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International Journal of Hydrogen Energy 32 (2007) 531 – 536 www.elsevier.


Experimental study of two phase separation in the Bunsen section of the sulfur–iodine thermochemical cycle
A. Giaconia, G. Caputo, A. Ceroli, M. Diamanti, V. Barbarossa, P. Tarquini, S. Sau ∗
ENEA, “Casaccia” Research Center, via Anguillarese, 301, 00060 S. M. di Galeria, Rome, Italy Available online 25 September 2006

Abstract The Bunsen reaction for the production of hydriodic and sulfuric acids from water, iodine and sulfur dioxide, has been studied with the evaluation of the effect of some operative parameters on product phase behavior. Results show that operative temperature has a minor effect on the phase behavior. In contrast, both iodine and water loads can be adjusted to enhance the downstream operations of the sulfur–iodine thermochemical water-splitting cycle: the effect of iodine and water excess on resulting phases purity, side reaction occurrence and acid concentration was studied and, then, the most favorable operative conditions defined. 2006 International Association for Hydrogen Energy. Published by Elsevier Ltd. All rights reserved.
Keywords: Hydrogen production; Sulfur–iodine thermochemical cycle; Bunsen reaction

1. Introduction In the prospective of a future energy scenario based on the intensive use of hydrogen as energy vector, sustainable production routes essentially based on the utilization of renewable raw materials and alternative (non-fossil) primary energy sources must be considered for the long term. Hence, the evaluation of all the viable processes for hydrogen production from water is a must and, in principle, thermochemical cycles one of the most interesting options. To date, the most widely studied thermochemical watersplitting cycle is the sulfur–iodine (S–I) cycle, consisting of the following three reactions involving sulfuric and hydriodic acids as intermediates: 2H2 O2 + I2 + SO2 → H2 SO4 + 2HI, 2HI → I2 + H2 ,
1 H2 SO4 → H2 O + SO2 + 2 O2 .

(1) (2) (3)

∗ Corresponding author. Tel.: +39 06 3048 6334; fax: +39 06 3048 6779.

E-mail address: (S. Sau).

Reaction (1), called Bunsen reaction, provides water-splitting into two acids (hydriodic and sulfuric) via reaction with iodine and sulfur dioxide. Afterward, produced HI and H2 SO4 are separated and sent to the concentration/decomposition sections for conversion to H2 and O2 by reactions (2) and (3), respectively (Fig. 1). Intense experimental and theoretical research activity has been carried out worldwide during the last decade to investigate the potentialities of this process [1–3] and, as a matter of fact, the scientific feasibility demonstration of the S–I chemical cycle has been recently achieved with a continuous bench scale loop [4,5]. Nevertheless, further effort is still required for process advancement and optimization, in order to evaluate the technological feasibility and the competitiveness of the process (energetic efficiency, costs, etc.). From the engineering point of view, the development of the three sections in which the whole cycle can be divided (Fig. 1) imposes the resolution of different problems. Hence, the sulfuric acid concentration/decomposition section (referred to as “sulfuric section”) is critical for the highest temperatures involved (800–1000 ◦ C), with consequent issues dealing with material corrosion and the coupling with the primary high temperature energy source, as well as the study of catalyst activity and stability [6–10]. Material resistance issues are also important for the development of the hydriodic acid concentration/decomposition section

0360-3199/$ - see front matter 2006 International Association for Hydrogen Energy. Published by Elsevier Ltd. All rights reserved. doi:10.1016/j.ijhydene.2006.08.015

A schematic of this simple apparatus is shown in Fig.532 A. can be carried out at relatively mild temperatures (< 120 ◦ C) to obtain high yields with a very small energy input (the reaction itself is exothermic in water media). reliable thermodynamic data for HI/I2 /H2 O mixtures are required for plant and process design. First. 2. and on the utilization of permselective membrane reactors. on the other hand. 2. 1). However. Bunsen reaction (1). it can be considered as the “key” step of the S–I thermochemical cycle. In practice. 2. process schemes based on reactive distillation. furthermore. the higher are the resulting capital and operative expenses. Materials and methods Phase behavior of the four-component H2 SO4 /HI/H2 O/I2 mixtures was investigated using a 50 mL jacketed quartz test tube whose temperature was controlled by means of a water/ ethylene glycol recirculation system and a thermostatic bath (Julabo). on HI concentration by extractive distillation.9%. For this reason. Aldrich) was added to a 57 wt% HI/H2 O liquid solution (Aldrich) past heating. Schematic of the sulfur–iodine thermochemical water-splitting cycle. since this section is interfaced to both the sulfuric and hydriodic concentration/decomposition sections (Fig. Apparatus used for liquid–liquid phase behavior tests. . in this case. sulfates in the HIx phase can lead to unwanted reactions with HI with possible sulfur or H2 S formation. on the other hand. electro-electrodialysis (EED) or more conventional distillation operations. on the other hand. Some experimental and theoretical studies reveal that a large iodine excess (x) is needed to enhance phase (product) separation and to avoid side reactions [15–17]. a selected amount of iodine (>99. have been proposed [11–14]. After complete iodine dissolution. 1. Therefore. deter- mines benefits on the management of the HIx section due to the lower iodine recirculation flow rates. while the identification (and subsequent development) of the most convenient route has not been realized: yet. A reduction in the iodine excess (x). I2 and HI traces into the sulfuric acid must be minimized because they can lead to poisoning of the catalyst used for sulfuric acid decomposition [7]. sulfuric acid thermostat sulfuric acid phase hydroidic acid phase (HIx) Fig. The larger the water excess (n). Hence. the operative conditions for this reaction must be optimized in order to reduce the possibility of side reactions (side products must be avoided especially for such a cyclic chemical process) and to obtain two concentrated acid streams to ease the operations in the other sections. ½ O2 HI/H2O H2 (for reaction 3) [10]. one of the major objective of the work presented here is to select the most suitable process conditions for the Bunsen reaction to obtain two separated liquid streams as pure and concentrated as possible in the two acids (sulfuric and hydriodic) to facilitate the processes in the downstream sections: first. the hydriodic acid phase will be referred to as “HIx phase” and this chemical process step can be described as follows: (x + 1)I2 + SO2 + (n + 2)H2 O → [H2 SO4 + (n − m)H2 O]Sulfuric phase + [2HI + (x)I2 + mH2 O]HIx phase . and the lower is the energetic efficiency of the entire chemical loop because of the higher heat duty for the concentration of both acids prior decomposition. / International Journal of Hydrogen Energy 32 (2007) 531 – 536 heat (600-950°C) Sulfuric section H2SO4 → SO3 + H2O → H2O + SO2 + ½ O2 SO2/H2O H2O H2SO4/H2O Bunsen section 2H2O + I2 + SO2 → H2SO4 + 2HI I2/H2O 2HI → I2 + H2 HIx section heat (300-450°C) Fig. water is reacted with I2 and SO2 to obtain hydriodic and sulfuric acids that can split into two liquid phases: a sulfuric phase (containing sulfuric acid and water) and a HI phase (containing HI with residual iodine and water). Giaconia et al.

10 as the iodine excess (x) was increased. Iodine concentration was determined by titration with a sodium tiosulfate (Na2 S2 O3 .84 0.16 0. with an anion column (Metrosep A SUP 4).2 0.527 H2 SO4 0.055 0.001 <0.A.15 0. iodine excess (x ) variable from 3.3 1. therefore. respectively). the upper sulfuric phase was quantitatively removed and the residual HIx phase weighted for density measurement and. Aldrich) and the residual amount of water were slowly added.30 0. (maximum experimental error on molar fractions rounded to the 2nd and 3rd decimal place is ±0.217 0.53 0.3 1.10 0.7 mM in NaHCO3 .001 <0.001 H2 O 0. less than a few unit percent of I2 and HI actually introduced in the vessel were transferred into the sulfuric phase: this amounts to < 4 mol% of HI and <1 mol% of I2 relative to the H2 SO4 in the sulfuric phase (Fig. and then weighted and analyzed. Aldrich) standardized solution.32 0.40 0.50 0. and afterwards the mixture was heated to the desired operative temperature.02 0.371 I2 0.003 0. always at 80 ◦ C.113 0.30 I2 0.106 0.86 0.6 g/mL. using a Metrohm 761 Compact Ionic Chromatograph. A quite different situation regards the amount of H2 SO4 transferred into the HIx phase: in all experiments the H2 SO4 initially loaded and lastly transferred into the HIx phase was . ranging from 3. / International Journal of Hydrogen Energy 32 (2007) 531 – 536 533 Table 1 Effect of temperature and Iodine concentration: water excess n = 11. 3 as molar ratios (Z) of HI and H2 SO4 in the HIx and sulfuric phases.9 to 16.217 0. The system was then energetically mixed and. As a result of the much higher iodine solubility in the HIx phase.84 0.48 0.051 0. Finally. Owing to solubility considerations.055 0.37 0.8 mM in Na2 CO3 and 1. while HI and sulfate content determined by ionic chromatography. kept at rest for at least 1 h to allow complete phase separation and equilibrium achievement.51 0.85 0.15 0. 4 ).033 Sulfuric phase compositiona HI 0. (98 wt%. Hence.85 0. temperature at equivalent iodine content was found to have an insignificant effect on the composition of the two phases (Table 1 and Fig. as well as to estimate the experimental accuracy. then.15 0. The absence of solid iodine in the bottom was checked by immersion of a glass bar. it was always quite easy to locate the phase boundary.02 0.001 H2 SO4 0. 3.572 0.001 <0. in agreement with what elsewhere reported [16].21 density (g/cm3 ) 1.2 3.004 0.001 0. Thus metered volumes of the supernatant sulfuric phase were sampled.6 a Composition expressed in molar fractions.001 0. relative to the total minus water. while the density of the sulfuric phase is always in the 1.001 0.37 0. In this case also the phase behavior at temperatures as high as 120 ◦ C was investigated.4 g/cm3 range regardless the iodine overall concentration (Table 1).15 0. Although both liquid phases appeared dark-red colored in the presence of iodine.14 0. a good segregation of the iodine-containing compounds was achieved under these conditions. 3.20 0. The eluent solution was 1. 95. the higher is the temperature the larger is the amount of iodine that can be loaded to the system. as the iodine load was increased both phases became purer in the two acids.6 0.14 0.572 0.069 H2 O 0.53).113 0.002.4 HIx compositiona HI 0.4 3.3 1.14 0.3–1.8 Sulfuric phase Sulfuric phase 80°C Sulfuric phase 95°C Sulfuric phase 120°C HIx phase 80°C HIx phase 95°C HIx phase 120°C feed 80°C feed 95°C feed 120°C 1.02 0.0 to 3. The corresponding plots are represented in Fig.14 0. Several samplings and analyses were made for each test to assess the repeatability of measurement and the effective physical equilibrium attainment.12 0. 3.0 0. Results are expressed in term of molar fractions. the 0.3 1.2 mol/molH2 SO4 (constant). afterwards.08 H2 O 0. washed with a KI solution and filtered in order to attest and quantify the possible solid sulfur formation. sulfuric/HIx phases volume ratio decreased from 3 up to ca.005 0.79 I2 0.01 and ±0.2 3.614 0. Results and discussion In Table 1 the composition and densities of both phases (HIx and Sulfuric) at different temperatures (80.093 0.0 mol/molH2 SO4 Entry T ◦C Feed compositiona HI 1 2 3 4 5 6 7 80 95 120 0.217 0. Particularly. Liquid–liquid phase behavior: effect of iodine excess.3 3.02 0.40 0. 120 ◦ C) and overall iodine concentration are reported. it was possible to operate at the highest temperature level (120 ◦ C) with a large amount of iodine (I2 overall molar fraction of about 0.01 0.86 0.30 HIx phase feed Z(HI) 0.48 0.02 0.271 0.0 Z(H2SO4) Fig. On the other hand.2 3.004 0.3 1.106 0.614 0.614 0. 3).004 0. regardless the temperature. Giaconia et al. Compositions expressed as molar ratios (Z) of the two acids relative to the total minus water.045 0.051 0. As shown in Fig.113 0. the density of the lower phase was rather sensitive to the iodine excess (x).0 3.16 0.503 0.32 0.359 0.00 0.3 1.4 0.055 0.004 0.62 H2 SO4 0. The composition of the lower HIx phase was at last determined by mass balance.47 0.01 density (g/cm3 ) 3.271 0.15 0.

/ International Journal of Hydrogen Energy 32 (2007) 531 – 536 0.09 0.53 at 120 ◦ C). The effect of temperature on the H2 SO4 partitioning is unclear. only at the largest I2 excess (molar fraction of 0. significantly reducing the management costs of the downstream HIx section. with x = 16) the amount of H2 SO4 relative to HI in the HIx phase was the order of 7 mol%.534 A.010 0. According to the results recently reported [17]. unless operating with a huge I2 load that would finally lead to high fixed and operative costs. Similarly to what earlier determined.002 0. being around 0. with only a slight decrease obtained with the increase in I2 excess (x). x (mol/molH2SO4) Fig. Water excess n = 11. In other words. sulfuric phase composition comprised <5 mol% of HI and <1. Giaconia et al.004 0.5 mol% of I2 relative to the H2 SO4 .06 0. Nevertheless.3 mol/mol. 16 the order of 15–25% (usually over 20%). the amount of H2 SO4 initially loaded and lastly transferred into the HIx phase was the order of 15–25%.04 (HI/H2SO4)Sulfuric phase 0.002 on molar fractions reported in Table 1 was estimated on values rounded to the 2nd and 3rd decimal place. x (mol/molH SO ) 2 4 4 8 16 iodine excess. the recovery of pure or highly concentrated HI for the subsequent decomposition step could be performed by high pressure distillation operations. after quantitative removal of H2 SO4 from the HIx phase. and results are represented in: composition (molar fractions) and densities of both phases (HIx and sulfuric) at two different temperature levels (80 and 95 ◦ C) are reported. such an unfavorable partitioning of the H2 SO4 practically determines a lower effective SO2 conversion than what predictable on the basis of reaction thermodynamics. The HI/H2 O ratio in the lower phase did not seem to vary sensibly with the iodine content.12 (H2SO4/HI)HIx phase 120°C mol/mol 0.000 80°C 95°C 120°C 4 8 16 iodine excess. being in the 9–15 mol% (relative to HI) in the other cases (Fig. 4. The increased water content did not affect the extent of contamination of both phases except for a slight increase of I2 and HI impurities in the sulfuric phase.15 80°C 95°C 0. as shown in Fig. 6.53 at 120 ◦ C. and almost not affected by the water addition (Fig. respectively: more precise data can be obtained only with more suitable but even much more complex sampling and analytical tools. the results of this semi-quantitative analysis have been confirmed by repeating each experiment more than a few times. x (mol/molH2SO4) Fig.00 (I2/H2SO4)Sulfuric phase 80°C 95°C 120°C 0. 7). the concentration of the HI in the HIx phase here determined should be higher than the corresponding predicted value for the azeotrope of HI/I2 /H2 O ternary mixtures at about 22 bar: hence. In fact it is reasonable that the H2 SO4 will be recovered from the HIx phase by reversing the Bunsen reaction and.01 and ±0. we observed that under the adopted conditions H2 SO4 concentration in the sulfuric phase was in the 47–50 wt%. where measured H2 SO4 concentration in the sulfuric phase was about 59 wt%. Again. with a concentration in the HIx phase in the 8–14 mol% range (relative to HI). Maximum experimental error of ±0.01 0. . 5). As far as the concentration of both acids in the corresponding phases is concerned. a certain dilution of both phases was observed when water overall concentration was increased: when the water excess (n) was increased from around 11 to 16 mol/mol.00 4 8 iodine excess. except for the experiment at the largest I2 content (molar fraction of 0.03 0. 0.02 0.2 mol/molH2 SO4 (constant). As expected. Effect of iodine excess on HI and I2 concentration in the sulfuric phase. Moreover. Effect of iodine excess on H2 SO4 concentration in the HIx phase.03 mol/mol 0.2 mol/molH2 SO4 (constant). This behavior is of major concern when we deal with purification of the HIx phase from H2 SO4 . The effect of water excess on liquid–liquid phase behavior was also studied by carrying out a set of experiments at different overall water content in the feed. reduced to SO2 and recycled back to the Bunsen reactor. therefore. Water excess n = 11.008 mol/mol 0.006 0. 5.

06 0.24 H2 SO4 0.113 0. results obtained suggest to minimize the water excess in the Bunsen reaction. (maximum experimental error on molar fractions rounded to the 2nd and 3rd decimal place is ±0. Moreover. Effect of water excess on H2 SO4 concentration in the HIx phase. since the addition of water did not lead to benefits on the degree of pureness of both phases.172 H2 SO4 0.014 0. n (mol/molH2SO4) Fig.32 0. Hence.16 0.055 0.8 expressed in molar fractions.15 0. The HIx /sulfuric phase volume ratios were rather unaffected by temperature and water excess.006 0. Increasing water excess (n) leads to a dilution of the acids (as expected). 50 to 41 wt%.88 I2 0.044 0.03 0.004 0.55 0.614 0. provided that distillation is carried out at pressures of at least 22 bar.0 3. Giaconia et al.01 0.00 11 13 16 ) 2SO4 water excess.12 0.63 0.86 0.8. and the HI/H2 O molar ratio in the HIx phase from 0.15 0. I2 excess x = 3.84 0. with respect of the reaction thermodynamics and kinetics constraints.614 0.9 mol/molH2 SO4 (constant).9.04 0. Our results show that: (1) Temperature and I2 content have little effect on the sulfuric acid and HI concentrations in the two phases.10).008 0.001 0.113 0.3 1.002 H2 SO4 0.A.090 0.50 0.695 0.02 535 density (g/cm3 ) 3.006 H2 O 0.53 0.192 0.012 0.15 0.659 0.01 and ±0.2 HIx compositiona HI 0.055 0. Concluding remarks Liquid–liquid phase behavior of products from the Bunsen reaction in the S–I thermochemical cycle has been investigated.3 1.000 11 13 16 water excess.217 0.3 1.010 0.86 0. 4. water excess (n) variable from 11.02 0.005 0.049 0.9 mol/molH2 SO4 (constant). This last result is in agreement with some earlier studies about side reaction occurrence in the Bunsen reaction [15]. 0. higher dilution of both acid streams lowers the energy efficiency of the cycle and increase the fixed and operative costs of the process. 6.13 0. respectively).044 Sulfuric phase compositiona HI 0.002.8 3.3.00 80°C 95°C 11 13 16 water excess. I2 excess x = 3. whilst the subsequent mol/mol .004 0. Finally.001 0. being in all experiments in the 3–4 range (Entries 1.695 I2 0.02 0.002 0.29 0. 2) we can recognize that temperature has not a significant effect on liquid–liquid phase behavior in the 80–120 ◦ C range and under the adopted composition.14 0. no sulfur formation was observed after all experiments provided that the sulfuric acid was slowly added when a large enough amount of I2 was dissolved. whereas HI concentration in the lower phase is always well over the azeotrope point [17]. n (mol/molH 80°C 95°C (I/H2SO4)Sulfuric phase mol/mol 0.3 1.100 0.01 0.09 0.006 0.2 2. n (mol/molH SO ) 2 4 80°C 95°C Fig.23 0.001 0. from the results described above (Tables 1.12 H2 O 0. H2 SO4 concentration in the sulfuric phase decreased from ca.15 0.12 0. Effect of water excess on HI and I2 concentration in the sulfuric phase.9 mol/molH2 SO4 (constant).33 to 0.001 0.02 0.62 I2 0.87 0.03 0.01 0.8 mol/molH2 SO4 Entry T ◦C Feed compositiona HI 1 8 3 9 10 80 95 0.19.2 to 15.30 0. / International Journal of Hydrogen Energy 32 (2007) 531 – 536 Table 2 Effect of temperature and water concentration: I2 excess x = 3.217 0. a Composition 0.12 density (g/cm3 ) 1. 7.005 0.12 (H2SO2/HI)HIx phase 0.0 2.172 0.05 (HI/H2SO4)Sulfuric phase mol/mol 0.090 H2 O 0.

Effects of process parameters of the IS process on total thermal efficiency to produce hydrogen from water. also in this latter case we found small practical improvements. [2] Brown LC. Giaconia et al. Pickard PS. [15].194:207–15.29:579–87. especially with regard to the hydriodic phase.233:347–54. Funk JF. Nakajima H. Investigation of 2 liquid phase separation characteristics on the iodine–sulfur thermochemical hydrogen production process. [11] Kasahara S. General Atomic Project 30047. Abe H. Onuki K. J Membrane Sci 2001. Petkovic LM. et al. Int J Hydrogen Energ 2000. Atlanta (Georgia. (3) We never observed secondary reactions in our experiments. Kameyama T. Shimizu S. References [1] Norman JH. and materials resistance. Nakajima H. if one lowers the mixture temperature the iodine content approaches the saturation point [16]. Futakawa M. Higashi S. A bench scale hydrogen production test by the thermochemical water-splitting iodine–sulfur process. A preliminary experiment concerning the Bunsen reaction under these conditions has already been carried out (this work will be completed within the next months) and the results indicate fast formation of the two phases with the expected compositions. Int J Hydrogen Energ 2005. Int J Hydrogen Energ 2004. / International Journal of Hydrogen Energy 32 (2007) 531 – 536 (2) Purity of both phases is almost unaffected by iodine content and temperature. this drastically decreases the acids concentration. Nakajima H. Diamanti M. [7] O’Keefe DR. 22–25 November 2005. This way we can carry out this exothermic reaction at a relatively mild temperature and using the lowest iodine excess (x). Nakajima H. Shimizu S. Kubo S. Choi H-S. Simulation study on the catalytic decomposition of hydrogen iodide in a membrane reactor with a silica membrane for the thermochemical water-splitting IS process.4 molI2 /molH2 SO4 on the I2 excess must be respected [15]. For these reasons we can assess that this is the smallest iodine initial molar fraction suitable for the Bunsen reaction. Stability of sulfuric acid decomposition catalysts for thermochemical water splitting cycles. A demonstration study on a closed-cycle hydrogen production by the thermochemical water-splitting iodine–sulfur process. Onuki K. Nomura M. Nakajima H. Upper bound and best estimate of the efficiency of the iodine sulphur cycle. Tayama I. Besenbruch GE. Experimental studies on side-reaction occurrence condition in the iodine–sulfur thermochemical hydrogen production process. [3] Kasahara S. Brutti S. Int J Hydrogen Energ 2006.61/0. 10–14 April 2005. Besenbruch GE. [14] Caputo G. Nomura thermal efficiency evaluation of HI synthesis/concentration procedures in the thermochemical water splitting IS process.46:141–9. According to the work of Sakurai et al. the iodine rate of dissolution at several temperatures. Ioka I. Onuki K. Membrane distillation of H2 O/HI mixtures for the sulfur–iodine thermochemical process. Hino R. June 2003. Catalytic decomposition of sulfuric acid in sulfur–iodine cycle for hydrogen production. Nakajima H.36:887–99. unless we use a very huge amount of iodine at 120 ◦ C. Hence. O’keefe DR. [4] Kubo S. taking into account a security gap. Masaki T. Proceedings of the 2005 AIChE spring national meeting. USA). J Membrane Sci 1999. Williamson DG. Onuki K. Int J Hydrogen Energ 2000. Onuki K.536 A. Finally. Felici C. [12] Hwang G-J. High efficiency generation of hydrogen fuels using nuclear power. [5] Kubo S. De Maria G. Onuki K. a temperature of at least 80 ◦ C seems a good choice to avoid this problem.22(3):325–69. Screening tests on materials of construction for the thermochemical IS process. as mentioned above. our future work will be mainly dedicated to phase purification. [13] Hwang G-J. 9–13 October 2005.22/0. Thermochemical water splitting for hydrogen production.25:605–11.11/0. and fluctuations of the mixture composition can produce formation of solid iodine. 1981. Other parameters do not produce significant improvements either in the phase purity or in the acids concentration.4 molI2 /molH2 SO4 . Kotera Y. [10] Onuki K. [15] Sakurai M. Fukuda K. However. [16] Sakurai M. we are close to the limit previously indicated. Borgard J. Iodide and HI in sulfuric phase are always 1–2% of the total. Schultz KR. Catalysis research in thermochemical water-splitting processes. Bull Chem Soc Jpn 1977. et al.50:2657–60.30: 619–26. Catal Rev—Sci Eng 1980. The only alternative is to increase the water excess (n) but. [9] Ginosar DM. GRI-80/0105. Ohya H. further studies must be performed. Vitart X. J Chem Eng Jpn 2003. Amir R. Kasahara S.06 (Entry 3) is the best choice for us. An oxygen-evolving step through the thermal splitting of sulfuric acid. Corr Eng 1997. Onuki K. (4) The reaction temperature of 80 ◦ C seems a good compromise between the exothermicity of the reaction and iodine dissolution. while sulfates in hydriodic phase are always more than 15% of the total. It follows that a temperature of 80 ◦ C and an initial molar fractions of HI/H2 O/I2 /H2 SO4 = 0.31:883–90. The study of thermochemical hydrogen preparation. in order not to have secondary reactions iodine excess (x) should be larger than 3. provided that the components are initially mixed at a temperature not over 80 ◦ C. Proceedings of the second European hydrogen energy conference. Glenn AW. Sau S. Lentsch RD. III. Hydrogen separation in H2 –H2 O–HI gaseous mixture using the silica membrane prepared by chemical vapor deposition.9 molI2 /molH2 SO4 . In our experiments with the lowest iodine content we had x = 3. [8] Barbarossa V. Tsukuba. [17] Goldstein S. especially on the viscosity of the two phases. Shimizu S. Japan.162:83–90. . Shimizu S. Shimizu S. [6] Dokiya M. and so. Norman JH. Hwang G-J. Proceedings of GLOBAL 2005. In order to implement a bench scale reactor for the Bunsen part of the S–I cycle. Furthermore.25:613–9. Nucl Eng Des 2004. Zaragoza (Spain). the condition x > 3.