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International Journal of Hydrogen Energy 30 (2005) 619 – 626 <a href=www.elsevier.com/locate/ijhydene Upper bound and best estimate of the efficiency of the iodine sulphur cycle Stephen Goldstein , Jean-MarcBorgard, Xavier Vitart CEA/DEN/DPC, CEN, Saclay, 91191 Gif sur Yvette, France Available online 21 August 2004 Abstract An upper bound and a best estimate of the efficiency of a thermochemical iodine sulphur water splitting cycle coupled with a High Temperature Reactor operating between 760 K and 1144 K are proposed in this publication. An upper bound of 51% is found assuming ideal reversible chemical reactions and constraints related to the heat exchange between helium and chemical process. It appears that the separations between water and sulphuric acid on one hand and water, HI and iodine on the other hand are the most energy consuming. The best estimate of the efficiency is found between 33% and 36% according to the assumptions made for the temperature pinch at the heat exchangers of the hydrogen production section. More realistic values can be obtained after having designed the heat exchangers of this section. 2004 International Association for Hydrogen Energy. Published by Elsevier Ltd. All rights reserved. Keywords: Reaction; Thermodynamic data; Efficiency 1. Introduction Among the large scale, cost effective and environmen- tally attractive hydrogen production processes, sulphur io- dine (I_S) thermochemical cycle [1] seems to be a quite promising one. This cycle was originally studied in the 1980s by General Atomics Co [2] (GA) and can be split into the following reactions: ( 9I ) + ( SO ) + ( 16H O ) ⇒ ( 2HI + 10H O + 8I ) + ( H SO + 4H O ) ( 393 K ), (1) L = ( 2HI + 10H O + 8I ) ⇒ ( 2HI ) + ( 10H O + 8I ) ( 500 K ), ( 2HI ) ⇒ H + ( I ) ( 600 K ), (2) (3) Corresponding author. Tel.: +33-1-6908-6410; fax: +33-1- 6908-6802. E-mail address: stephen.goldstein@cea.fr (S. Goldstein). L = ( H + SO + 4H O ) ⇒ ( H SO ) + ( 4H O ) ( H SO ) ( H SO ) ⇒ ( H SO ) ( 570 K ), ( 630 K ), ⇒ ( SO ) + ( H O ) ( 670 K ), ( SO ) ⇒ ( SO ) + 1 O ( 1140 K ). (4) (5) (6) (7) The temperatures between brackets are approximate and de- pend upon the pressure which is not necessarily uniform in the different parts of the cycle. The first reaction, called Bunsen reaction, proceeds exothermically in liquid phase and produces two immisci- ble aqueous acid phases which compositions are indicated between brackets: L phase which is aqueous sulphuric acid and L phase which is a mixture of hydrogen iodide, iodine and water named HI . In the second reaction, HI is sepa- rated from L . This separation is the most critical phase of the cycle. Reaction (3) is the thermal decomposition of HI. Roth and Knoche [3] proposed to perform reactions (2) and 0360-3199/$30.00 2004 International Association for Hydrogen Energy. Published by Elsevier Ltd. All rights reserved. doi:10.1016/j.ijhydene.2004.06.005 " id="pdf-obj-0-2" src="pdf-obj-0-2.jpg">

International Journal of Hydrogen Energy 30 (2005) 619 – 626

International Journal of Hydrogen Energy 30 (2005) 619 – 626 <a href=www.elsevier.com/locate/ijhydene Upper bound and best estimate of the efficiency of the iodine sulphur cycle Stephen Goldstein , Jean-MarcBorgard, Xavier Vitart CEA/DEN/DPC, CEN, Saclay, 91191 Gif sur Yvette, France Available online 21 August 2004 Abstract An upper bound and a best estimate of the efficiency of a thermochemical iodine sulphur water splitting cycle coupled with a High Temperature Reactor operating between 760 K and 1144 K are proposed in this publication. An upper bound of 51% is found assuming ideal reversible chemical reactions and constraints related to the heat exchange between helium and chemical process. It appears that the separations between water and sulphuric acid on one hand and water, HI and iodine on the other hand are the most energy consuming. The best estimate of the efficiency is found between 33% and 36% according to the assumptions made for the temperature pinch at the heat exchangers of the hydrogen production section. More realistic values can be obtained after having designed the heat exchangers of this section. 2004 International Association for Hydrogen Energy. Published by Elsevier Ltd. All rights reserved. Keywords: Reaction; Thermodynamic data; Efficiency 1. Introduction Among the large scale, cost effective and environmen- tally attractive hydrogen production processes, sulphur io- dine (I_S) thermochemical cycle [1] seems to be a quite promising one. This cycle was originally studied in the 1980s by General Atomics Co [2] (GA) and can be split into the following reactions: ( 9I ) + ( SO ) + ( 16H O ) ⇒ ( 2HI + 10H O + 8I ) + ( H SO + 4H O ) ( 393 K ), (1) L = ( 2HI + 10H O + 8I ) ⇒ ( 2HI ) + ( 10H O + 8I ) ( 500 K ), ( 2HI ) ⇒ H + ( I ) ( 600 K ), (2) (3) Corresponding author. Tel.: +33-1-6908-6410; fax: +33-1- 6908-6802. E-mail address: stephen.goldstein@cea.fr (S. Goldstein). L = ( H + SO + 4H O ) ⇒ ( H SO ) + ( 4H O ) ( H SO ) ( H SO ) ⇒ ( H SO ) ( 570 K ), ( 630 K ), ⇒ ( SO ) + ( H O ) ( 670 K ), ( SO ) ⇒ ( SO ) + 1 O ( 1140 K ). (4) (5) (6) (7) The temperatures between brackets are approximate and de- pend upon the pressure which is not necessarily uniform in the different parts of the cycle. The first reaction, called Bunsen reaction, proceeds exothermically in liquid phase and produces two immisci- ble aqueous acid phases which compositions are indicated between brackets: L phase which is aqueous sulphuric acid and L phase which is a mixture of hydrogen iodide, iodine and water named HI . In the second reaction, HI is sepa- rated from L . This separation is the most critical phase of the cycle. Reaction (3) is the thermal decomposition of HI. Roth and Knoche [3] proposed to perform reactions (2) and 0360-3199/$30.00 2004 International Association for Hydrogen Energy. Published by Elsevier Ltd. All rights reserved. doi:10.1016/j.ijhydene.2004.06.005 " id="pdf-obj-0-6" src="pdf-obj-0-6.jpg">

Upper bound and best estimate of the efficiency of the iodine sulphur cycle

Stephen Goldstein , Jean-MarcBorgard, Xavier Vitart

CEA/DEN/DPC, CEN, Saclay, 91191 Gif sur Yvette, France

Available online 21 August 2004

Abstract

An upper bound and a best estimate of the efficiency of a thermochemical iodine sulphur water splitting cycle coupled with a High Temperature Reactor operating between 760 K and 1144 K are proposed in this publication. An upper bound of 51% is found assuming ideal reversible chemical reactions and constraints related to the heat exchange between helium and chemical process. It appears that the separations between water and sulphuric acid on one hand and water, HI and iodine on the other hand are the most energy consuming. The best estimate of the efficiency is found between 33% and 36% according to the assumptions made for the temperature pinch at the heat exchangers of the hydrogen production section. More realistic values can be obtained after having designed the heat exchangers of this section. 2004 International Association for Hydrogen Energy. Published by Elsevier Ltd. All rights reserved.

Keywords: Reaction; Thermodynamic data; Efficiency

1. Introduction

Among the large scale, cost effective and environmen- tally attractive hydrogen production processes, sulphur io- dine (I_S) thermochemical cycle [1] seems to be a quite promising one. This cycle was originally studied in the 1980s by General Atomics Co [2] (GA) and can be split into the following reactions:

(9I 2 ) 1 + (SO 2 ) g + (16H 2 O) 1

(2HI + 10H 2 O + 8I 2 ) 1

+(H 2 SO 4 + 4H 2 O) 1

(393 K ),

(1)

L 2 = (2HI + 10H 2 O + 8I 2 ) 1

(2HI) g + (10H 2 O + 8I 2 ) 1

(500 K ),

(2HI) g H 2 + (I 2 ) 1 (600 K ),

(2)

(3)

Corresponding author. Tel.: +33-1-6908-6410; fax: +33-1-

6908-6802.

E-mail address: stephen.goldstein@cea.fr (S. Goldstein).

L 1 = (H 2 + SO 4 + 4H 2 O) 1

(H 2 SO 4 ) 1 + (4H 2 O) 1

(H 2 SO 4 ) 1 (H 2 SO 4 ) g

(H 2 SO 4 ) g

(570 K ), (630 K ),

(SO 3 ) g + (H 2 O) g

(670 K ),

(SO 3 ) g (SO 2 ) g +

1

2

O 2

(1140 K ).

(4)

(5)

(6)

(7)

The temperatures between brackets are approximate and de- pend upon the pressure which is not necessarily uniform in the different parts of the cycle. The first reaction, called Bunsen reaction, proceeds exothermically in liquid phase and produces two immisci- ble aqueous acid phases which compositions are indicated between brackets: L 1 phase which is aqueous sulphuric acid and L 2 phase which is a mixture of hydrogen iodide, iodine

and water named HI x . In the second reaction, HI is sepa- rated from L 2 . This separation is the most critical phase of the cycle. Reaction (3) is the thermal decomposition of HI. Roth and Knoche [3] proposed to perform reactions (2) and

0360-3199/$30.00 2004 International Association for Hydrogen Energy. Published by Elsevier Ltd. All rights reserved.

doi:10.1016/j.ijhydene.2004.06.005

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620 S. Goldstein et al. / International Journal of Hydrogen Energy 30 (2005) 619 – 626

Fig. 1. Sketch of the I_S cycle.

(3) in the same reactive distillation column. Reaction (4) is

the separation of L 1 in H 2 SO 4 and H 2 O. Up to now only distillation has been proposed for this separation. Several distillation flowsheets are found, ranging from the simple column [4] to multi effect arrangements [5,7]. This step is energy consuming due to the large number of water moles to evaporate. Reactions (5)–(7) proceed in gas phase and pro-

duce H 2 O, SO 2 and oxygen. These gases are cooled down before to bubble in the Bunsen reactor to separate oxygen from SO 2 and H 2 O. Due to the fact that reaction (7) is in- complete, a residual quantity of SO 3 is found in the hot gases at the outlet of reaction (7). This SO 3 is recombined to H 2 O in a reactor where the reverse of reaction (6) is per- formed and the produced diluted H 2 SO 4 is recycled in reac- tion (4). Membrane separation of oxygen is considered by certain teams to shift to the right reaction (7) and to increase the partial pressure of SO 2 in the Bunsen reactor. Besides this separation has the advantage to reduce the amount of H 2 SO 4 recycled. The whole cycle can be divided into three sections according to the GA nomenclature [2], we shall call section I reaction (1), section II reactions (4)–(7) and sec- tion III reactions (2) and (3). A sketch of the cycle is shown Fig. 1. In this paper, we would like first to find an upper bound of the efficiency of this cycle. Therefore, in the next section, we assumed that the energy requirements of reactions (1)–(7) are the minimum prescribed by the thermodynamics, and that the decomposition reaction (7) is complete, therefore no H 2 SO 4 is recycled. In Section 3, we review the published efficiency calculations and present our best assessment of section III. A more realistic efficiency of the whole cycle is then deduced.

Finally, we conclude with the R&D needs to bring this cycle to an industrial level.

2. Efficiency bound

We define the thermal efficiency th as the ratio of the en- thalpy of the hydrogen and oxygen recombination reaction at ambient temperature and pressure H H 2 O (T a ) = 286 kJ/mol to the total heat requirement of the cycle:

0

th =

0

H H 2 O (T a )

Q + W/ r

,

Q and W are the heat and work requirements and r the effi- ciency of the conversion system. We used for the numerical calculations r = 0.5, which corresponds to the efficiency of the current high temperature reactors projects. Let H , S and G be the enthalpy, entropy and Gibbs free enthalpy of a chemical reaction at a given temperature T . Each reaction of the cycle is supposed to be performed at a temperature for which G is as close as possible to zero. The condition G = 0 cannot be fulfilled systemati- cally due to possible constraints. The reactants are brought from ambient temperature and pressure to the reaction con- ditions, and the products are brought back from the reaction conditions to the ambient conditions. The heat capacities of reactants and products are supposed to be equal, there- fore the heat content of the products can be recovered by the reactants. Phase changes or separations are considered as independent reactions, therefore no phase change occurs during heating of the reactants or cooling of the products.

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621

Thus, the heat Q and work W requirements of each re- action are:

Q T S,

W H T S = G,

W + Q = H.

The signs , are replaced by = when the reactions are reversible. If the turbine, that produces W , is included in the system, then we must consider the heat Q a rejected to the ambient temperature T a . In this case:

W = 0,

Q 1

T a

T

H T a S,

Q Q a = H.

All the energy input is heat, and in the reversible case, the turbine is supposed to have a Carnot efficiency, which is too optimistic. Consequently we shall use the first formulation. Hence, the heat requirement is:

G

r

+ ( H G)

if H G > 0

and

G

r

if H G < 0.

In the latter case, the reaction is exothermic and the heat of reaction is lost, or can be recovered for internal use if T is high enough.

2.1. Thermodynamic data of the reactions

The optimum pressures of the three sections of the cycle are not equal due to thermodynamicreasons. The temper- ature of section I must be higher than the melting point of iodine but not too high to avoid the occurrence of the reverse reaction. Therefore, we assumed that this reaction (1) is per- formed at 400 K and 2 bar. The pressure of section II must be low, due to the fact that the number of gaseous moles is increasing, therefore, the low pressure shifts the reactions towards completion. We have chosen 1 bar for this section. Finally, the best pressure for section III is 50 bar. The more the pressure of this section is high, easier is the distillation of HI, because, the position of the azeotrope depends upon the pressure. 50 bar seems a reasonably high value. Of course, pumping power is needed to adjust the pressures. It will be taken into account in the energy balance. The Bunsen reaction (T = 400 K, p = 2 bar ) can be split into four elementary reactions:

(SO 2 ) g + (2H 2 O) 1 (H 2 SO 4 ) 1 + H 2 ,

(I 2 ) 1 + H 2 (2HI) g ,

(8)

(9)

(H 2 SO 4 ) 1 + (4H 2 O) 1 (H 2 SO 4 · 4H 2 O) 1 , (10)

(2HI) g + 8I 2 + (10H 2 O) 1 2(HI · 5H 2 O) 1 + 8I 2 . (11) Eqs. (8) and (9) are endothermicand their heats of reac- tion can be computed with standard thermodynamic tables [8]. One finds for (8): H = 53 kJ/mol, G = 95 kJ/mol

S. Goldstein et al. / International Journal of Hydrogen Energy 30 (2005) 619 – 626 621

Fig. 2. Thermodynamicdata for reaction (7), p = 1 bar.

S. Goldstein et al. / International Journal of Hydrogen Energy 30 (2005) 619 – 626 621

Fig. 3. Thermodynamicdata for reaction (6), p = 1 bar.

and for (9) H = 34 kJ/mol, G = −11 kJ/mol. Reac- tions (10) and (11) stand for the exothermicdissolutions of H 2 SO 4 and HI in water. Their heats of solution, computed using Engels strong acid model [9], are: H =−58 kJ/mol,

G = −40 kJ/mol for (10), and H = −122 kJ/mol, G = −116 kJ/mol. In (11) iodine is supposed to have no influence on the heat of solution. This assumption is probably wrong because evidence of ion solvation with iodine molecules has been demonstrated in several papers. Calabrese [10] for ex-

ample, shows experimentally that I

  • 3 ions exist in dilute so-

lutions and theoretically that I 2x H + should exist as well. Unfortunately, there is no direct measurement of the heat of the Bunsen reaction. We shall then assume that we can add the heats of (4)–(7), which gives 93 kJ/mol. The data for reactions (7), (6) and (3) are found for ex- ample in [8] and are represented Figs. 2–4. Given the fact that the sulphuric acid boils at 612 K at 1 bar and that the heat of vaporisation is 58 kJ/mol, we can draw the Q/T diagram of section II (Fig. 5):

We assumed that the maximum helium temperature was 1144 K and the return to the reactor temperature was 760 K. The pinch point was taken equal to 17 K. We have now all the inputs to calculate the total heat request.

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622 S. Goldstein et al. / International Journal of Hydrogen Energy 30 (2005) 619 – 626

Fig. 4. Thermodynamicdata for reaction (3), p = 50 bar.

622 S. Goldstein et al. / International Journal of Hydrogen Energy 30 (2005) 619 – 626

Fig. 5. QT diagram of section II.

  • 2.1.1. Section II

Reaction (4): The temperature has a slight influence on the heat requirement of this reaction. Therefore, we supposed that this reaction is the reverse of reaction (10). Hence, H = 58 kJ/mol and G = 40 kJ/mol. The reaction can be performed with 40 kJ of mechanical work and 18 kJ of heat. The heat demand is then: 18+40/0.5 = 98 kJ/mol. Reaction (5): Heat demand: 58 kJ/mol. Reaction (6): According to Figs. 3 and 5, the reaction is performed at G = 0, therefore, the heat demand is T S = 94.3 kJ/mol.

Reaction (7): Due to the pinch of 17 K, the reaction occurs with a slightly positive G i.e: G = 4.5 kJ/mol and H = 97.6. The heat request is then: (97.6 4.5) + 4.5/0.5 =

  • 102 kJ/mol.

Hence, the total amount of heat request for this section is: 98 + 58 + 94.3 + 102 = 352.3 kJ/mol.

  • 2.1.2. Section III

Reaction (2) is the reverse of reaction (11), but occurs at higher temperature and pressure. At 500 K and 50 bar, we have H = 66 kJ/mol and G = 77 kJ/mol. Due to the fact that the mixing enthalpy depends upon the tempera- ture, we cannot assume that the specific heats of the reac- tants and products are the same. Therefore we shall take H = 122 kJ/mol (opposite of reaction (11)) and G = 77 kJ/mol. Hence the heat requirement is: (122 77) + 77/0.5 = 199 kJ/mol.

Reaction (3): According to Fig. 4, G = 12 kJ/mol, H = −24 kJ/mol, therefore the heat request is 12/0.5 = 24 kJ/mol. The two reactions occurring in the same reactor, we added the G and H , which results in G = 89 kJ/mol and H = 98 kJ/mol. The heat requirement is then: 89/0.5 + 98 89 = 187 kJ/mol.

2.1.3. Pumping power

The pumping power (mechanical efficiency of 0.75) to raise the pressure of SO 2 from 1 to 2 bar is RT L n (2)/0.75 = 3 kW and the pumping power of section III (see next section)

is 5.3 kW. The additional heat due to the pumping power is then (3+5.3)/0.5 = 17 kW. According to these figures, an upper bound for the effi- ciency is: th = 286/(352 + 187 + 17) = 0.51. It can be noticed that the separation steps (Eqs. (2) and (4)), are the most energy consuming (98 and 199 kJ/mol).

3. Best estimate of the efficiency

Many estimations are found in the literature, either for the whole cycle or for sections II or III taken separately. The first efficiency estimation was published by GA [2] in 1981. H 2 SO 4 was separated from water by a constant pressure

multi effect distillation and HI was separated from HI x by using phosphoricacid that had to be regenerated. The total efficiency was 0.47. Other papers deal with the heat demand of section II. In a

recent work GA [7] using a more accurate thermodynamic model, estimated the heat demand at 420 kJ/mol. The pres- sure of the distillation stages ranged from 35 to 0.07 bar. The reason of this variation is to recover the maximum heat for internal use in the first stages of the distillation. Ozturk [5] proposed a flowsheet where the produced oxygen is used to boil by direct contact the sulphuric acid. The heat demand was 441.5 kJ/mol. In an alternative flowsheet, Schepers [6] proposed an increasing pressure multi effect distillation pro- cess. The heat demand could be decreased to 389 kJ/mol.

S. Goldstein et al. / International Journal of Hydrogen Energy 30 (2005) 619 – 626

623

Finally the author [4] found that with a simple distillation column a heat demand was 520 kJ/mol. The conclusion of these results is that there should be a compromise between efficiency and complexity and therefore cost of this section and that the optimum design is not necessarily the one with the minimum heat request. In the following we shall take the GA value of 420 kJ/mol as a best estimate value. Much less results are available for section III, due to the lack of thermodynamic data of the HI x mixture. Roth and Knoche [3] calculated a reactive distillation column and external circuits and found an overall heat request of 237 kJ/mol. The research teams of JAERI use electrodialysis to concentrate HI in HI x before to distillate the enriched HI x , but no best estimate efficiency calculation is yet published. The calculation of the reactive distillation of section III is very difficult because of the complex behaviour of the vapour–liquid equilibrium of HI x . In the next section we describe briefly the model used and we give preliminary results concerning the heat requirement of this section.

3.1. Available experimental data

Experimental data are available for the binary systems I 2 –H 2 O, HI–H 2 O and for the ternary HI–I 2 –H 2 O. The I 2 –H 2 O system has been studied by Kracek [11] in 1931. He measured the solubility of iodine in water and put in evidence a miscibility gap lying between the solid–liquid equilibrium point at 385.3 K (very close to the melting point of iodine: 386.7 K) and an upper temperature of approxi- mately 553 K. At 385.3 K, the light aqueous liquid contains a very small amount of iodine (0.05 mol %) and the heavy liquid 98 mol % of iodine. Total pressures of HI–H 2 O mixtures have been measured by Wüster [12] and the mixing enthalpies by Vanderzee and Gier [13]. This system exhibits an azeotrope whose precise location depends on temperature and pressure. At ambient temperature, the azeotrope corresponds to a molar fraction of HI of almost 15%. For HI concentrations higher than the azeotrope, the vapour phase is very rich in HI, and for high temperatures (> 500 K ), HI might be dissociated in the vapour phase in H 2 and I 2 . The kinetics of this reaction is in principle very slow but possible catalytic effects or hydrogen production in the liquid phase might appear as discussed by Berndhauser [14]. We shall assume in this paper that the decomposition reaction of HI takes place only in the vapour phase. These experimental results have been used by Engels [9] to fit the binary interaction parameters of his model, using the Wilson model for the calculation of the activity coefficients. Detailed total pressure measurements for the HI–H 2 O–I 2 ternary system for a [HI]/[H 2 O] ratio up to 0.19 and var- ious iodine concentrations are found in Neumann [15]. A synthesis of these results has been published by Engels and Knoche [16]. Experimental location of borderlines of the ternary phase diagram are found in [2]. From these results, it appears that the liquid phase exhibits two miscibility gaps

which are the extensions in the ternary diagram of those found for the binaries I 2 –H 2 O and HI–H 2 O. The I 2 –H 2 O miscibility gap tends to disappear rapidly with increasing HI concentration probably because of the formation of polyio-

dides ions like I

3

or I 2 H + .

  • 3.2. Neumann’s thermodynamic model

The

thermodynamicmodel

for the H 2 O–HI–I 2 –H 2

reactive-liquid–liquid–vapour system proposed by Neu- mann is based on the following assumptions:

hydrogen is only present in the gas phase; the vapour phase is ideal, despite high pressures; the following solvation reaction is taken into account in the liquid phase [9]:

mH 2 O + HI ↔ {(mH 2 O, H + ) + I } with

m = 5,

HI decomposition 2 HI H 2 + I 2 takes place in the gas phase only.

The NRTL activity coefficient model is used to take into account the non-ideality of the liquid phase and the binary interaction parameters (including solvent-complex) have been estimated by Neumann [15] from the experimental data of Engels and Knoche [16] for the H 2 O–HI–I 2 –H 2 sys- tem. The entire thermodynamical model includes solvation equilibrium, mass balances, HI decomposition equilibrium in vapour phase and vapour–liquid-phase equilibrium. With such model, the phase diagrams can be calculated with confidence on the left-hand side of the binary azeotropic H 2 O–HI or for low iodine content. Uncertainties remain for high iodine contents (> 20%) and high temperatures (> 540 K ). The main features of this model have been published in [4]. We recall here the behaviour of the ternary mixture at 22 bar, which is the pressure chosen by Roth and Knoche [3] for their reactive distillation calculation.

  • 3.3. Ternary system HII 2 H 2 O

A fundamental aspect for the reactive distillation design is the influence of I 2 concentration on the maximum bubble temperature of the ternary system H 2 O–HI–I 2 . The calcu- lated results are presented on Fig. 6. Each curve corresponds to the bubble curve of a ternary system H 2 O–HI–I 2 with constant I 2 mole fraction varying in the interval: 1 (pure I 2 ), 0 (binary H 2 O–HI). Thus the last curve on the right is the bubble curve of the binary H 2 O–HI with a maximum azeotrope at x HI = 0.133. The crest line, locus of the maxi- mum bubble points, joins the pure I 2 point (T = 359.17 K ) to the binary azeotrope H 2 O–HI (T = 245.13 C). Fig. 7 shows the ternary diagram of the system H 2 O–HI–I 2 at 22 bar, limited to the region of interest for the reactive distillation design. We have notably reported the

  • 624 S. Goldstein et al. / International Journal of Hydrogen Energy 30 (2005) 619 – 626

624 S. Goldstein et al. / International Journal of Hydrogen Energy 30 (2005) 619 – 626

Fig. 6. Influence of I 2 on the maximum bubble temperatures.

624 S. Goldstein et al. / International Journal of Hydrogen Energy 30 (2005) 619 – 626

Fig. 7. Ternary diagram of the system H 2 O–HI–I 2 .

singular points: pure I 2 (origin) and pure H 2 O; the binary azeotrope H 2 O–HI and the binary heteroazeotrope H 2 O–I 2 . The distillation frontier is the projection of the crest shown in Fig. 6. Note that a linear approximation of this frontier is not correct. Finally, Fig. 7 shows the liquid–liquid–vapour domain for low HI content.

This diagram gives information on feasible distillation paths at 22 bar. Thus, as mentioned by Roth and Knoche [3], from the feed composition (HI/H 2 O/I 2 = 0.1/0.51/0.39), we could obtain pure iodine as residue and, by dissociation of HI, a distillate with H 2 , the feed point being just on the right of the distillation frontier. The straight line in Fig. 7

S. Goldstein et al. / International Journal of Hydrogen Energy 30 (2005) 619 – 626 625
S. Goldstein et al. / International Journal of Hydrogen Energy 30 (2005) 619 – 626
625
Fig. 8. Flowsheet of section III.
Table 1
Energy requirements and temperatures
Table 2
Inlet/outlet streams compositions
Component
Load (kW)
Tin (K)
Tout (K)
Stream
H 2 O
HI
I 2
H 2
Total mol/s
E1
482
393
575.4
Entry
10.2
2
7.8
0
20
E2
69.1
584
548.4
Exit 1
0.987
0.004
0.117
0.333
1.441
E3
369.6
548.4
393
Exit 2
9.21
1.33
8.02
0
18.56
Column boiler
310
584
584
Column condenser
221
548.4
548.4
Pump
5.3
Separator
61.6
548.4
548.4

represents the mass balance and gives the composition of the distillate we could obtain without chemical reaction (HI/H 2 O = 0.17/0.83). As a matter of fact we see that the number of water moles to evaporate is significant. Finally, we present Fig. 7 the liquid profile obtained by simulation of a reactive distillation column, with HI dissociation in the vapour phase. This profile follows very closely the distilla- tion frontier. These preliminary simulation and thermody- namics results give the basis for the optimal design of the reactive distillation process [17].

3.4. Flowsheet of section III

The above Neumann’s model has been implemented in the chemical engineering code PROSIM and we proceeded by trial and error to converge on the flowsheet of Fig. 8 . The pump P raises the pressure to 50 bar and the valve V brings it back to 2 bar. The column has 25 stages, feed is at stage 18 (stage No 1 is the upper stage). Heat exchanger E2 cools the residue at the same temperature as the condenser:

548.4 K. The liquid vapour separator S condenses part of the steam and HI of the distillate. This additional condensa- tion occurs because the composition of the distillate and the residue are different. The energy requirements of the main components are found in Table 1 and the stream composi- tions in Table 2.

The heat released by E2 and E3 can be partly recovered

by E1. The amount of heat recovered depends on the tem- perature difference assumed between the primary and the secondary circuit, which depends on the size of the heat exchangers. To size the heat exchangers, the physical prop- erties of the fluids are needed, but are not known. A priori these physical properties are not very favourable. For exam- ple, the Prandtl number for liquid iodine is P r = 1500 at 400 K and P r = 1600 for pure HI at 230 K. Anyway, in this paper, the heat exchangers are not dimensioned and we as- sumed minimum temperature differences between primary and secondary sides of the heat exchangers of 10 and 20 K. The heat recovered can then be deduced from the QT dia- grams of E1 and E2+E3+E4. We find that, if the temperature difference is 10 K, then the net heat request is 37 kW, and if the temperature difference is 20 K, it is 63.5 kW. Due to the fact that the temperature difference between the condenser and the boiler is small (35.6 K), a water heat pump can be used to raise the temperature of the heat released at the condenser and to use it for the boiler. The total heat released at the condenser of the column and the separator is 221+61.6 = 282.6 kW at 548.4 K. The total heat request at the boiler of the column is 310 kW at 584 K. If we assume 5 K of temperature drop between the condenser of the column and the boiler of the heat pump, and 5 K between the condenser of the heat pump and the boiler of the column, then the heat pump has to transfer 282.6 kW from 543.4 K to a temperature of 589 K. Now, a water heat pump operating at these temperatures and with

  • 626 S. Goldstein et al. / International Journal of Hydrogen Energy 30 (2005) 619 – 626

one mole of water circulating, can transfer 272.3 kW of heat with a mechanical work of 37.1 kW (assuming 0.75 mechanical efficiency for the pump). In our case we need then 282.6/272.3 = 1.04 mol of water. The heat recovered is then 1.04(272.3 + 37.1 0.75) = 312 kW, which is almost the heat required at the boiler of the column. The total heat demand for one mol of H 2 produced is finally: (37 + (37.1 1.04 + 5.3)/0.5)/0.333 = 375 kW if the temperature difference is 10 K and (63.5 + (37.1 1.04 + 5.3)/0.5)/0.3331 = 454 kW if the temperature difference is 20 K. It can be noticed that in this flowsheet, the number of mol/s at the entry is exactly that at the exit of the Bunsen re- action. The H 2 production being only 0.333 mol/s, it means that an important quantity of materials must be recirculated between sections III and I. Typically, 20/0.333 = 60 mol/s must enter section III. The head losses of such a mass flow rate have not been taken into account. The best estimate of the efficiency with today’s knowledge and a temperature difference of 10 K for the heat recovery between E1 and E2, E3 is then 286/(375+420) = 0.36. If the temperature difference is 20 K, the efficiency becomes 286/(454+420) = 0.33.

4. Conclusion—R&D needs

With the current reactions (1)–(7), widely adopted for the iodine sulphur cycle, we found an upper bound of the efficiency of 0.51. This value has been found by calculating the heat and work requirements of the reactions, assuming that they were reversible and a maximum temperature of the helium of 1144 K. A best estimate could be calculated as well by taking the latest GA value for the heat request of section II together with a reactive distillation calculation of section III. We found a value comprised between 0.33 and 0.36, depending on the temperature difference assumed for the heat recovery between E2+E3 and E1. These figures will be more accurately specified in the future when the heat exchangers will be sized. They do not take into account the head losses due to the large material circulation. Many improvements can be imagined to rise both these figures:

Reduction of the amounts of iodine and water in the Bun- sen reaction. We have seen that these excesses of iodine and water burden heavily the heat balances of both sections II and III. Use of membranes at various steps of the cycle: To sepa- rate SO 2 from O 2 , to separate liquid H 2 O from H 2 SO 4 , to separate HI from HI x (electrodialysis or distillation mem- branes?) and finally to separate H 2 from (HI+ H 2 O) g . Many teams, in particular in Japan, currently work actively on

these topics. Membranes can be foreseen if their permeabil- ity and selectivity are high enough. Finally the HI x section still represents a real chemical engineering challenge. Additional thermodynamic measure- ments are necessary and the best distillation design has to be found. Further experiments are planned, to be performed by the Commissariat à l’Energie Atomique (CEA), in order to improve the database of the ternary mixture, more specif- ically at high iodine contents and to measure the vapour partial pressures as well.

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