinent reactions, and describes the latest advances in solar thermochemical reactor technology.

A 300kW Solar Chemical Pilot Plant for the Carbothermic Production of Zinc

In the framework of the EU-project SOLZINC, a 300-kW solar chemical pilot plant for the production of zinc by carbothermic reduction of ZnO was experimentally demonstrated in a beam-down solar tower concentrating facility of Cassegrain optical configuration. The solar chemical reactor, featuring two cavities, of which the upper one is functioning as the solar absorber and the lower one as the reaction chamber containing a ZnO/C packed bed, was batch-operated in the 1300–1500 K range and yielded 50 kg/h of 95%-purity Zn. The measured energy conversion efficiency, i.e., the ratio of the reaction enthalpy change to the solar power input, was 30%. Zinc finds application as a fuel for Zn/air batteries and fuel cells, and can also react with water to form high-purity hydrogen. In either case, the chemical product is ZnO, which in turn is solar-recycled to Zn. The SOLZINC process provides an efficient thermochemical route for the storage and transportation of solar energy in the form of solar fuels.

Experimental Investigation of the Solar Carbothermic Reduction of ZnO Using a Two-cavity Solar Reactor

Zinc production by solar carbothermic reduction of ZnO offers a CO 2 emission reduction by a factor of 5 vis-a-vis the conventional fossil-fuel-based electrolytic or Imperial Smelting processes. Zinc can serve as a fuel in Zn-air fuel cells or can be further reacted with H 2 O to form high-purity H 2 . In either case, the product ZnO is solar-recycled to Zn. We report on experimental results obtained with a 5 kW solar chemical reactor prototype that features two cavities in series, with the inner one functioning as the solar absorber and the outer one as the reaction chamber. The inner cavity is made of graphite and contains a windowed aperture to let in concentrated solar radiation. The outer cavity is well insulated and contains the ZnO-C mixture that is subjected to irradiation from the inner graphite cavity. With this arrangement, the inner cavity protects the window against particles and condensable gases and further serves as a thermal shock absorber. Tests were conducted at PSIs Solar Furnace and ETHs High-Flux Solar Simulator to investigate the effect of process temperature (range 1350-1600 K), reducing agent type (beech charcoal, activated charcoal, petcoke), and C:ZnO stoichiometric molar ratio (range 0.7-0.9) on the reactor s performance and chemical conversion. In a typical 40-min solar experiment at 1500 K, 500 g of a ZnO-C mixture were processed into Zn(g), CO, and CO 2 . Thermal efficiencies of up to 20% were achieved.

A two-cavity reactor for solar chemical processes: heat transfer model and application to carbothermic reduction of ZnO

A 5 kW two-cavity beam down reactor for the solar thermal decomposition of ZnO with solid carbon has been developed and tested in a solar furnace. Initial exploratory experiments show that it operates with a solar to chemical energy conversion efficiency of about 15% when the solar flux entering the reactor is 1300 kW/m2, resulting in a reaction chamber temperature of about 1500 K. The solid products have a purity of nearly 100% Zn. Furthermore, the reactor has been described by a numerical model that combines radiant and conduction heat transfer with the decomposition kinetics of the ZnO–carbon reaction. The model is based on the radiosity exchange method. For a given solar input, the model estimates cavity temperatures, Zn production ra4tes, and the solar to chemical energy conversion efficiency. The model currently makes use of two parameters which are determined from the experimental results: conduction heat transfer through the reactor walls enters the model as a lumped term that reflects the conduction loss during the experiments, and the rate of the chemical reaction includes an experimentally determined term that reflects the effective amount of ZnO and CO participating in the reactor. The model output matches well the experimentally determined cavity temperatures. It suggests that reactors built with this two-cavity concept already on this small scale can reach efficiencies exceeding 25%, if operated with a higher solar flux or if one can reduce conduction heat losses through better insulation and if one can maintain or improve the effective amount of ZnO and CO that participates in the reaction.

Towards the Industrial Solar Carbothermal Production of Zinc

Based on the experimental results of a 300 kW solar chemical pilot plant for the production of zinc by carbothermal reduction of ZnO, we performed a conceptual design of a 5 MW demonstration plant and of a 30 MW commercial plant. Zinc can be used as a fuel for zinc-air batteries and fuel cells, or it can be reacted with water to form high-purity hydrogen. In either case, the chemical product is ZnO, which in turn is solar recycled to zinc. The proposed thermochemical process provides an energy efficient route for the conversion, storage, and transportation of solar energy in the form of solar fuels.

Solar Thermal Reduction of ZnO Using CH4:ZnO and C:ZnO Molar Ratios Less Than 1

The solar thermal reduction of ZnO, using solar process heat and CH 4 or C as reducing agent, is investigated for CH 4 :ZnO or C:ZnO molar ratios ranging from 0 (thermal decomposition at above about 2000°C) to 1 (stoichiometric reduction at above about 1000°C). At 1400°C, in thermodynamic equilibrium ZnO can be completely reduced using a CH 4 :ZnO molar ratio of 0.3 and produces one fuel (Zn-metal) rather than two for the stoichiometric case (Zn and syngas). The maximal reactor thermal efficiency without heat recovery from the offgas, defined as the ratio of the heating-value of the zinc produced to the total thermal energy input, is 55%. CO 2 -emissions are reduced by a factor of 10-15 compared to fossil-fuel-based zinc-production technologies. For a closed materials cycle, in which power is extracted from the solar zinc using a fuel cell and the ZnO formed is recycled to the solar reactor, the total exergy efficiency, defined as the work output of the fuel cell to the thermal energy input, varies between 30 to 40% when based on the absorbed solar power in the reactor. These efficiency values are very encouraging, especially since the solar ZnO/Zn cycle allows-in contrast to other regenerative power plants-to store and transport solar energy.

Solar Carbothermic Reduction of ZnO in a Two-Cavity Reactor: Laboratory Experiments for a Reactor Scale-Up

Solar energy can be stored chemically by using concentrated solar irradiation as an energy source for carbothermic ZnO reduction. The produced Zn might be used for the production of electricity in Zn-air fuel cells or of H 2 by splitting water. In either case the product is again ZnO which can be reprocessed in the solar process step. This innovative concept will be scaled up to 300 kW solar input power within the so-called SOLZINC-project. In this paper we report on experimental results obtained with a two cavity reactor operated at solar power inputs of 3-8 kW in a solar furnace. The objective was to generate input data which are necessary for designing the scaled up reactor, such as the effect of process temperature (1100-1300°C) and carrier gas (N 2 and CO) on the overall reaction rate. Furthermore, construction materials were tested and a variety of carbonaceous materials were screened for their use as reducing agents by means of thermogravimetric measurements. As a result, beech charcoal was chosen as the standard reducing agent.

Indirectly Irradiated Solar Receiver-Reactors for High-Temperature Thermochemical Processes

A solar receiver-reactor concept for high-temperature thermochemical applications involving gas and condensed phases is presented. It features two cavities in series. The inner cavity is an enclosure, e.g. made of graphite, with a small aperture to let in concentrated solar power. It serves as the solar receiver, radiant absorber, and radiant emitter. The outer cavity is a well-insulated enclosure containing the inner cavity. It serves as the reaction chamber and is subjected to thermal radiation from the inner cavity. The advantages of such a two-cavity reactor concept are outlined. A radiation heat transfer analysis based on the radiosity enclosure theory is formulated and results are presented in the form of generic curves that indicate the design constraints. High energy absorption efficiency can be achieved by minimizing the aperture area, by maximizing the size of the inner cavity, and by constructing it from a material of high emissivity.Copyright

Experimental Investigation of a Packed-Bed Solar Reactor for the Steam-Gasification of Biomass Charcoal

Gasification of coal, biomass, and other carbonaceous materials for high-quality syngas production is considered using concentrated solar energy as the source of high-temperature process heat. The solar reactor consists of two cavities separated by a SiC-coated graphite plate, with the upper one serving as the radiative absorber and the lower one containing the reacting packed bed that shrinks as the reaction progresses. A 5-kW prototype reactor with an 8 cm-depth, 14.3 cm-diameter cylindrical bed was fabricated and tested in the High-Flux Solar Simulator at PSI, subjected to solar flux concentrations up to 2300 suns. Beech charcoal was used as a model feedstock and converted into high-quality syngas (predominantly H2 and CO) with packed-bed temperatures up to 1500 K, an upgrade factor of the calorific value of 1.33, and an energy conversion efficiency of 29%. Pyrolysis was evident through the evolution of higher gaseous hydrocarbons during heating of the packed bed. The engineering design, fabrication, and testing of the solar reactor are described.Copyright

Solar Carbothermic Production of Zinc From Zinc Oxide: Solzinc

In late 2004, the pilot Solzinc solar reactor was commissioned. The European Union and the Swiss Federal Office of Science and Education are funding this project to demonstrate the technical feasibility and the economical potential of producing Zn by reducing zinc oxide with the aid of concentrated solar energy and a small amount of carbon at a close to industrial scale. The zinc can be used as a means to store solar energy in a chemical way, e.g. suited to release electricity in Zinc-air fuel cells. This allows on demand use, boosting the availability of solar energy. Furthermore, as the Zinc-air fuel cells’ waste is ZnO, we get a cyclic process by reducing this ZnO in the Solzinc solar reactor. Numerous lab tests and numerical studies of the chemical and thermal behavior of the solar carbothermic ZnO reduction process were conducted by the Swiss Paul Scherrer Institute, the Swiss Federal Institute of Technology, the Israeli Weizmann Institute and the French CNRS Processes, Materials and Solar Energy laboratory. An indirectly heated beam-down reactor concept was chosen and influencing parameters, such as the type of carbon, the stoichiometry of the ZnO-C mix and the process temperature were explored. Based on these findings the technology was scaled up for the pilot plant for about 0.25 MW solar input leading to a designed zinc production rate of 50kg/h. The Swedish company ScanArc Plasma Systems AB developed a special quench system to produce zinc dust directly from the gaseous zinc exhausted from the solar reactor. The dust’s characteristics were adapted to the requirements of the Zn-air fuel cells developed by the German company ZOXY Energy System AG. The resulting zinc can be easily stored and transported for generating electricity as needed. In 2004, the pilot reactor, the quench system and extensive instrumentation were installed at the Weizmann Institute’s solar facilities to process batches of up to 500 kg of ZnO-C mixture. After cold testing of the installation and fulfilling all safety requirements, the first batches were processed. This paper explores the results of the commissioning to show the technical feasibility of this process to produce zinc and to store solar energy.Copyright