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GA–A24972 HIGH EFFICIENCY GENERATION OF HYDROGEN FUELS USING SOLAR THERMAL-CHEMICAL SPLITTING OF WATER (SOLAR THERMO-CHEMICAL SPLITTING FOR H2) ANNUAL REPORT FOR THE PERIOD OCTOBER 1, 2003 THROUGH SEPTEMBER 30, 2004 by B.W. McQuillan, L.C. Brown, G.E. Besenbruch, R. Tolman, T. Cramer, B.E. Russ, B.A. Vermillion, B. Earl, H.-T. Hsieh, Y. Chen, K. Kwan, R. Diver, N. Siegal, A. Weimer, C. Perkins, and A. Lewandowski Prepared under Solar Thermochemical Hydrogen Grant No. DE-FG36-03G013062 for the US Department of Energy and F03-STCH2-002 for the University of Nevada Las Vegas Research Foundation DECEMBER 2010 DISCLAIMER This report was prepared as an account of work sponsored by an agency of the United States Government. Neither the United States Government nor any agency thereof, nor any of their employees, makes any warranty, express or implied, or assumes any legal liability or responsibility for the accuracy, completeness, or usefulness of any information, apparatus, product, or process disclosed, or represents that its use would not infringe privately owned rights. Reference herein to any specific commercial product, process, or service by trade name, trademark, manufacturer, or otherwise, does not necessarily constitute or imply its endorsement, recommendation, or favoring by the United States Government or any agency thereof. The views and opinions of authors expressed herein do not necessarily state or reflect those of the United States Government or any agency thereof. GA–A24972 HIGH EFFICIENCY GENERATION OF HYDROGEN FUELS USING SOLAR THERMAL-CHEMICAL SPLITTING OF WATER (SOLAR THERMO-CHEMICAL SPLITTING FOR H2) ANNUAL REPORT FOR THE PERIOD OCTOBER 1, 2003 THROUGH SEPTEMBER 30, 2004 by B.W. McQuillan, L.C. Brown, G.E. Besenbruch, R. Tolman, T. Cramer, B.E. Russ, B.A. Vermillion, B. Earl,* H.-T. Hsieh,* Y. Chen,* K. Kwan,* R. Diver,† N. Siegal,† A. Weimer,‡ C. Perkins,‡ and A. Lewandowski# *University of Nevada, Las Vegas. †Sandia National Laboratories ‡University of Colorado #NREL Prepared under Solar Thermochemical Hydrogen Grant No. DE-FG36-03G013062 for the US Department of Energy and F03-STCH2-002 for the University of Nevada Las Vegas Research Foundation GENERAL ATOMICS PROJECT 30232 DECEMBER 2010 1. INTRODUCTION This work investigates the possibility of economic thermochemical production of hydrogen from water, using concentrated solar energy as the heat source. The first effort, the subject of this year’s work, was to investigate all possible thermochemical cycles to determine which cycles might be well suited to use with concentrating solar energy devices. The effort was then to (1) find and organize information on known thermochemical water-splitting cycles, (2) define the important characteristics of the solar devices which would affect cycle selection, (3) define quantifiable criteria that could be easily used to screen the cycles for use with each solar device, eliminating unsuitable cycles, and (4) performing a semi-rigorous evaluation of the cycles that passed the initial screening, to find those cycles that required the least thermal energy to produce hydrogen. The first three items together make-up our Phase 1 screening task and the fourth item is our Phase 2 screening task. 2. PHASE 1 SCREENING The goal of Phase 1 screening was to list all thermochemical cycles and then, on the basis of pertinent criteria and quantitative metrics, to rank the potential that a cycle could be economically implemented, and to remove from further consideration those cycles having low potential for ultimate success. As the criteria varied with the type of solar device, the scoring had to be repeated for each solar device. Objective measures were found to assign a criteria score for each cycle, and then points (0– 10 pts) were assigned to the range of scores. For instance, on criteria 2 (number of difficult separations), a given cycle would have a score of 4 separations, and 4 separations would be assigned 2 points. Thus, each cycle would be assigned 0–10 points, on each of 16 criteria. Each criterion was then weighted (so as to be more or less important), to yield a total score. The weighting of criteria was usually “the same” across the 4 different solar devices, but on criterion 8, each device had a separate weighting. This total score was then normalized so that the final score corresponds to the percent of maximum possible points. 2.1. The Phase 1 Criteria The following 16 criteria were constructed as quick and simple measures of potentially viable thermochemical criteria (Table 1). Each criteria is worth 0-10 points. Criteria 1-6. Economic Considerations Criterion 1. The number of steps or fundamental reaction equations in the cycle. A two step cycle would seem to be less complex than a 5 step cycle: fewer movements of material, fewer separations, fewer chemicals-all other things being equal. 1 " # $ % & ' ( ) * + #" -%*'!%"$ @ LC C B A ( ( ( #" *,"'&+ -%*' A LC C B A @ ? & & & * +(*,"'&+,( -%*'!%"$ B LC C B A @ " " " " $%&,+ -&&' * !33+3-3 ,3"33 3 3 &333 333 '33 !3+3313%3 333 33 -3&3*3"33 &33 3"33 3 3 3$33 C 3- %3$3 - 3 '3-3+3 3* 33'33 3 "3*3*33 $33" % % % % !%"$$%&,+ 3*3 3&3 * 0""2"& & 1*' & &!1*"+' $' &+ $#$"'0"+& $#$"&'0"+& $#$"&+$,+ $#$"+$,+ ,$'0"+ '&6%,$ '&6'**'+". 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riterion 2. Number of difficult separations. A very abbreviated flow diagram was constructed and used to determine the number of “difficult” separations needed, based solely on the fundamental equations of the cycles, for a viable process. The following types of separations were deemed difficult: * solid-solid separations, where the products are two solids * solid-liquid separations, where a filtration or other means would be needed * liquid-liquid separations, where two liquids (miscible or immiscible) were found. * gas-gas separations, such as separating O2 from HCl. * Aqueous/non-aqueous, such as dehydrating aqueous H2SO4 to make anhydrous H2SO4 Gas-liquid and gas-solid separations were deemed “easy” and not counted. Two other assumptions were made in this evaluation. First, the details of the separation were not evaluated. We looked solely at the fundamental separations to be made, not how we would do such. However, those evaluating the cycles had some discretion to say “if I cool the products by 100°C, I then change a difficult gas-gas separation into an easy gas-liquid separation, thereby improving the process and removing one gas-gas separation from the count.” Second, since many steps are at equilibrium and do not proceed to completion, there would be recycle of all liquid and gas reactants from the product stream. We presumed solid reactants went to products completely. A significant fraction of the difficult separations resulted from recycle of gas or liquid reactants. Criterion 3. Number of elements The more elements present is a measure of the number of species to be dealt with. The greater the number of chemicals used indicates a more complex process. Criterion 4. Abundance of chemicals One would want to use very common chemicals and elements-they would be less expensive and readily available in large quantities. So this criterion looks at the abundance of the scarcest element in the cycle, and assigns points based on that limiting abundance. Criterion 5. Use of non-corrosive chemicals Corrosive chemicals lead to the use of more expensive non-corroding equipment.