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Primary Production Industrial Insight

Improving the Electrolytic Process for


Magnesium Production
R.L. Thayer and R. Neelameggham

Magnesium Corporation of America has the ongoing success of the process. The mental chlorine issues at the facility. This
completed a development program designed use of older electrolysis technology, how- technical project had two distinct com-
to improve the performance efficiency of the ever, has led to increased labor and en- ponents: the improvement of magne-
electrolysis system and eliminate operating ergy expenses, along with increased en- sium-chloride cell feed purity and im-
chlorine losses. This work has culminated vironmental losses of chlorine. To re- provement of electrolyzer performance.
in the recent modernization of the process. solve the problems, the company has The feed-purity project was directed to-
The conversion has provided a number of modernized its electrolysis process, im- ward the cost-effective reduction of oxy-
operating benefits including significant re- proving efficiency and reducing costs. gen, iron, and carbon in the MgCl2 cell
ductions in labor costs, energy costs, main- feed. The electrolysis project involved
MODERNIZATION OBJECTIVES
tenance costs, and environmental releases. designing and evaluating various
This paper will review the development, A modernization program was initi- electrolyzer concepts that would reduce
design, environmental impact, and cost ben- ated six years ago to improve produc- energy consumption, eliminate chlorine
efit of the project. tion efficiency and to eliminate environ- losses, and require less operating labor.
The technical objectives would
INTRODUCTION
need to be carried out in a
MagCorp, the oldest primary brownfield installation with
magnesium producer in the minimal interruption to ongo-
United States, has operated elec- ing magnesium production. The
trolytic processes for 30 years. At cost of the project would need to
its Utah production facility, the be significantly more favorable
Great Salt Lake provides unique than a greenfield project.
advantages in preparing of
SYSTEM DEVELOPMENT
MgCl 2 for electrolysis. The
MagCorp production process Development of the feed-pu-
uses the anhydrous magnesium- rity project included a thorough
chloride preparation method, review of the options available
which was developed through a to meet the objectives. The exist-
combination of pilot plant data ing MagCorp process utilizes
and empirical optimization. Us- continuous magnesium-chloride
ing solar recovery of brine from chlorinators with a high through-
the Great Salt Lake, a pure mag- put capacity. This productivity
nesium-chloride brine is col- is realized through the use of
lected at a low cost. After several proper reactant control as well
chemical treatment steps, MgSO4 as iron-chloride reaction inter-
is converted and boron impuri- mediates. Elimination of the re-
ties removed. The purified brine sidual carbon and iron from the
is then flash-dried to remove the reaction has been a major tech-
majority of water before the ma- nical obstacle. Work that began
terial is carbo-chlorinated to Figure 1. MagCorp process flow sheet. in 1996 to determine the best
eliminate all residual oxygen methods to remove these impu-
content. rities culminated in the addition of a
The carbo-chlorination process pro- chlorination component to the process.
duces a molten magnesium-chloride Cl2 Gas to Impure This chlorination step utilized a propri-
feedstock for use in several types of Recovery/ MgCl2 Inlet etary technique of vertical chlorination,
monopolar electrolyzers that have been Recycle which was found to be efficient from
installed in the Rowley facility. These both a cost and a process perspective.
designs include magnesium cells with The electrolysis project began with a
and without diaphragms. The major review of available technical options.
products from the electrolysis area in- Eleven different electrolyzer concepts
Proprietary were tested over a three-year period be-
clude chlorine gas, which is reused in Contact Area
the process or sold, and magnesium fore a final design was chosen. The selec-
metal, which is vacuum harvested and tion criteria included overall perfor-
directed to the casting plant. Recovered mance, operating simplicity, ruggedness,
metal is refined, alloyed, and cast into and projected maintenance costs.
more than 30 different product lines, Cl2 Gas Purified
MgCl2 Outlet MgCl2 PURIFICATION
including direct chilled billet. Inlet
PROJECT
The low cost of magnesium-chloride
production and the flexibility of the fa- The electrolytic production of magne-
cility casting system have contributed to Figure 2. A tertiary MgCl2 chlorinator. sium is a complex process that can be

2001 August • JOM 15


simplified into two major steps: tem to the electrolyzers required
preparation of magnesium chlo- replacement of the existing mo-
ride and the subsequent electroly- bile equipment fleet. The new
sis of the salt. Preparation of mag- units incorporated static suction-
nesium chloride is the key to suc- line technology and much larger
cessful electrolysis and all mag- capacity (11.5 tonne vs. 3.2
nesium electrolyzers must be de- tonne). These modifications re-
signed to handle the specific ca- sulted in a substantial reduc-
pabilities of the feed-preparation tion in the increase of MgCl2
step. Magnesium-chloride purity impurities due to handling. The
at MagCorp has historically aver- old transport system observed
aged 0.70% non-electrolyte im- an average impurity increase
purities, which is significantly of 500 ppm compared to 100
higher than the 0.20% maximum Figure 3. Cell feed MgO vs. CE/sludge. ppm with the new system.
designed for most high-efficiency CELL FEED
electrolyzers. The technical ob- PERFORMANCE
jective required significant impu-
rity removal with minimal Impurities in magnesium-chlo-
changes in infrastructure. ride feed reduce the efficiency of
The original MagCorp chlori- electrolysis. The effects of these
nation system utilizes refractory impurities (MgO, Fe, and C in
lined cells arranged in a primary the MagCorp system) have been
and secondary process scheme. studied and discussed in a num-
These units utilize chlorine ber of literature sources. The in-
sparging tubes to introduce gas teraction of these components
into the reactors. Process kinetics with magnesium metal collec-
are driven by reactant control, tion and their effect on direct
reactant contact (control of chlo- current (DC) cell electrode sur-
rine vapor bubble size), residence Figure 4. Cell CE vs. cell feed Fe/C.
faces has been accurately re-
time, and mixing. The modified viewed by Strelets.1 Figures 3–4
system would require the follow- illustrate the effects of these com-
ing changes: layout. The chlorinators were also al- ponents in the electrolysis area as mea-
• Process modifications for improved tered to eliminate air introduction into sured in the MagCorp system.
impurity removal the reactors. These modifications dra- Product purity improved signifi-
• Upgraded control system to opti- matically improved reliability, cleanli- cantly with modifications to the MgCl2
ness, and control of the system. feed-preparation process, while oper-
mize reaction kinetics
Equipment modifications down- ating costs decreased by 10%. Figure 5
• Improved product surge handling illustrates the results of feed-prepara-
stream of the tertiary chlorination step
and purity control included additional product surge ca- tion technology improvements at the
• Improved design of existing chlo- pacity and new mobile feed hauling facility, where high-quality magnesium-
rinators to optimize performance equipment to transport MgCl2 to the cell chloride cell feed is produced for less
• Improved feed delivery system to rooms. The surge units provided signifi- than $0.056/kg.
the electrolyzers cant capacity within a controlled envi- MAGNESIUM ELECTROLYSIS
Significant process testing resulted in ronment to maintain MgCl2 purity. These PROJECT
the decision to add tertiary chlorination to units also incorporated equipment de-
the system. This involved installation of a signed to provide precipitative removal Due to the labor, energy, and rebuild
proprietary vertical chlorinator to remove of carbon and other impurities. expenses associated with the equipment,
residual oxygen and iron. The chlorinator The magnesium-chloride delivery sys- magnesium electrolysis is the most cost-
was designed using standard intensive processing step in the
contactor hydraulics and was 0.8 electrolytic method of production.
0.70 Vast amounts of information are
modified through pilot testing. 0.7
0.62
Construction materials were 0.6 available detailing theoretical and
Impurity (%)

0.5
optimized through thorough 0.4 0.40 practical designs of magnesium
field testing. The final product 0.3 0.25 0.27 electrolyzers, including mono-
incorporated a rugged design 0.2 0.18 0.17 polar diaphragm units, monopolar
0.1 0.10 0.11
with appropriate gas intro- 0.05 0.01 0.0 diaphragmless units, and multi-
0.0
duction, liquid distribution 1980 1990 2000 polar units. All of these electro-
(molten MgCl 2 ), efficient MgO Fe C Total lyzers can be designed to operate
contactor area, and appropri- at various power levels and inter-
Figure 5. Historical cell feed impurity levels. electrode distances. Small design
ate offgas handling for recy-
cling the high-strength chlo- changes can induce significant dif-
0.6
Fraction of Historical Area Cost

rine exiting the column. ferences in cell performance and


0.5 0.485
Existing chlorination equip- can significantly alter cell-feed
0.4
ment was upgraded with the in- 0.351 purity requirements.
stallation of an electronic control 0.3 MagCorp, which operated
scheme for reactant, power, and 0.2 0.185 monopolar diaphragm electro-
0.129
gas handling. The chlorinators 0.1 0.074 lyzers (IG Farben based) for 25
0.022
were modified to accept a verti- 0.0 years, realized increased produc-
cal electrode design (vs. horizon- Labor Energy Maintenance tivity and improved chlorine-col-
tal), which provided an oppor- Historical Modernized lection capability when it in-
tunity to improve the refractory Figure 6. Historical vs. modernized costs. stalled a diaphragmless electro-

16 JOM • August 2001


Table I. MagCorp Electrolyzer Comparison
emissions have greatly improved,
as has work-place hygiene.
Item Diaphragm Cell Diaphragmless Cell M Cell Worker exposure to both chlorine
Operating Temperature 704–760∞C 704–760∞C 676–704∞C and cell thermal emissions have
Chlorine Strength 70% 80% >96% been reduced 45% and 30%, re-
Chlorine Recovery 85% 98% 99.9% spectively. Chlorine collection has
Power Efficiency (Min/Max) kwh/kg 18.8 to 19.9 16.6 to 18.8 12.1 to 14.3
Voltage 6.5 to 7.0 6.0 to 6.3 4.5 to 5.0
improved significantly, with
Production (Max) 1.0 t/d 1.4 t/d 2.8 t/d greater than 99.9% capture due to
Melt Capacity 20 t 42 t 91 t the proprietary metal collection
system. The strength of the gen-
Table II. Comparison of Industrial DC Cells* erated chlorine is exceptional
(greater than 96%), which im-
Power Unit
Company Cell Cell Type Voltage Efficiency Production
proves the economy of down-
stream gas cleaning and recycling.
Norsk-Hydro2 DLE Monopolar 5.3 V 13.0 kwh/kg >4.0 t/d A number of considerations are uti-
Alcan Int.3 MP3 Multipolar NA 10.5 kwh/kg NA
MagCorp3 M-Cell Monopolar 5.0 V 12.6 kwh/kg 2.8 t/d
lized in selecting electrolyzer designs,
AVISMA4 Bottom Entry Monopolar 4.7 V 13.5 kwh/kg 0.7 t/d including performance, operating sim-
UKTMP (Kaz)4 Top Entry Monopolar 4.8 V 13.2 kwh/kg 1.8 t/d plicity, and process ruggedness. These
*Competitor information was derived from published reports and the basis of evaluation in each category may be inconsistent. factors vary somewhat by individual
industrial site, and have a significant
lyzer at the facility in the 1980s. Disad- The impact of the new cell design to impact on the overall economics of
vantages of early electrolyzer designs the MagCorp electrolysis system has electrolyzer performance. Selected per-
include excess labor requirements, un- been significant. The technical challenge formance comparisons of magnesium
favorable chlorine recovery, and lim- of installing an advanced electrolyzer in electrolyzers are presented in Table II.
ited unit productivity. A new electro- an existing facility was overcome with CONCLUSIONS
lyzer would be designed to provide minimal process interruption. The key
the following: elements involved in the project included The successful modernization of the
• Compatibility with improved the following: MagCorp electrolysis system required
• Electrical System—The electrolyzer several years of development and ex-
MgCl2 feed
DC power system was replaced tensive technical support. The result
• A 30% reduction in energy con- has been a 20% reduction in overall
with new rectifier and busbar ca-
sumption production costs. The installed cost of
pacity, which allowed cell power
• A 300% productivity improvement delivery of more than 300 KA. The the MagCorp feed purification system
• A significant reduction in labor high-efficiency busbar, coupled and electrolysis upgrade was $1,200 per
and maintenance requirements with the new electrolyzer design, tonne of annual magnesium produc-
• Improved environmental and hy- resulted in improved power effi- tion, which compares favorably to the
giene performance ciencies. Actual performance lev- $3,000 to $15,000 per tonne of greenfield
• Ability to absorb process upsets els of 13.31 kwh/kg Mg (includ- capacity reported by various Eastern
The new electrolyzers, referred to as ing all busbar) have been demon- and Western organizations.
M cells, are large-scale, monopolar strated at the plant site, with in- The installation of this system has
diaphragmless electrolyzers. These units cell power consumption averag- demonstrated that it is technically fea-
utilize large electrodes, a reduced inter- ing 12.52 kwh/kg Mg. The electri- sible to retrofit existing production fa-
electrode distance (less than 30 mm), cal performance of the system is cilities with equipment that provides
and channeled magnesium collection. expected to improve with addi- excellent results. The significant ben-
Significant development work was re- tional experience. efits of this approach can provide older
quired to optimize the performance re- • Labor Utilization—The increased producers with the efficiencies required
lationship between current density, elec- scale of the M cell system has pro- to compete in the high-quality magne-
trode geometry, electrode gap, magne- vided a framework for reduced op- sium market with reasonable rates of
sium collector arrangement, cell ther- erating labor. Older MagCorp return on facility investments. The tech-
mal balance, and overall current effi- electrolyzers provide 1.0 to 1.4 nological approach can also provide the
ciency. The final design concept is an tonnes of magnesium per unit day. framework for significant volume ex-
advanced version of the successful The M cells produce up to 2.8 tonnes pansions should the need arise due to
diaphragmless electrolyzer. The design of magnesium per day, which sig- future market growth.
modifications used on the M cell system nificantly reduces the number of References
resulted in the following advantages: operating units. This change, in con-
1. Kh.L. Strelets, Electrolytic Production of Magnesium (Spring-
• No requirement for control of cell junction with the improved feed field, VA: NTIS: Jerusalem Publishing, 1977).
electrolyte level delivery system, has reduced area 2. Oddmund Wallevik et al., “Magnesium Electrolysis—A
MonopolarViewpoint,”MagnesiumTechnology2000,ed.H.I.Kaplan,
• No requirement to replace graphite labor requirements by 83%. J. Hyrn, and B. Clow (Warrendale, PA: TMS, 2000), pp. 13–16.
anodes • Maintenance—Maintenance costs of 3. J. Christensen, D. Creber, and G. Holywell, “The Evolution
of Alcan’s MPC Technology,” Proc. First Israeli Int. Conf. on
• No requirement to desludge the units the M cell system are dramatically Magnesium Science and Technology (Beer Sheva, Israel: Mg
improved from older electrolyzer Rsch. Inst., Ltd., 1997).
• Greater than 99.9% collection of 4. G. Shekhovtsov et al., “Magnesium Electrolytic Produc-
designs. This is due to the design tion Process,” Proc. First Israeli Int. Conf. on Magnesium
chlorine ruggedness, design simplicity, and Science and Technology (Beer Sheva, Israel: Mg Rsch. Inst.,
• No requirement for cell heat ex- an improved electrode cooling sys-
Ltd., 1997).

changer or alternating current heat- tem. Maintenance requirements have R.L. Thayer is vice president of operations and R.
ing system Neelameggham is a technical development scientist at
been reduced 60%. At less than $0.11/ Magnesium Corporation of America.
• Improved chlorine compartment in- kg Mg, cell-rebuild expenses associ-
For more information, contact R.L. Thayer, Mag-
tegrity ated with the M cells are competitive nesium Corporation of America, Operations
A comparison of the historical perfor- with advanced cell designs in other Building, 238 North 2200 West, Salt Lake City,
mances of the major MagCorp operations. Utah 84116 USA; fax (801) 596-1132; e-mail
electrolyzer designs is shown in Table I. • Environmental—Environmental rthayer@magnesiumcorp.com.

2001 August • JOM 17

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