ARTICLE IN PRESS

Journal of Light Metals xxx (2001) xxxxxx

www.elsevier.com/locate/ligandmet

F
2 A thermochemical analysis of the production of anhydrous MgCl2

OO
3 Georges J. Kipouros a, Donald R. Sadoway b,*
4 a
Department of Mining and Metallurgical Engineering, Dalhousie University, 1360 Barrington Street, Halifax, Nova Scotia, Canada B3J 2X4
5 b
Department of Materials Science and Engineering, Massachusetts Institute of Technology, Cambridge, MA 02139-4307, USA

PR
6 Abstract
7 The electrolytic production of magnesium requires high-purity, anhydrous magnesium chloride which has a high anity for
8 water and is found in nature as a plurality of hydrates (MgCl2
nH2 O, n 1, 2, 4, 6, 8, 12). Their dehydration is nontrivial and can
9 be accompanied by hydrolysis leading to the production of undesirable oxycompounds of magnesium. Through an analysis of the
10 relevant thermochemistry this paper indicates how to prevent hydrolysis and make electrolytic-grade, anhydrous MgCl2 . 2001
11 Published by Elsevier Science Ltd.

12 Keywords: Magnesium; Hydrolysis; Dehydration; Thermochemistry

D
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13 1. Introduction 2. Background 38

14 With a density of 1:74 g=cm3 magnesium is 4.5 times A cubic kilometer of seawater contains approxi- 39
15 lighter than steel and 1.6 times lighter than aluminum mately a million tones of magnesium, more than has 40
EC
16 [1]. The mechanical properties of magnesium castings ever been produced in one year by all the magnesium 41
17 make them competitive with aluminum castings. When plants in the world. Furthermore, seawater contains 42
18 hot worked, magnesium is the easiest to deep draw of only 3.7% of the total magnesium present in the earth's 43
19 the common metals and requires the least energy to crust. Clearly, magnesium resources are ubiquitous and 44
20 machine. It has superior damping capacity owing to its virtually inexhaustible. 45
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21 high specic stiness. Due to its reactivity, magnesium is never found in 46

22 The expectation of increased utilization of magne- nature in its free state but rather in compounds: as 47
23 sium in automotive applications has stimulated renewed chlorides MgCl2
12H2 O in seawater (0.250.55%), in 48
24 commercial interest in this metal [2]. In fact, at this underground brines (up to 20%), and in salt deposits 49
25 moment, the combined tonnage of announced greeneld such as carnallite MgCl2
KCl
6H2 O, and as car- 50
26 projects exceeds total global production capacity [3]. By bonates in the ores dolomite MgCO3
CaCO3 and 51
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27 far the dominant extraction technology is molten salt magnesite MgCO3 . Less important are the surface 52
28 electrolysis of magnesium chloride to produce liquid minerals, kieserite MgSO4
H2 O, kainite MgSO4
53
29 magnesium and chlorine gas. While electrolytic reduc- KCl
3H2 O and langbeinite 2MgSO4
K2 SO4 . Fi- 54
30 tion appears straightforward, the process cannot be nally, magnesium can be found in certain waste streams 55
31 sustained without the availability of high-purity feed, in concentrations high enough to warrant commercial 56
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32 i.e., anhydrous magnesium chloride. Owing to its high interest. For example, asbestos tailings contain magne- 57
33 anity for water as evidenced by the large number of sium in the form of serpentine Mg3 Si2 O5 OH4 [4]. 58
34 hydrates (MgCl2
nH2 O, n 1, 2, 4, 6, 8, 12), the pro- In the electrolytic production of magnesium, mag- 59
35 duction of anhydrous magnesium chloride is not trivial. nesium chloride is dissolved in a solvent consisting of a 60
36 In an eort to help workers in the eld avoid the pitfalls, multicomponent solution of alkali and alkaline-earth 61
37 the present paper presents the relevant thermochemistry. chlorides. The action of electric current drives faradaic 62
processes that produce liquid magnesium and chlorine 63
gas through the decomposition of magnesium chloride. 64
The temperature of operation is typically between 700C 65
and 750C. Magnesium droplets form on the steel 66
*
Corresponding author. Fax: +1-617-253-5418. cathode, and chlorine bubbles form on the carbon an- 67
E-mail address: dsadoway@mit.edu (D.R. Sadoway).

1471-5317/01/$ - see front matter 2001 Published by Elsevier Science Ltd.

PII: S 1 4 7 1 - 5 3 1 7 ( 0 1 ) 0 0 0 0 4 - 9
 ARTICLE IN PRESS
2 G.J. Kipouros, D.R. Sadoway / Journal of Light Metals xxx (2001) xxxxxx

68 ode. Both cell products rise to the surface of the elec-

69 trolyte where they are collected. As these reactions
70 proceed the electrolyte is depleted of magnesium chlo-
71 ride, which must be periodically added to the melt.
72 While the stoichiometry of the magnesium chloride sets
73 the molar ratio of cell products at 2:1 chlorine:magne-

F
74 sium, on a volumetric basis the ratio is 5800:1! One
75 might argue that the electrolysis of magnesium chloride

OO
76 produces chlorine, and magnesium is the by-product.
77 Magnesium metal was rst produced electrolytically
78 by Faraday in 1833. Modern electrolytic cell technology
79 emerged in Germany in the late 19th century. Today
80 there are several variants 1 but all can be traced back to
81 the I.G. Farben cell which uses anhydrous MgCl2 as

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82 feed. In the 1930s, Dow developed a cell designed to
83 accept partially hydrated MgCl2 as feed. Since 1998, all
84 electrolytic magnesium is produced by anhydrous tech-
Fig. 1. Phase diagram of the magnesium chloride water system
85 nology.
(schematic).
86 Although it is not the only harmful impurity present
87 in MgCl2 , water is an unwanted component of the cell
88 feed for many reasons: form in the MgCl2 O2 H2 system. In the event of hy- 115

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89 1. At electrolysis temperatures hydrolysis occurs, i.e., drolysis, one can expect to nd magnesium bound not 116
90 the water of hydration in MgCl2
nH2 O does not re- only to chlorine, but also to oxygen and hydrogen, e.g., 117
91 main intact, but instead dissociates. This generates MgOHCl (see Eq. (4)). 118
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92 highly reactive hydrogen and oxygen species which At room temperature the most fully hydrated form of 119
93 attack MgCl2 to produce hydrogen chloride gas and magnesium chloride is the hexahydrate, MgCl2
6H2 O. 120
94 various oxycompounds of magnesium. Hydrogen Its dehydration proceeds by the following reaction: 121
95 chloride attacks the equipment and renders the chlo- MgCl2
6H2 Os MgCl2
4H2 Os 2H2 Ov 1
96 rine produced at the anode unmarketable. Some oxy-
EC
97 compounds are insoluble in the electrolyte and cause over the temperature range 298390 K, where the solid 123
98 sludging. hexahydrate is stable. 124
99 2. Soluble oxycompounds can participate in parasitic The dehydration of MgCl2
4H2 O occurs by con- 125
100 electrochemical reactions on the carbon anode con- version to the dihydrate by the reaction: 126
101 suming it in the process. This attendant dimensional MgCl2
4H2 Os MgCl2
2H2 Os 2H2 Ov 2
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102 instability means suboptimal cell operation, e.g., un-

Dehydration of the solid dihydrate by conversion to the 128
103 desirable changes in joule heating rates and electro-
monohydrate occurs by the reaction: 129
104 lyte circulation patterns.
105 3. Soluble oxycompounds can react with nascent mag-
106 nesium droplets forming a surface lm that prevents
CO

107 their coalescence.

108 3. The thermochemistry of the hydrates of MgCl2

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109 Magnesium chloride is very hygroscopic. As shown in

110 Fig. 1, water can become chemically bound to form a
111 series of hydrate compounds (MgCl2
nH2 O, n 1, 2, 4,
112 6, 8, 12) [5]. It should be noted that MgCl2 and H2 O, the
113 two terminal components of the phase diagram depicted
114 in Fig. 1, are only two of the stable compounds that

1
The dierences between the I.G. Farben cell and the VAMI cell can
be attributed to the Russian practice of producing anhydrous feed
from carnallite. VAMI is the acronym for the All-Union Aluminum Fig. 2. Vapor pressures of H2 O and HCl over the hydrates of mag-
and Magnesium Institute. nesium chloride.
 ARTICLE IN PRESS
G.J. Kipouros, D.R. Sadoway / Journal of Light Metals xxx (2001) xxxxxx 3

MgCl2
H2 Os MgCl2
H2 Os H2 Ov 3 measured. Thus, absent these data, accurate determi- 181
nation of the PHCl =PH2 O ratio is not possible. Just the 182
131 over the temperature range where the dihydrate is sta- same, it is easy to appreciate that if dehydration of the 183
132 ble. monohydrate occurs under conditions that yield molten 184
133 It should be noted that dehydration of the dihydrate MgCl2 containing a small amount of dissolved MgOHCl 185
134 can also proceed by hydrolysis: such that aMgOHCl =aMgCl2 0:01, then the ratio of 186

F
MgCl2
2H2 Os MgOHCls HClg H2 Ov 4 PHCl =PH2 O necessary to chlorinate the impurity is greater 187
by a factor of 100 compared to the situation in which 188

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136 Reaction (4) is inhibited by the greater vapor pressure of there is no liquid phase. Thus, dehydration at higher 189
137 water generated by reaction (3), which occurs simulta- temperatures requires attendant changes in process 190
138 neously. Hydrolysis can be prevented by the use of HCl chemistry. By way of example, Magnola employs a so- 191
139 according to Le Chatelier's Principle provided that the called superchlorinator [7]. 192
140 partial pressure of HCl exceeds the value calculated by A nal note on the dehydration of magnesium chlo- 193
141 Eq. (4). Fig. 2 plots the temperature dependence of this ride concerns the stability of the oxychloride, MgOHCl, 194

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142 threshold PHCl . which can decompose according to the reaction 195
143 The nal stage in dehydrating magnesium chloride is
MgOHCls MgOs HClg 8
144 to remove the last water of crystallization from the solid
145 monohydrate by the reaction: The decomposition temperature of MgOHCl, i.e., the 197
MgCl2
H2 Os MgCl2s H2 Ov 5 temperature at which the pressure of HCl reaches 1 atm, 198
is calculated [5] to be 828 K. Above this temperature the 199
147 The hydrolysis reaction corresponding to Eq. (5) is oxychloride formed during dehydration will be con- 200
MgCl2
H2 Os MgOHCls HClg
149 Fig. 2 shows variation in the partial pressure of HCl
6

D verted entirely to MgO according to reaction (8). Solu-

bilities of the various oxidation products have been
determined [8]. Hydroxychloride formation and its eect
201
202
203
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150 with temperature for Eq. (6). on melt chemistry is probably more complex than it 204
151 Reactions (5) and (6) can be combined to express the appears, as there many hydroxychloride species reported 205
152 hydrolysis of MgCl2 as in literature. To complicate further the issue, some of 206
MgCl2s H2 Ov MgOHCls HClg 7 these hydroxychlorides are reported to have hydrates. 207
Due to the complexity of the system some authors refer 208
EC

154 which allows a calculation of the minimum ratio of to the retained water as ``occluded'' water. Table 1 209
155 PHCl =PH2 O to avert hydrolysis. As shown in Fig. 2, the shows the formulae of all the hydroxychlorides and their 210
156 vapor pressure of HCl under these circumstances is hydrates for which powder diraction les (PDF) have 211
157 considerably higher than that of H2 O. This suggests that been reported in the cards of the Joint Committee on 212
158 unless precautions are taken, the hydrolysis reaction (7) Powder Diraction Standards (JCPDS). Although the 213
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159 will proceed in preference to the dehydration reaction plethora of the proposed hydroxychlorides may cast 214
160 (5). Alternatively, hydrolysis can be averted when the doubt on their existence, nevertheless, it testies to the 215
161 applied partial pressure of HCl exceeds that shown in complexity of the MgCl2 O2 H2 system. 216
162 Fig. 2 for reaction (7). In industrial practice, kinetics, which do not appear 217
163 In the light of the above reactions (1)(7), the dehy- to have been extensively studied in this system, play a 218
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164 dration of MgCl2
6H2 O will produce anhydrous MgCl2 major role. Indeed, spray drying under optimum con- 219
165 as long as the nal step, reaction (5), is performed under ditions can produce material with 1% H2 O and 1% 220
166 a blanket of HCl at a partial pressure given in Fig. 2. It MgO, although normal practice gives 25% H2 O and 2 221
167 has been reported [6] that the entire dehydration se- 5% MgO. 222
168 quence starting from hexahydrate is conducted under To avoid some of the problems presented by the de- 223
169 HCl. The thermodynamic analysis presented in [5] hydration of hydrated magnesium chloride, other 224
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170 shows that up to reaction (4) it is not necessary to use chemistries for cell feed preparation have been investi- 225
171 HCl provided that no liquid phase is present. gated. Some of these, particularly those involving am- 226
172 In an attempt to improve the kinetics of the process, monium chloride salts, have been tested at the pilot 227
173 workers may be tempted to conduct dehydration at el- plant level. These include dehydration of double salts 228
174 evated temperatures where either the hydrates or the and chlorination of magnesium oxide. 229
175 product MgCl2 are present as liquid. Under these cir- Magnesium chloride and potassium chloride form a 230
176 cumstances, the value of the partial pressure of HCl hydrated double salt called carnallite, 231
177 capable of preventing hydrolysis is substantially higher KCl
MgCl2
6H2 O. Since KCl is also a major compo- 232
178 than that shown in Fig. 2. Unfortunately, the thermo- nent of the electrolyte, one option in cell feed prepara- 233
179 dynamic properties of multicomponent chloride melts tion is to produce anhydrous KCl
MgCl2 directly from 234
180 containing dissolved oxycompounds have not been carnallite. Proponents of the use of carnallite have ar- 235
 ARTICLE IN PRESS
4 G.J. Kipouros, D.R. Sadoway / Journal of Light Metals xxx (2001) xxxxxx

236 gued that it is easier to dehydrate than MgCl2
nH2 O. 413 K

237 Closer examination shows this not to be the case. NH4 Cl
MgCl2
4H2 Os ! NH4 Cl
MgCl2
2H2 Os
238 The dehydration of carnallite proceeds according to 2H2 Ov 13
239 the reactions
KCl
MgCl2
6H2 Os KCl
MgCl2
2H2 Os 4H2 Ov 433 K
NH4 Cl
MgCl2
2H2 Os ! NH4 Cl
MgCl2s

F
9
2 H2 Ov 14
241 and

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KCl
MgCl2
2H2 Os KCl
MgCl2s 2H2 Ov 509 K
NH4 Cl
MgCl2s ! NH4 Clv MgCl2s 15
10
243 accompanied to a certain extent by hydrolysis according Heating ammonium carnallite to 450 K will result in 269
244 to reaction (7). Although it appears that dehydration of dehydration according to reactions (12)(14). In a sec- 270
245 carnallite is similar to that of magnesium chloride, there ond step, reaction (15) is carried out by maintaining a 271

PR
246 is a signicant dierence between the two. Any hy- temperature of 573 K. The last step should be conducted 272
247 droxychloride generated during the dehydration of car- upon complete removal of the water of crystallization, 273
248 nallite forms a solid solution with it. Upon melting, the otherwise hydrolysis will occur via reaction (11). The 274
249 hydroxychloride dissociates according to patent literature [9] describes several variations of this 275
method of dehydration. Dehydration of ammonium 276
MgOHCl MgOH Cl 11 chloride in an ammonia atmosphere or in the presence 277

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251 thereby generating cationic impurities, which can inter- of an organic phase is also described [10]. 278
252 fere with the electrochemical reduction of magnesium in Recently dehydration of ammonium double salts, 279
253 the electrolytic cell. To prevent hydrolysis a blanket of which has its merits, has been tried at the pilot plant 280
254 dry hydrogen chloride gas should be present. Thus, the
TE scale. It seems that the higher energy consumption may 281
255 process is in practice as complicated as the dehydration oset the advantages. Carnallite dehydration has been 282
256 of magnesium chloride and appears to oer no advan- used on an industrial scale in Russia and recently in 283
257 tages over the latter. Furthermore, long-term cell feed- Israel. Ammonium carnallite dehydration has been 284
258 ing with dehydrated carnallite eventually requires either practiced at the laboratory scale by the authors of the 285
EC
259 that pure MgCl2 make-up be added or that supporting present paper. The product anhydrous MgCl2 was then 286
260 electrolyte be withdrawn to keep its composition within sublimed in an inert atmosphere containing SOCl2 to 287
261 limits. give a highly puried material for spectral studies 288
262 Another double salt is ammonium carnallite, [11,12]. 289
263 NH4 Cl
MgCl2
6H2 O. Dehydration occurs by the fol- Diculties in the dehydration of MgCl2
6H2 O led to 290
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264 lowing steps: the development of processes for the direct chlorination 291
373 K of magnesium oxide. Magnesium oxide can be produced 292
NH4 Cl
MgCl2
6H2 Os ! NH4 Cl
MgCl2
4H2 Os by calcination (1000C) of either magnesite or mag- 293
2H2 Ov 12 nesium hydroxide precipitated by mixing seawater with 294
dolime. 295
CO

Table 1
PDF for reported hydroxides of magnesium and their hydrates

Formula Name File number Year

MgClOH Magnesium chloride hydroxide 24726 1970

Mg2 OH3 Cl b-magnesium chloride hydroxide 12410 1954
UN

MgOHCl Magnesium chloride hydroxide 3100 1944

Mg(OH)Cl Magnesium chloride hydroxide 11328 1953
Mg2 ClOH3 Magnesium chloride hydroxide 12120 1958
Mg2 ClOH3
4H2 O Magnesium chloride hydroxide hydrate 36388 1982
Mg3 Cl2 OH4
2H2 O Magnesium chloride hydroxide hydrate 12133 1958
Mg10 Cl2 OH18
5H2 O Magnesium chloride hydroxide hydrate 12123 1958
Mg3 ClOH5
4H2 O Magnesium chloride hydroxide hydrate 12122 1958
Mg3 OH5 Cl
4H2 O Magnesium chloride hydroxide hydrate 7420 1949
Mg2 OH3 Cl
2H2 O Magnesium chloride hydroxide hydrate 7419
Mg3 OH5 Cl
3H2 O Magnesium chloride hydroxide hydrate 7416
Mg2 OH3 Cl
4H2 O Magnesium chloride hydroxide hydrate 7412
Mg10 OH18 Cl
5H2 O Magnesium chloride hydroxide hydrate 7409
Mg2 OH3 Cl
3H2 O Magnesium chloride hydroxide hydrate 7403
 ARTICLE IN PRESS
G.J. Kipouros, D.R. Sadoway / Journal of Light Metals xxx (2001) xxxxxx 5

296 The chlorination of magnesium oxide can be repre- tapped periodically into crucibles and fed to the elec- 347
297 sented by the reaction trolysis cells. 348
New environmental restrictions have forced re-ex- 349
MgOs Cl2g MgCl2s 1=2O2g 16
or l
amination of the carbochlorination process for two 350
299 where MgCl2 is solid below 987 K and molten above this main reasons. First, under certain conditions environ- 351
300 temperature. The thermodynamics of the process are mentally unacceptable polychlorinated hydrocarbons 352

F
301 explained in [5,8]. may be produced [15] and second, the chlorination 353
302 At 1300 K, which is the temperature at which in- furnaces are not easy to control. For improved eciency 354

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303 dustrial chlorinators operate, the oxygen content of the it is necessary to optimize the charge with respect to 355
304 gas should be kept below 1.4 mol% at 1 atm total particle size distribution, particle porosity, activity of 356
305 pressure. Failure to do so will result in oxidation of the reducing agent, i.e., grade of carbon, as well as with 357
306 MgCl2 , i.e., reaction (16) proceeds to the left. In indus- respect to the concentrations of certain impurities. 358
307 trial practice, to achieve an acceptable rate of chlori- While the focus of this article has been the dehydra- 359
308 nation, the pressure of oxygen will be allowed to tion of various forms of MgCl2
nH2 O, the production 360

PR
309 increase above the equilibrium value. This necessitates of electrolytic-grade, anhydrous MgCl2 , implies material 361
310 the use of a suitable reducing agent such as carbon to act free of impurities. Impurities not only contaminate the 362
311 as an oxygen sink. metal but also interfere with the operation of the elec- 363
312 Carbochlorination occurs by the reaction trolytic cells and aect their productivity. This is due to 364
the fact that, even at trace concentration levels, impu- 365
MgOs Cl2g Cs MgCl2l COg 17 rities can adversely change the physical properties of the 366
electrolyte. 367

D
314 The reaction products are very stable. Thus, when a
Sources of MgCl2 can also contain oxides and sul- 368
315 stream of chlorine gas passes through a mixture of MgO
fates, as well as boron. Table 2 shows the maximum 369
316 and C maintained at a constant temperature of 1300 K
permissible levels of commonly occurring impurities. 370
TE
317 the gas phase will consist almost entirely of CO provided
When cell feed is produced by dehydration of hy- 371
318 that equilibrium is achieved. On the other hand, since
drated magnesium chloride concentrated from seawater 372
319 most industrial chlorination reactors have been designed
or brines, sulfates are removed as calcium sulfate. It was 373
320 to consume a minimum amount of reagent (carbon) and
found [5] that the solubility of CaSO4 decreases as 374
321 do not operate isothermally, the gas phase tends to be a
MgCl2 content increases. For a brine containing 35% 375
EC
322 mixture of CO, CO2 , Cl2 and volatile chlorides.
MgCl2 the solubility of CaSO4 is 1.37 g/l. A similar trend 376
323 Carbon monoxide itself, however, is also a reducing
has also been observed for MgSO4 . At this stage of brine 377
324 agent initiating a strongly exothermic reaction:
concentration the sulfates are precipitated by the addi- 378
MgOs Cl2g 2COg MgCl2l CO2g 18 tion of CaCl2 . This treatment also results in precipita- 379
tion of other solids, such as clays and silica. In 380
RR

326 Proper control of the temperature of the chlorination exceptional cases BaCl2 may be added to remove the last 381
327 furnace is essential for its successful operation. traces of sulfate. Following this, boron is removed by 382
328 In a patent [13] the carbochlorination of magnesium ion exchange [8] or solvent extraction [14]. In the sea- 383
329 carbonate (instead of magnesium oxide) by chlorine and water process, after MgOH2 has been dissolved in HCl 384
330 carbon monoxide gases in a packed bed reactor to the excess calcium is precipitated along with magnesium 385
CO

331 produce anhydrous molten magnesium chloride is de- by the addition of sulfuric acid. 386
332 scribed. The reaction is The residual sulfate is then removed by the intro- 387
MgCO3s COg Cl2g MgCl2l 2CO2g 19 duction of small amounts of barium carbonate or bar- 388
ium chloride. 389
334 Carbon dioxide is removed from the top of the reactor,
335 and anhydrous molten magnesium chloride is with-
UN

Table 2
336 drawn below the packed bed. The energy requirements Maximum permissible levels of impurities in electrolytic cell feed
337 are claimed to be low, and the kinetics favorable. The
338 one attempt to commercialize the process was unsuc- B 0.001%
339 cessful. MgO 0.2%
SO4 0.05%
340 A detailed description of chlorination technology as Fe 0.005%
341 it applies to MgO in general has been given elsewhere Ca 0.2%
342 [14]. Magnesium oxide mixed with carbon and magne- H2 Oa 0.1%
343 sium chloride acting as a binder is formed into pellets, Tib 0.005%
344 which are dried and fed into the top of an electrically Mnb 0.1%
345 heated shaft furnace while chlorine enters at the bottom. a
For anhydrous feed.
346 In a continuous operation molten magnesium chloride is b
For MgCl2 recycled from Ti, Zr plants.
 ARTICLE IN PRESS
6 G.J. Kipouros, D.R. Sadoway / Journal of Light Metals xxx (2001) xxxxxx

390 When cell feed is prepared by carbochlorination of designs must reduce internal cell resistance. Improved 433
391 magnesium oxide, impurities are removed by dierent diaphragmless cells and bipolar-array electrode cong- 434
392 reactions. For example, the other oxides present as im- urations are two possibilities that in the past have not 435
393 purities in MgO are also carbochlorinated by reactions been fully exploited due to materials limitations. How- 436
394 such as ever, the advent of a new generation of high perfor- 437
mance materials now oers a new opportunity for 438

F
CaOs Cs Cl2g CaCl2l COg 20
success. For example, some of the candidate materials 439
2Fe2 O3s 3Cs 6Cl2g 4FeCl3v 3COg 21 for inert anodes [16] and wettable cathodes [17] that 440

OO
have been researched by the aluminum industry may 441
SiO2s 2Cs 2Cl2g SiCl4v 2CO2g 22 nd utility in advanced magnesium cell designs. Last, 442
and most radically, is the prospect of totally avoiding 443
2Al2 O3s 3Cs 6Cl2g 4AlCl3:v 3CO2g 23 chloride metallurgy by direct electrolysis of MgO from a 444
molten oxide electrolyte to produce magnesium metal 445
399 These reactions waste chlorine and carbon. Further-
and oxygen gas [18]. 446

PR
400 more, not all the above reactions go to completion, and
401 the remaining oxides, particularly SiO2 , MgO, and
402 Al2 O3 form a slag, the removal of which complicates the
Acknowledgements 447
403 operation.
404 Sulfates are also chlorinated according to the fol-
The authors wish to acknowledge the Natural Science 448
405 lowing reactions:
and Engineering Research Council (NSERC) of Canada 449
MgSO4s Cs Cl2g MgCl2l SO2:g CO2g (GJK) and the MacVicar Foundation at the Massa- 450

D
chusetts Institute of Technology (DRS) for partial - 451
24
nancial support. 452
TE
CaSO4s Cs Cl2g CaCl2l SO2g CO2g
25
References 453
408 Finally, up to 50% of the moisture present can evaporate
409 upon introduction into the furnace, while the rest is [1] E.A. Brandes (Ed.), Smithells Metals Reference Book, sixth ed., 454
EC
410 chlorinated according to the reactions Butterworths, London, 1983. 455
[2] G.J. Kipouros, Bringing magnesium to automobiles, in: H. 456
2H2 Ov 2Cl2g Cs 4HClg CO2g 26 Mostaghasi (Ed.), Materials Solutions for Environmental Prob- 457
lems, The Metallurgical Society, Canadian Institute of Mining, 458
H2 Ov Cl2g Cs 2HClg COg 27 Metallurgy, and Petroleum, Sudbury, Ont., Canada, August 17 459
20, 1997, pp. 265267. 460
461
RR

[3] R.E. Brown, Magnesium industry growth in the 1990 period, in:
H.I. Kaplan, J.N. Hryn, B.B. Clow (Eds.), Magnesium Technol- 462
413 4. Implications for producing electrolytic cell feed ogy 2000, TMS, Warrendale, PA, 2000, pp. 312. 463
[4] K. Watson, P. Ficara, M. Charron, J. Peacey, E. Chin, G. Bishop, 464
The magnola demonstration plant: a valuable investment in 465
414 It is somewhat ironic that the least dense structural technology development and improvement, in: H.I. Kaplan, J.N. 466
415 metal, magnesium, which can reduce energy consump- Hryn, B.B. Clow (Eds.), Magnesium Technology 2000, TMS, 467
CO

416 tion when used as a material for vehicular construction, Warrendale, PA, 2000, pp. 2730. 468
417 is one of the most energy-intensive metals to produce [5] G.J. Kipouros, D.R. Sadoway, The chemistry and electrochem- 469
istry of magnesium production, in: G. Mamantov, C.B. Maman- 470
418 with presently available technologies. Thus eorts to tov, J. Braunstein (Eds.), Advances in Molten Salt Chemistry, vol. 471
419 reduce the cost of production must address the energy 6, Elsevier, Amsterdam, 1987, pp. 127209. 472
420 requirements of extraction and bring them closer to the [6] P.M.D. Pinfold, Primary magnesium production at Becancour, 473
421 theoretical minima. An understanding of the scientic in: M. Sahoo, P. Pinfold (Eds.), Extraction, Rening, and 474
UN

422 principles of the relevant chemistry and electrochemistry Fabrication of Light Metals, Pergamon Press, Oxford, 1991, pp. 475
4353. 476
423 serves to specify these theoretical limitations and to [7] P. Ficara, E. Chin, T. Walker, D. Laroche, E. Palumbo, C. Celic, 477
424 guide research and development in this regard. M. Avedesian, Magnola: a novel commercial process for the 478
425 In electrolytic processes, high-purity cell feed prepa- primary production of magnesium, in: M. Avedesian, R. Guil- 479
426 ration is energy-intensive. New chemistries for energy- bault, D. Ksinsik (Eds.), Light Metals 1996, The Metallurgy 480
427 ecient dehydration of MgCl2 may be found through Sociecty of CIM, Montreal, Canada, 1996, pp. 183195. 481
[8] J.E. Vindstad, Hydrolysis of and oxide solubilities in melts related 482
428 better understanding the dehydration process. As for the to electrolytic magnesium production, Ph.D. Thesis 81, Norwe- 483
429 electrolysis operation itself, improvements in energy ef- gian Institute of Technology, Trondheim, February 1996, p. 114. 484
430 ciency will accrue from decreasing the cell voltage. This [9] G.J. Kipouros, Magnesium and other reactive metals: have they 485
431 can be accomplished through changes in cell design and matured?, J. Metall. 47 (12) (1995) 3839. 486
432 the use and development of new materials. New cell
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487 [10] R.J. Allain, A new eceonomical process for making anhydrous [15] L. Ongstad, et al., Environmental aspects of magnesium produc- 502
488 magnesium chloride, in: C.J. McMinn (Ed.), Light Metals 1980, tion by electrolysis, in: M.M. Avedesian, L.J. Larouche, J. 503
489 TMS/AIME, Warrendale, PA, 1979, pp. 929936. Masounave (Eds.), Advances in Production and Fabrication of 504
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496 511

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501 by J. Schmorak).

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