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Zinc Electrodes: Solar Thermal Production
C Wieckert, Paul Scherrer Institute, Villigen, Switzerland M Epstein, The Weizmann Institute of Science, Rehovot, Israel G Olalde, PROMES-CNRS, Font-Romeu Odeillo, France n, Scanarc Plasma Technologies AB, Hofors, Sweden S Sante A Steinfeld, Paul Scherrer Institute, Villigen, Switzerland, and ETH Zurich, Zurich, Switzerland
& 2009 Elsevier B.V. All rights reserved.

Introduction
Although used for many decades for special applications such as the powering of hearing aids, it is only in the last few years that zincair batteries/fuel cells have gradually entered the market for high-tech uses such as power generation for mobile phones, notebooks, and uninterruptible power supplies or other stationary applications. The batteries have also been tested in the transportation sector for several years. Some innovative companies are driving the development of more efcient and less expensive batteries. Several methods of recharging the spent zinc negative electrodes have been used, namely electrical and mechanical (i.e., feeding new zinc into the battery) methods. In all these processes, the production or recovery of zinc involves an appreciable consumption of energy, which is usually derived from fossil fuels. The use of solar energy offers a sustainable option to recharge a zincair battery. For electrically rechargeable zincair batteries this may be performed with solar electricity (e.g., produced in photovoltaic or concentrated solar power plants), whereas for mechanically rechargeable zincair batteries direct mechanical recharging is

possible: the zinc oxide accumulated in the spent electrodes can be reduced to zinc in a high-temperature chemical reactor heated by concentrated solar energy, as shown schematically in Figure 1. The rst proposals to produce zinc with concentrated solar energy were developed in the early 1970s, but only recently have signicant research and development programs on candidate processes been conducted. Besides producing zinc for electricity generation in zincair batteries, the solar zinc production by thermal dissociation of zinc oxide can be part of a two-step, thermochemical, water-splitting cycle. In the second nonsolar step, the solar-produced zinc reacts with steam to generate hydrogen, as illustrated in Figure 2. In summary, the three main driving forces for the development of solar zinc production processes are: solar electricity generation via storable and transpor table zinc (solar recharging of spent zincair battery

electrodes) from a cyclic ZnOZn process; solar production of hydrogen using a cyclic ZnOZn process; and solar production of metallic zinc as a commodity without or with drastically reduced emissions of carbon dioxide.

Concentrated solar radiation Zn

Chemical reactor

Products

Reactants

ZnO

Fuel cell

Zincair fuel cell/battery

Either C or CH4 or no reductant

Electricity

Figure 1 Basic scheme of the solar ZnO/Zn cycle for electricity production.

469

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470 Secondary Batteries Zinc Systems | Zinc Electrodes: Solar Thermal Production
Solar fuels based on ZnO/Zn reactions
Solar tower

The solar zinc route for electricity generation

The solar zinc route for hydrogen generation

Centralized applications

Solar receiver

Heliostat field

Combined cycle

Electricity

Zinc oxide Coal natural gas biomass

Solar dissociation:

ZnO = Zn + 0.5O2 Syn-gas

Processing to commodities

Solar carbothermic: ZnO + C = Zn + CO ZnO + CH4 = Zn + 2H2 + CO

Shift reactor Zinc

CO + H2O = CO2 + H2

Methanol, etc.

H2O
H2/CO2 separator CO2

Electricity

Zincair battery Zn + 0.5O2 = ZnO

Hydrolyser
Zn + H2O = ZnO + H2

Hydrogen

Decentralized and mobile applications Zinc oxide

H2/O2 fuel cell

H2 + 0.5O2 = H2O

Electricity

Decentralized and mobile applications

Figure 2 Scheme summarizing different process options provided by the solar Zn production technologies. Reproduced with permission from Wieckert C, Meier A, Palumbo R, and Steinfeld A (2001) Solar fuels based on ZnO/Zn reactions. In: ETSF22nd Conference on Energy Technologies for a Sustainable Future: Transitions to Solar Hydrogen. PSI, Villigen, Switzerland, 23 November, 2001, http://ene.web.psi.ch/news/ETSF/ETSF.html (accessed 25 April).

An overview of the research activities and reports on the development status of several zinc production processes using concentrated solar energy is presented below. The focus is on the application for zincair batteries.

Cyclic Process Options for Solar Recovery of Zinc from Zinc Oxide
As indicated in Figures 1 and 2, there are several candidate processes for solar zinc production. A fossil-fuelfree process based on the direct thermal dissociation of zinc oxide proceeds at a reasonable reaction rate at a temperature of above about 1750 1C according to
ZnO-Zn 1 2 O2 I

Signicant research and development activities associated with this process are currently performed at the Paul Scherrer Institute (PSI) and the Swiss Federal Institute of Technology Zurich (ETH) in Switzerland, as well as at the University of Colorado in the USA. Critical challenges are the development of materials for the solar reactor that can withstand the required high temperatures and nding a means to separate the product gases of zinc (g) and

oxygen so as to avoid their recombination. Very fast quenching offers the most promising solution for the latter problem. Fundamentally less difcult are processes in which zinc oxide is mixed with a carbonaceous reducing agent, e.g., carbon (C), as in conventional zinc production processes, or methane (CH4). Both the carbothermic reduction of zinc oxide with a solid carbon source (SOLZINC process, reaction [II]) and zinc oxide reduction with methane (SynMet process a solar process for co-producing zinc and synthesis gas (hydrogen and carbon monoxide) by reacting zinc oxide and methane, reaction [III]) proceed at more favorable temperatures of about 11001200 1C. In addition, the separation of gaseous zinc from the off-gas can benet from conventional metallurgical know-how. For example, in the vertical retort process for conventional zinc production, gaseous zinc is condensed out of similar off-gas mixtures containing zinc.
ZnO C-Zn CO ZnO CH4 -Zn CO 2H2 II III

An overview of different technological options for producing solar fuels from ZnOZn cyclic processes is

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Secondary Batteries Zinc Systems | Zinc Electrodes: Solar Thermal Production 471

presented in Figure 2. The reaction enthalpies and other key parameters of the three zinc production processes under consideration are listed in Table 1. It is important to note that the fraction of the energy content of the products stored in the zinc is much higher for the SOLZINC process using solid carbon as reducing agent (reaction [II]) than for the SynMet process using methane (reaction [III]). Reactions [II] and [III] assume stoichiometric mixtures of zinc oxide and carbon or methane, respectively. It is desirable to minimize the amount of reducing material as much as possible. Introducing the stoichiometry factor a for the molar mixtures of CZnO and CH4ZnO, the overall steady-state reaction equation for understoichiometric mixtures exemplied by the SOLZINC process is
ZnO aC-Zn 2a 1CO 1 aCO2 0:5rar1 IV

For comparison, conventional pyrometallurgical processes for zinc production use about 4.5 mol of carbon per

mol of zinc oxide. The minimum temperature required to transform completely all of the zinc oxide to zinc at thermodynamic equilibrium as a function of the stoichiometry factor a is shown in Figure 3. Process operation is attractive for mixtures close to 0.5 mol of C per mol of zinc oxide and 0.25 mol of methane per mol of zinc oxide, as moderate operation temperatures are combined with low consumption of reducing agents. Furthermore, most of the energy contained in the products is stored in the zinc, as practically all of the offgas is oxidized (see Figure 4). Working with an even lower proportion of reducing agent would require much higher temperatures as part of the zinc oxide needs to be dissociated thermally according to reaction [I]. Exploratory experiments as well as kinetic considerations have indicated, however, that it is difcult to realize a strongly understoichiometric process (e.g., ao0.7 for the SOLZINC process), owing to the strong conversion of carbon monoxide to carbon dioxide (in the case of using solid carbon) or carbon monoxide and hydrogen to carbone dioxide and water (in the case of using methane) that has to be achieved in the reactor. Furthermore, the issue of

Table 1 Process

Key data for different Zn production processes ZnO-Zn 1/2 O2 2335 K 460 kJ mol1 1 Lab Large, fundamental issues ZnO C-Zn CO SOLZINC 1220 K 350 kJ mol1 0.56 Pilot Medium, just engineering issues ZnO CH4-Zn CO 2H2 SynMet 1110 K 447 kJ mol1 0.32 Lab Medium, engineering issues

T(DG 0) DH 0 HVZn/(HVZn HVoff-gas) Development status Challenge level

HV heating value

ZnO + 2000 ZnO Zn + 1800

1 2

1 2

C Zn +

1 2

CO2

O2 C

Temperature (C)

1600 1400 ZnO 1200 1000 ZnO + 800 0.0

1 4

CH4 ZnO No ZnO

No ZnO ZnO + C Zn + CO CH4 Zn + 0.2

1 4

CO2 + 0.4

1 2

H2O 0.6 0.8 1.0

ZnO + CH4 Zn + CO + 2H2

Stoichiometry factor ( = mol CH4/mol ZnO; = mol C/mol ZnO)

Figure 3 Thermodynamic equilibrium investigation of mixtures of ZnO/C and ZnO/CH4: minimal temperature required to completely transform all ZnO into Zn as a function of the stoichiometric factor a. Reproduced with permission from Wieckert C and Steinfeld A (2002) Solar thermal reduction of ZnO using CH4:ZnO and C:ZnO molar ratios less than 1. ASME Journal of Solar Energy Engineering 124: 5562.

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Heat value fractions in Zn (=QZn /(QZn + Qoff-gas)) 1.0 0.9 0.8 ZnO + C 0.7 Q zn/(Q zn + Qoff-gas) 0.6 0.5 0.4 0.3 0.2 0.1 0.0 0.0 ZnO + CH4

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

Stoichiometry factor ( = mol C/mol ZnO; = mol CH4/mol ZnO)

Figure 4 Fraction of heating value of Zn compared to total heating value of the process products as a function of the stoichiometry factor a for ZnO/C and ZnO/CH4 mixtures.

zinc condensation from the respective gases without major recombination becomes relevant. In the next three sections, a brief review of the stateof-the-art technology will be given for the solar production of zinc from zinc oxide by carbothermic reduction with solid carbon (SOLZINC process, reaction [II]), by reduction with methane (SynMet process, reaction [III]), and by thermal dissociation without any reducing agent (reaction [I]). Emphasis is on the SOLZINC route, as the development of this process is the most advanced.

sketched in Figure 2, allows placing the zinc production plant on the ground in contrast to mounting it on top of a solar tower. In the European research project SOLZINC, the two-cavity reactor was selected for optimization and up-scaling to a pilot plant with a concentrated solar power input of approximately 300 kW. This pilot plant is described in more detail below.

Major Factors Inuencing the Carbothermic Process

Reaction [IV] describes the overall reaction for a given stoichiometry factor a. It is well known that the dominating reaction is a gassolid reaction between carbon monoxide and zinc oxide, rather than a solidsolid reaction between zinc oxide and carbon. Thus, the two reactions
ZnO CO-Zn CO2 V

Solar Carbothermic Zinc Production: The SOLZINC Process

Several solar reactor schemes have been proposed for reaction [II] and reactor prototypes have been built and tested at a laboratory scale of 510 kW input of concentrated solar power. The so-called two-cavity reactor developed at PSI in Switzerland is shown in Figure 5. A xed bed of zinc oxide and carbon, basically at atmospheric pressure, is heated indirectly by a thin separation wall, which is heated on the other side by concentrated solar radiation. The product gases, mainly zinc and carbon monoxide, leave the reactor through a condenser, in which the zinc condenses and sublimates to a zinc dust. The latter is separated from the residual off-gas in a ceramic lter. This solar reactor concept is designed for a beamdown optical system with the concentrated solar radiation entering from above. Such an optical conguration, as

and
C CO2 -2CO VI

occur simultaneously and superimpose to give reaction [IV] under quasi-steady-state conditions. Hence, the effective reaction kinetics of the carbothermic zinc oxide reduction strongly depend on the type of reducing agent, the temperature, and the stoichiometry. As the xed bed is heated by irradiating the top surface layer, the overall reaction rate is proportional to the exposed surface area of the bed.

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Lambertian target 45 mirror

Secondary concentrator Window

Upper cavity

Lower cavity

SiC lining Filter

Separation wall

ZnOC

Gas outlet

Condenser 15 cm

Figure 5 Laboratory-scale SOLZINC two-cavity solar reactor developed at Paul Schever Institute (PSI) for studying the carbothermic ZnO/C process and reactor components like wall materials. The incident concentrated solar radiation is deected by the 451 mirror from horizontal to vertical beam. The Lambertian target on the left is used to position the reactor and to measure the incoming solar power. upl S, Frommherz U, and Wieckert C (2006) Solar carbothermic reduction of ZnO in a two-cavity Reproduced with permission from Kra reactor: Laboratory experiments for a reactor scale-up. ASME Journal of Solar Energy Engineering 128: 815.

Table 2 Typical characteristic data of reducing materials pretested as reducing agents for the SOLZINC process (C is the xed carbon without C in volatiles) Name Beech charcoal powder Starlight Anthrazit Campana Kalzinat Type Beech charcoal Coal (Vietnam) Petcoke (Argentina) Petcoke Provider Chemviron SSM-Coal SSM-Coal RAG Additive Particle size o200 mm powder powder C (%) 83 90.5 89.7 98 Volatiles (%) o13 6 10 0.5 Ash % (Tfus,red) o4(14151C) 3.5 0.3(14001C) 0.5

Feedstock Materials A number of different industrial carbon sources have been characterized by means of thermogravimetric analysis (TG), in which ZnOC mixtures are placed on a balance and heated at a constant rate, during which the weight loss is monitored as a function of both temperature and time. Some properties of selected sample materials are listed in Table 2. Typical results from TG runs are presented in Figure 6. The molar ratio between carbon and zinc oxide is 0.8:1. Plotted is the change in weight of the samples

relative to the initial value as a function of temperature; the heating rate is 10 K min1 for all experiments. All curves show a nearly constant, or slightly decreasing, region at lower temperatures where the volatiles are evaporated prior to the main reaction of zinc oxide and carbon as indicated by a steep loss in weight. The gaseous products are transported away by the carrier gas ow. Once the remaining weight is unchanged, the main reaction is over. The earlier the reaction occurs (i.e., lower temperature) and the steeper the decrease in mass (i.e., fast reaction), the better is the carbon material for the solar process. For example, the main reaction occurs at

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474 Secondary Batteries Zinc Systems | Zinc Electrodes: Solar Thermal Production
100

lzi Ka

80

t na

a an mp Ca

Beec

Weight (%)

60

Sta

h cha rcoal

h rlig t

40

20

0 600

700

800

900

1000 1100 Temperature (C)

1200

1300

1400

Figure 6 Thermogravimetric test results for investigating the reactivity of ZnO/C mixtures using different carbonaceous materials. The upl S, Frommherz U, graphs show the relative reduction of the sample weight, starting from 100%. Reproduced with permission from Kra and Wieckert C (2006) Solar carbothermic reduction of ZnO in a two-cavity reactor: Laboratory experiments for a reactor scale-up. ASME Journal of Solar Energy Engineering 128: 815.

9501100 and 10001300 1C for beech and Starlight charcoal, respectively. Higher temperatures are required to yield a similar reaction rate with Campana coal and Kalzinat (a petroleum coke). Other criteria for the suitability of a carbon source for the process include low ash content, high ash fusion temperature, industrial availability, and acceptable market price. Based on these considerations, beech charcoal was chosen as the standard input material for further investigations at both the laboratory scale and the pilot plant scale. As beech charcoal is a biomass-derived material, it allows for a carbon dioxide-neutral process in spite of its carbon content. Nevertheless, it is important to note that other reducing materials may also be used, although at slightly higher operation temperatures or lower production rates. Comparison of a carbon source of low reactivity with beech charcoal yields similar temperature differences for achieving a specied reaction rate in both thermogravimetric and solar tests at the laboratory scale. Thus simple TG analysis can be used for screening and selecting carbon materials. Industrial quality zinc oxide (Grillo 2011) has been used as well as chemically pure zinc oxide material (Fluka). In contrast to carbon, no signicant inuence of the type of zinc oxide on the reaction rate has been observed. Temperature Dependence The zinc production rate per unit surface area of the xed bed, as established in laboratory-scale tests, is given

in Figure 7. The data were obtained by using the solar reactor shown in Figure 5. There is a strong increase in zinc production with increasing temperature. These investigations, together with tests of different solar reactor construction materials at the laboratory scale, produced the necessary know-how to realize a pilot plant for the novel solar carbothermic zinc oxide reduction process.

Engineering Design of the SOLZINC Pilot Plant

The main components of the SOLZINC pilot plant are depicted in Figure 8. The key innovative features of the system are as follows: use of the beam-down optics of the solar tower plant to introduce the concentrated solar radiation into the

reactor placed on the ground, two-cavity xed-bed solar reactor (with 500 kg batch capacity of the feed mixture allowing for one batch per operation day at the design conditions), quenching system using recycled cold product gas (mainly carbon monoxide) to dilute the hot products exiting the reactor and producing zinc dust. By adjusting the quenching conditions, the reactivity of this zinc dust (mainly determined by the particle size distribution and the amount of surface oxidation) is optimized for application in zincair batteries manufactured by ZOXY Energy Systems, a German partner in the SOLZINC project.

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0.2

475

0.18

0.16

0.14

Mol min1 O (=Zn)

0.12

Beech charcoal, 4.5 I N2 min1 0:8:1 Beech charcoal, 9 l N2 min1 0:8:1 Beech charcoal, 1.5 l N2 min1 0:8:1 Beech charcoal, 4.5 l N2 min1 0:9:1 Beech charcoal, 1.5 l N2 min1 0:9:1 Act. C., 7 l N2 min1 0.8:1 (ETH) Act. C., 7 l N2 min1 0.8:1 Act. C., 6 l N2 min1 0.8:1 PetCoke, 4.5 l N2 min1 0.8:1 Linear (4.5 l N2 min1 0.8:1)
+

0.1

0.08

0.06
+

0.04

0.02

1350

1400

1450

1500

1550

1600

Temperature of top of reaction chamber (K)

Figure 7 Summary plot of Zn production rates of the SOLZINC laboratory-scale solar reactor (Figure 5) as a function of the reaction chamber temperature. Indicated are the carbon material, the amount of carrier gas (N2), and the stoichiometry of the mixture (mol C:mol ZnO). ETH, Swiss Institute of Technology Zurich. Reproduced with permission from Osinga T, Frommherz U, Steinfeld A, and Wieckert C (2004) Experimental investigation of the solar carbothermic reduction of ZnO using a two-cavity solar reactor. ASME Journal of Solar Energy Engineering 126: 633637.

Solar Concentrating System The beam-down optical conguration of the solar tower plant of the Weizmann Institute of Science (WIS) in Israel consists of a eld of heliostats (two-axis tracking, spherically curved mirrors) that focus the sun rays onto a hyperbolical reector at the top of the tower to redirect sunlight to a nal concentrator (compound parabolic concentrator (CPC)) located at ground level. A photograph of the facility is shown in Figure 9; the optical path is indicated. The CPC has a 220-cm-diameter entrance, a 46-cm-diameter exit, and a truncated height of 500 cm. The system delivers about 300 kW of concentrated solar radiation. The exit of the CPC is closely coupled to the aperture of the reactor. Solar Reactor A schematic of the two-cavity solar reactor is shown in Figure 10. It features two cavities in series: the upper one functions as the solar absorber and the lower one as the reaction chamber. With this arrangement, the upper cavity protects the window against particles and condensable gases and further serves as a thermal shock

absorber. The upper cavity has a 48-cm-diameter aperture covered with a 60-cm-diameter, 12-mm-thick quartz window mounted on a water-cooled copper ring, together with inlet ports for window ushing with inert carrier gas. A 0.8-cm-thick graphitesilicon carbide (SiC) partition separates the two cavities. The lower cavity is a 140-cm-diameter, 0.8-m-high cylindrical unit that contains the batch of ZnOC mixture. The maximum initial height of the batch is 0.5 m, which corresponds to about 500 kg of the ZnOC mixture that allows for a full day of operation. Overnight, the reactor cools down and can be recharged with a new batch in the early morning. For this purpose, the lower part of the lower cavity can be easily disconnected from the upper part and removed downward. Both upper and lower cavities have a steel outer shell, lined with 1-cm-thick insulation material of 0.03 W m1 K1 thermal conductivity, a 17.5-cm-thick alumina (Al2O3)silica (SiO2) layer (l 0.3 W m1 K1), and 0.8-cm-thick silicon carbide plates. The silicon carbide inlet pipe carries inert gas or recycled off-gas (carbon monoxide) to displace product gases. The window in the upper cavity is ushed with an inert gas ow (FUG in Figure 8), which exits through small gaps in the partition

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476 Secondary Batteries Zinc Systems | Zinc Electrodes: Solar Thermal Production

Hyperbolic mirror

Secondary concentrator
FC FUG

Chimney
T TQG6

Quartz window Inner recycling loop

T TRP2 T TQG7

F FQ3 Off-gas analyzer

N2
FC FLG
P DPL

Solar reactor
Flux

F FQ2

V6

T
TLP1 T
TLP2-8

T
TQG3

Cyclone

Bag filter

T TLP9

T TS3

Quench/cooler

T TQG4

Fan Zn fine dust

Off-gas to reactor (outer recycling loop) Zn dust

T FQ1

V7

F: Flow meter FC: Flow controller T: Thermocouple DP: Differential pressure sensor
Figure 8 Flow diagram of the SOLZINC solar chemical pilot plant featuring the solar concentrating system, the solar reactor, the off-gas system, and some of the diagnostic instrumentation. Reproduced with permission from Wieckert C, Guillot E, Epstein M, et al. (2007) A 300 kW solar chemical plant for the carbothermic production of zinc. ASME Journal of Solar Energy Engineering 129(2): 190196.

plates between the upper and the lower cavity. The silicon carbide off-gas pipe is electrically heated in the start-up phase to prevent zinc condensation, and extends into the quenching section. Off-Gas Handling System A photograph of the solar reactor and the off-gas quenching and treatment system installed next to the exit of the reactor is given in Figure 11. The off-gas treatment system is designed for producing zinc dust. Product gases exiting the reactor are quenched in a cooler with recycled, cold off-gas (inner recycling ow in Figure 8). This results in the formation of zinc dust, which is partially separated in a cyclone. Fines are further transported by a fan and recycled to the quenching chamber where they grow further by condensation of more gaseous zinc. The speed of the fan is controlled at a rate that complies with the desired pressure in the solar reactor, namely 00.5 kPa above the ambient pressure. A gasdust fraction leaves this inner loop and the respective nes are separated downstream in a back lter. The cleaned off-

Figure 9 Solar facility at the Weizmann Institute of Science. The yellow arrows indicate the optical path of the sunrays from the heliostat eld to the hyperbolic mirror on top of the solar tower into the SOLZINC pilot plant, which is mounted in the white building below the hyperbolic mirror. Reproduced with permission from Wieckert C, Guillot E, Epstein M, et al. (2007) A 300 kW solar chemical plant for the carbothermic production of zinc. ASME Journal of Solar Energy Engineering 129(2): 190196.

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Upper cavity above separation plates 300 KW Upper part (stationary) Quartz window

Lower part

Carrier gas inlet

Off-gas pipe with heater

Lower cavity (reaction chamber) 140 cm ZnOC batch

Figure 10 Design sketch of the SOLZINC pilot solar reactor. Reproduced with permission from Wieckert C, Guillot E, Epstein M, et al. (2007) A 300 kW solar chemical plant for the carbothermic production of zinc. ASME Journal of Solar Energy Engineering 129(2): 190196.

Figure 11 Photo of the SOLZINC pilot-scale solar plant in operation. To the right of the solar reactor, parts of the off-gas system can be seen, including the quench/cooler system, the cyclone for Zn dust separation, and part of the bag lter. Reproduced with permission n S, and Steinfeld A (2006) Pilot scale solar carbothermic reduction of ZnO to Zn. In: from Wieckert C, Epstein M, Olalde G, Sante Kongoli F and Reddy RG (eds.) Proceedings of the Sohn International Symposium on Advanced Processing of Metals and Materials, vol. 4, pp. 221236. San Diego: TMS (The Minerals, Metals and Materials Society).

gas containing mainly carbon monoxide is partially recycled back into the reactor and serves as a carrier gas (outer loop). The remaining gas leaves the system through a chimney. In an industrial plant, the heating value of this gas will be used (e.g., to drive a heat engine). Alternatively, the carbon monoxide in the off-gas can be converted to hydrogen via a watergas shift process. With regard to the balance-of-plant, (1) cooling water is

supplied to the copper mounting ange of the quartz window, for the wall cooling of the cooler, and for the CPC; and (2) nitrogen is employed for ushing the quartz window from the inside, for supplying further carrier gas for sweeping product gases (optionally, can be substituted by off-gas from the outer recycling loop), and for purging the pressure sensor pipes in the dusty section of the plant. In addition, a large number of thermocouples,

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pressure sensors, and ow meters are used to control and monitor the process.

Experimental Results from SOLZINC Pilot Plant

The pilot plant was operated successfully with zinc production rates of up to 50 kg h1. Only minor hardware problems were encountered, which could be solved by modications of the process parameters and small hardware changes. The readings of some selected sensors, indicated in Figure 8, during a typical test operation are presented in Figure 12, and some characteristic data for selected test days are summarized in Table 3. Here the zinc production rate is calculated from the ow rate of oxygen in the form of carbon monoxide and

carbon dioxide, based on the recorded off-gas composition and the total off-gas ow rate. This oxygen originates from the zinc oxide in the solar reactor. The reaction increases as a result of the use of an increasing number of heliostats. The temperature at the bottom of the reactor increases as the depth of the insulating xed bed above shrinks owing to the carbothermic reduction. This is a further good indicator of the completion of the reaction (emptying of the reactor) in addition to the off-gas analyses. A summary of many test days is given in Figure 13. The zinc production rate is plotted as a function of the temperature above the xed bed. Also, the stoichiometry factor a was varied by loading different ZnOC mixtures into the solar reactor. A strong increase in the overall reaction rate with increasing temperature above the xed bed is observed, whereas the effect of the stoichiometry appears to be minor.

1700 TRP2 1500 TLP1

0.9 0.8 0.7

1300 0.6 Temperature (K) 1100 0.5 0.4 TLP8 0.3 700 kmol Zn h1 500 TLP9 300 11.02 h 0.2 0.1 0 12.14 h 13.26 h 14.38 h 15.50 h 17.02 h

900

Figure 12 Readings of major temperature sensors during a typical operation of the pilot plant (run C in Table 3) (see Figure 8 for the location of the sensors TRP2, TLP1, TLP8, and TLP9. Also given is the production rate, calculated from the readings of the online CO and CO2 analyses). Reproduced with permission from Wieckert C, Guillot E, Epstein M, et al. (2007) A 300 kW solar chemical plant for the carbothermic production of zinc. ASME Journal of Solar Energy Engineering 129(2): 190196.

Table 3 Experiment

Process parameters and reaction rate for selected experiments of the SOLZINC pilot plant (Initial bed height 12 cm). A 0.9 6 3 06 500 1440 0.64 4 B 0.9 6 3 16 500 1390 0.44 o1 C 0.9 6 39 010 350 1450 0.67 o1 D 1 6 39 010 350 1460 0.7 o1 E 0.8 6 39 010 350 1470 0.61 o1

Stoichiometry a C/ZnO N2 ow rate in upper chamber (Nm3 h1) N2 ow rate in lower chamber (Nm3 h1) Outer recycled gas ow rate (Nm3 h1) Inner recycled gas ow rate (Nm3 h1) At maximum power input (plateau): Tlower cavity TLP1(K) Zn molar ow rate (maximal) (kmol h1) Batch height after test (cm)

Zn production rate (kmol h1)

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TLP1 (K) 1493 0.8 0.7 0.6 dmZn/dt (kmol h1) 0.5 30 0.4 0.3 0.2 10 0.1 0.0 0.67 0 0.77 20 1449 1408 1370 1333 1299 50 = 0.9 =1 = 0.8
Linear (a = 0.9)

479

40 dmZn/dt (kg h1)

0.69

0.71

0.73

0.75

1000/TLP1 (1 K1)

Figure 13 Arrhenius type plot of the overall Zn production rate as a function of the temperature TLP1 above the xed bed of ZnO/C mixture. Reproduced with permission from Wieckert C, Guillot E, Epstein M, et al. (2007) A 300 kW solar chemical plant for the carbothermic production of zinc. ASME Journal of Solar Energy Engineering 129(2): 190196.

Process Products X-ray diffraction analysis of samples collected in the cyclone and the bag lter indicated a zinc purity of about 95% (the remainder was zinc oxide). Samples from deposits in the pipes showed similar purity. A zinc oxide content of a few mol% is desirable, because the zinc oxide layer reduces the reactivity of the zinc dust to a level that is suitable for its use in zincair batteries and is also common in conventional commercial zinc dust production. The reactivity of the zinc dust with air was examined in separate laboratory tests and found to be suitable for negative electrodes in zincair batteries. Note that it is state-of-the-art to produce zinc in other forms (e.g., zinc powder from molten zinc), if required, by using a modied off-gas system. Efciencies Two forms of efciency are used to characterize a solar pilot plant: (1) The thermal efciency (Zthermal) of a solar reactor is dened as the fraction of the solar power input into the reactor from the CPC that is net absorbed (Qabsorbed) as sensible and process heat (reaction enthalpy), i.e.,
Zthermal Qabsorbed Qsolar 1

(HVZn) and carbon monoxide (HVCO) to the sum of the solar energy input (Qsolar) and the heating value of the carbon consumed (HVC), i.e.,
Zprocess HVZn HVCO Qsolar HVC 2

Qsolar is calculated by a transient ray-tracing program that takes into account the individual heliostats used during the solar experiments. The model is validated by calorimetric tests. For example, for run A (see Table 3), QsolarE280 kW, HVZn 63 kW, HVCO 36 kW, HVC 60 kW; hence ZthermalE30% and ZprocessE30%. Losses are mainly due to reection of the concentrated sunlight at the quartz window, reradiation through the aperture, heat conduction through the walls, and heating of the reactor walls. Efciencies of between 50% and 60% are expected for larger, optimized SOLZINC plants.

Conceptual Design of a SOLZINC Demonstration Plant

The encouraging results from the pilot plant operation support the conclusion that a demonstration plant based on the same technology is feasible. A ow sheet with anticipated mass ow rates for a 5-MW demonstration plant is shown in Figure 14. A conceptual design of the three major components, namely the beam-down optical system, the solar reactor, and the off-gas system, is briey described as follows.

(2) The process efciency (Zprocess) is dened as the ratio of the lower heating values of solar-produced zinc

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480 Secondary Batteries Zinc Systems | Zinc Electrodes: Solar Thermal Production
Chimney 2.16 th1 0.32 th1 C ZnO 5.3 MW Solar irradiation Aperture Inner recycling loop Batch mixer 50 m2 Separator Solar reactor Quench/cooler Key data: Cfix: ZnO = 0.8 beech charcoal thermal = 55% gas motor = 40% 1.74 th
1

0.5 MW Electric power

Gas motor

Bag filter

Fan 0.1 th1 Zn fine dust

Zn(g)

Recycled off-gas to reactor (outer loop)

1.66 th1 Zn dust

95% Zn, 5% ZnO

Figure 14 Estimated mass and energy ow rates of a 5-MW SOLZINC solar demonstration plant for Zn dust production. Reproduced n S, and Steinfeld A (2006) Pilot scale solar carbothermic reduction of ZnO with permission from Wieckert C, Epstein M, Olalde G, Sante to Zn. In: Kongoli F and Reddy RG (eds.) Proceedings of the Sohn International Symposium on Advanced Processing of Metals and Materials, vol. 4, pp. 221236. San Diego: TMS (The Minerals, Metals and Materials Society).

Beam-Down Optical System A preliminary heliostat eld layout designed with a raytracing software program is displayed in Figure 15: In this, 186 heliostats, each with a reective surface area of 54 m2, focus the sunlight via a hyperbolic mirror into seven identical hexagonal secondary concentrators (one at the center, six at the periphery). At the design point, 5.3 MW of concentrated solar thermal power leaves through the 80 cm-diameter exits of the seven secondary concentrators and enters the solar reactor. The ground area covered by the heliostats is approximately 200 200 m. A 30 MW, commercial size, beam-down optical system was also designed to conrm the feasibility of the beam-down technology for industrial use.
200

150 Meters (m)

100

50

0 100 50

0 Meters (m)

50

100

Solar Reactor Based on the results for the reaction rate per surface area, obtained during pilot plant operation, the solar reactor of the 5 MW demonstration plant has a oor area of 50 m2, which corresponds to a diameter of about 7.5 m. The ZnOC batch required for full-day operation is fed via screw feeders into the reaction chamber and its top level is evened out. The concentrated solar radiation exiting the seven secondary concentrators heats a single, large, reactor chamber. Six refractory columns support a number of silicon carbide rods, which, in turn, support the separation plates between the upper and the lower chambers. Sketches of the solar reactor with the seven

Figure 15 Layout of a 5-MW heliostat eld with 186 heliostats (about 10 000 m2 total surface) aiming at a hyperbolic reecting mirror on a tower of 59 m height. The tower stands at the location x 0 m, y 0 m.

quartz windows accepting the concentrated solar radiation are shown in Figure 16. Zinc Quench and Off-Gas System The estimated zinc production rate is 1.7 t h1. The offgas system is designed for producing zinc dust (about 1 mm in size). Depending on the desired application of

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Secondary Batteries Zinc Systems | Zinc Electrodes: Solar Thermal Production 481

252 cm height

5m

Figure 16 Conceptual design sketches of a 5-MW SOLZINC solar demonstration reactor. Reproduced with permission from Wieckert C, n S, and Steinfeld A (2006) Pilot scale solar carbothermic reduction of ZnO to Zn. In: Kongoli F and Reddy RG Epstein M, Olalde G, Sante (eds.) Proceedings of the Sohn International Symposium on Advanced Processing of Metals and Materials, vol. 4, pp. 221236. San Diego: TMS (The Minerals, Metals and Materials Society).

the produced zinc, however, other state-of-the-art off-gas treatment solutions are equally possible. For example, liquid zinc can be produced, which, in turn, can be atomized to zinc powder (typical size about 100 mm), e.g., by impinging the outowing melt with a high-velocity gas jet. Likewise, the melt can be cooled to produce ingots.

Process Economics
The conceptual design of the demonstration plant was used to evaluate the approximate costs of the different components, namely heliostats, secondary concentrators, solar reactor, and off-gas system. Preliminary offers were received for most parts of the demonstration plant and these enabled a sound cost estimate to be made. The total investment costs were found to be of the order of 6M h. These current cost estimates are expected to decrease signicantly in the future, e.g., owing to mass production of the heliostats, which constitute a major cost factor (quoted costs of 180 h per m2 of heliostat surface were used in the current estimate, but heliostat costs below 130 h per m2 are anticipated in the long run). Cost estimates for a fully commercial, 30 MW plant are about 18M h (using 130 h per m2 for the heliostats). Zinc production costs can then be derived with reasonable assumptions regarding solar radiation at the plant location, as well as operational and manpower salaries. The resulting long-term costs of 130170 h per ton of zinc (depending, for example, on the manpower salaries at the plant location) are very competitive. It should be noted that costs for replacing consumed/lost zinc oxide are not included in this calculation, in contrast to those for the used carbon. The reported costs are relevant if the solar-produced zinc is used as a commodity. For an economical

evaluation of electricity generation via the ZnOZn cyclic process, it is necessary to add the costs for the zincair batteries and the equipment/cost for preparing the batteries with the solar-produced zinc and for separating the potassium hydroxide electrolyte from the spent zinc oxide after battery discharge, prior to returning the zinc oxide back into the solar reactor. With best-guess assumptions for these steps, electricity costs of 0.15 h per kWh were calculated for a future 30-MWscale solar plant and of 0.300.40 h per kWh for a 5-MW demonstration solar plant.

Solar Reduction of ZnO with Methane: The SynMet Process

The reduction of zinc oxide with methane proceeds according to reaction [III] using concentrated solar energy. The so-called SynMet process has been tested at PSI in Switzerland using a prototype 5 kW solar reactor illustrated schematically in Figure 17. It consists of an insulated cylindrical cavity (length 240 mm, diameter 110 mm) that contains a 6 cm-diameter windowed aperture to let in concentrated solar energy. The quartz window (diameter 240 mm, thickness 3 mm) is cooled and protected from condensable gases by an auxiliary gas ow. Both reactants, methane and zinc oxide, are introduced at ambient temperature; zinc oxide powder is continuously fed axially. Short pulses of methane are simultaneously injected through a tangential inlet nozzle at the site where the zinc oxide particles fall. The pulsed gas ow results both in the formation of a dense cloud of particles that absorbs incoming solar radiation efciently and in a decrease in the gas ow rate needed for distributing the zinc oxide in the reactor cavity. The chemical products zinc vapor and syngas continuously exit the cavity via a tangential outlet port located at the front, behind the aperture.

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482 Secondary Batteries Zinc Systems | Zinc Electrodes: Solar Thermal Production
ZnO + CH4

Cavity receiver

CPC Quartz window Zn + 2H2 + CO

Figure 17 Design sketch of a laboratory-scale solar reactor for reaction of ZnO and CH4 (SynMet process) CPC compound parabolic ller R, Haeberling P, and Palumbo RD (2006) Further advances toward the concentrator. Reproduced with permission from Mu development of a direct heating solar thermal chemical reactor for the thermal dissociation of ZnO(s). Solar Energy 80(5): 500511.

The reactants in the solar reactor were directly exposed to solar power uxes exceeding 2000 kW m2. Reactants were continuously fed at ambient temperature, heated by direct radiation to above 1350 K, and converted to zinc and syngas during mean residence times of 10 s. A typical chemical conversion of 100% was attained for zinc oxide and up to 96% for methane. The thermal efciency was in the 1522% range and may be increased by recovering the sensible and latent heat of the products. Zinc is gained in the form of a dust; alternatively, the generation of liquid zinc or zinc powder is possible.

SolarThermal ZnO Dissociation

The thermal dissociation of ZnO with highly concentrated solar energy is being investigated at PSI in Switzerland and at the University of Colorado in the USA at a power level of 510 kW. Major challenges include the selection of reactor materials capable of withstanding operation temperatures of about 1800 1C in an oxidizing atmosphere, and the separation of the product gases Zn(g) and oxygen without major recombination to zinc oxide. The prototype 10 kW solar reactor under development at PSI is shown in Figure 18. It is a rotating cavity, in which centripetal acceleration developed from the rotational movement forces the reactant ZnO(s) to cover the cavity wall, which thereby creates an efcient use of

the cavity space for radiation heat transfer to the ZnO(s). The feeder extends periodically into the cavity for feeding; most of the time, it is parked outside the cavity within the quench tube. The reactor is composed of an inner cavity wall that is impervious to gas diffusion but is capable of functioning at the decomposition temperature of ZnO(s) in a corrosive environment containing ZnO(s), Zn(g), and oxygen. A layer of ZnO(s) of the desired thickness is spread over this surface. Insulation, which is resistant to high temperatures, is packed behind this layer. An inert gas is swept across the reactor window and carries the products to the quench zone. The ZnO(s) powder feeder is water cooled and integrated into the ZnO2 quench unit. The cold feeder is isolated from the hot cavity with a zirconia radiation shield, as shown in Figure 18. The product gases ow between the feeder and a water-cooled rotating cylinder wall. The cold wall and the injection of cold argon promote the quenching of Zn(g) to Zn(s).

Closing the ZnOZn Cycle: Interface Issues

The required steps for a complete cyclic ZnOZn process are illustrated schematically in Figure 19. The zincair battery manufacturer ZOXY Energy Systems performed exploratory experiments concerning the suitability of ne zinc dust (from condensation of

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9

10

3 4 2 1

Figure 18 Design sketch of the ZIRRUS reactor for solar thermal dissociation of ZnO: 1 rotating drum, 2 actuation, 3 aperture, 4 cavity, 5 screw feeder, 6 product outlet port, 7 rotary joint, 8 working uids, 9 insulation, 10 quartz window. Reproduced with permission from Steinfeld A and Meier A (2004) Solar fuels and materials. Encyclopedia of Energy, vol. 5, pp. 623637, ISBN 0-12-176480-5. Elsevier Inc.
Electricity from concentrated solar radiation via Zn/ZnO cyclic process Solar irradiation Off-gas

Heliostats, tower, CPC

Off-gas treatment

KOH +H2O

CH4 or C Solar reactor for ZnO reduction

Quench/Zn condensation

Zn

Preparation of anodes

Preparation ZnO for solar reactor Zn stream (Zn), in situ Zn/ZnO stream (Zn/ZnO) potentially including storage and/or transport Other stream, in situ KOH (+ H2O)

ZincAir battery

Electricity

KOH stream (option)

Figure 19 Scheme of the Zn/ZnO cyclic process to electricity production via zincair batteries showing the interfaces between the two main components solar reactor and zincair battery. CPC, compound parabolic concentration.

zinc) and more coarse zinc powder (from atomizing liquid zinc) as substitutes for the electrolytically produced zinc sponge presently used in their standard zincair batteries. For this purpose, ZOXY investigated a variety

of battery designs to examine the dependence of several performance parameters and found a design, which was denoted as PZ 280, as most suitable. The molar concentration of the potassium hydroxide electrolyte was

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484 Secondary Batteries Zinc Systems | Zinc Electrodes: Solar Thermal Production

also varied. Test campaigns were conducted with atomized zinc produced from zinc(l) and with nucleated zinc dust (Harzer Zinkoxide). For direct comparison, the same tests were performed with standard zinc sponge. The results of the above exploratory tests are summarized in Table 4 and they appear to be promising in that equivalent performance was recorded for the zinc sponge and for the zinc powder. The nucleated dust (typical particle size 2 orders of magnitude smaller) also
Table 4

behaved similarly, but it required a somewhat higher electrolyte concentration. The reactivity of zinc dust in the electrolyte plays an important role. It depends on the size distribution and on the zinc oxide fraction of the zinc particles. The zinc oxide typically forms a passivation layer around a zinc kernel. The process conditions during quenching of Zn(g) to zinc dust were adjusted in order to produce zinc dust with a reactivity acceptable for the battery.

Results of discharging tests of zincair batteries with different Zn anodes PZ 280 Grillo Powder 200 761.53 520 PZ 280 ZOXY Sponge 795.14 B539,00 600 3 310.6 354.4 0.597 0.682 600 3 302.6 345.6 0.561 0.641 600 6 5 330.4 0.520 0.635 600 3 3 173.4 0.287 0.334 PZ 280 Harzer zinkoxide Dust 3 760.24 520 PZ 280 Harzer zinkoxide Dust 3 774.48 520.

ZOXY cell type Zn origin Zn type Typical Zn size, mm Anode weight, g Zn weight, g Sponge weight, g Electrolyte, mL Electrolyte concentration, mol L1 Capacity, Ah Energy, Wh Specic capacity, Ah g1 Specic energy, Wh g1

Tower reflector Coal/coke

Village n

Zn To town Tower Secondary concentrator Reactor Building Heliostat field Anode production/ ZnO washing Zn ZnO ZnO ZnO

Zn

Village 1 Village 2

Figure 20 Schematics of one of the most promising scenarios using the SOLZINC technology: rural electrication. Reproduced with n S, and Steinfeld A (2006) Pilot scale solar carbothermic reduction of ZnO to permission from Wieckert C, Epstein M, Olalde G, Sante Zn. In: Kongoli F and Reddy RG (eds.) Proceedings of the Sohn International Symposium on Advanced Processing of Metals and Materials, vol. 4, pp. 221236. San Diego: TMS (The Minerals, Metals and Materials Society).

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Washing of Spent Zinc Electrodes After battery discharge, one is left with a mixture of zinc oxide, some unreacted zinc, and potassium hydroxide electrolyte. Spent zinc electrodes were washed with water to separate off the potassium hydroxide prior to reusing the zinc oxide in the solar reactor. The zinc oxide products resulting from these exploratory tests with zinc powder electrodes were then investigated at WIS and PSI for their performance in the carbothermic zinc oxide reduction process. Mixtures of washed spent zinc electrodes with beech charcoal powder were found to demonstrate very good reactivity.

with solid carbon (e.g., coal or biomass): SOLZINC process; and (3) use of methane as a reducing agent: SynMet process. Option (2) has been developed to a pilot scale for a zinc production rate of 50 kg h1, whereas the others are currently being investigated at the laboratory scale. Preliminary tests have been conducted using solar-produced zinc as the negative active material for zincair batteries, followed by subsequent washing of the spent electrodes after discharging in order to separate the potassium hydroxide electrolyte. Further development of these solarbased ZnOZn cyclic processes to produce electricity is required. Solar-made zinc nds application not only in zincair batteries but also for hydrogen production via hydrolysis and as a material commodity.

Application Scenarios
There are a large number of different scenarios for using the solar ZnOZn cycle for the production of solar electricity via zincair batteries, for example, on-site continuous zinc production (storage of zinc between day and night), on-site electricity production for peak hour pro duction (requires higher investment for the zincair

Nomenclature
Symbols and Units
dmZn/dt Qabsorbed Qsolar T Tfus,red a DG DH 0 gprocess gthermal k CPC ETH PSI TG WIS zinc production rate (kmol h 1) power absorbed for the chemical reaction (kW) solar power entering the reactor (kW) temperature (K) fusion temperature of ash under reducing conditions (1C) stoichiometric factor in mol C per mol ZnO and mol CH4 per mol ZnO Gibbs free energy change per mol of reactant (kJ mol-1) enthalpy change per mol of reactant (kJ mol 1) process efciency of the solar chemical process thermal efciency of a solar reactor thermal conductivity (W m 1 K 1) compound parabolic concentrator Swiss Institute of Technology Zurich Paul Scherrer Institute thermogravimetric analysis Weizmann Institute of Science

batteries), transport of zinc for stationary use (grid connected), transport of zinc for stationary use (off grid), and transport of zinc for onboard use in vehicles.

Each of these options shows specic advantages and disadvantages with respect to competing technologies. Thus, further research and development is required to realize commercialization. The SOLZINC is expected to be particularly competitive for rural electrication applications of the type suggested in Figure 20: A central SOLZINC plant produces zinc for zincair batteries to generate electricity in nearby villages or small towns, which are not connected to the main power grid. The detached villages are e.g. powered by a local mini-grid. With about two billion people still not connected to main power lines, such a decentralized solution might be valuable for a large number of locations, e.g., in rural Africa or South America. Contacts with institutions working in rural electrication projects conrm the relevance of this concept, which should be further explored.

Abbreviations and Acronyms

Conclusions
The thermochemical production of zinc using concentrated solar radiation as the energy source of high-temperature process heat is a promising option for the sustainable recharge of spent zincair batteries. Different processes for the solar zinc oxide reduction are under development, namely (1) thermal dissociation; (2) carbothermic reduction

See also: Secondary Batteries Metal-Air Systems: ZincAir: Electrical Recharge; ZincAir: Hydraulic Recharge; Secondary Batteries Zinc Systems: Zinc Electrodes: Overview.

Further Reading
Berman A and Epstein M (1998) The kinetic model for carboreduction of zinc oxide. Journal of Physics IV France 9: 319--324.

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