The Refractory or " Fireless Cooker" Method of Producing Magriesium

THE development of huge production facilities and of new or improved processes for manufacturing magnesium from its raw sources has been an outstanding achievement of this war. Furthermore, a t least one new method has reached a stage of pilot production that offers promise. Its potentialities seem to indicatc that a reduction in cost and simplification or elimination of problems incident to the use of at least one of the present processes are quite within the realm of possibility. Although magnesium of very high purity (99.9 per cent and higher) is obtained, and the rate of recovery reasonable (60 to 70 per cent). the ferrosilicon reduction proccss is open to a scrious objection, which a t the time its use was proposed was thought to be sufficient to raise some doubts as to its success, at least on a high production basis. The temperature range a t which the reac2100" to tion is carried out-namely, 2150~F.-is very close to the failure temperature of the material of which the retort is made. I t is so close that for a time it was assumed it might make commercial use of the process an impossibility. However, a t the time under discussion, the demand for magnesium was so great
This paper is based on research work done by Surface Combustion, under the supervision of t h e War Metallurgy Committee, for the War Production Board a s "restricted' Project NRC-520. I t s publication has been authorized by t h e Office of Production Research a n d Development of the War Production Board. Manuscript received a t the office of t h e Institute Nov. j, 1944;revised July 2 . 1945 Issued a s T P 1941 in METALSTECHNOLOGY, December 1 9 4 5 . Listed for the New York Meeting, which was cancrled. ' Director of Research. Surface Combustion Corporation, Toledo, Ohio.

that it was fclt by those who had to go ahead and produce this essential metal that the emergency warranted their taking a chance on this process. Subsequent developments have fully justified thc soundness of their decision. Fortunately for the war effort, when the plants were put into operation it was discovered thaf although the retorts did collapse in rather short ~ e r i o d sof time, as predicted, they could be blown back into operable shape by application of highpressure air. This practical method of operationso relievcd thesituation that the problem disappeared. Nevertheless, if thc proccss had not been successful, or the production of magnesium by the electrolytic process had not been able to keep pace with demands, our war program would have been seriously impaired.

FIRELESS COOKER''PROCESS
For this reason a program was set up and assigned for the development of a new method that had been suggested to the War Production Board in 1941. I t is believed justifiable in terming the method "new" for scveral reasons: ( I ) while utilizing the same (ferrosilicon) process as the I'idgeon, hence involving similar rcactions, the type of retort or furnace is essentially different, (2) the method of operation, reaction temperaturcs, etc., differ materially, and, most important of all, (3) the problems to be overcome in making the process successful were not and could not havc been anticipated by anything previously known about the Pidgcon process. As will be shown later, the briquetting process, the condenser, the furnace lining

94

T H E REFRACTORY OR "FIRELESS COOKER" METHOD OF PRODUCING XAGNESIUM

and other parts of the equipment, all had to be studied and revised before success was possible, even on the limited basis established by the pilot installation. I t has, therefore, been deemed advisable to disclose the method a t this time, especially since some of the problems overcome may be of value in other fields of development and may also indicate the path to be followed in any further development of the process. The term "fireless cooker" was applied to the process because it most aptly indicates the general method involved in obtaining the desired result. I t consists fundamentally in charging briquettes compcsed of dolomite and ferrosilicon (as in the Pidgeon process) into a refractorylined, vacuum-tinht steel shell, which has previously been heated to a maximum temperature of z700F. 'The steel shell is then evacuated and the heat stored in the heated refractory furnishes the necessary heat for reaction, while simultaneously cooling to a temperature of zzooF. The development of the process can most conveniently be divided into three parts: ( I ) laboratory and experimental plant development, (2) preliminary pilot-plant tests, including construction, revisions, etc., and (3) production runs, results, con elusions, future possibilities, and so forth.

variety of minor design points-all were virtually unknown. The first period of the work, therefore, lasted nearly two yearsuntil early in 1942.
OF PRODUCTION BRIQUETTES

In preparing the briquettes used in the production of magnesium the procedure is, in gencral, as follows. Dolomite, calciummagnesium carbonate CaMg(COJ2, is first calcined, leaving a residue of lump lime composed of equal molecular parts of CaO and MgO. The lime is then mixed with 75 per cent ferrosilicon in such proportions that the amount of silicon is chemically equivalent to the amount of magnesium, thus providing the following reaction:

zMgO.Ca0

+ Si + (Fe) = a M g (vapor) + CazSi02+ (Fe)

However, it is possible to produce two distinctly different types of briquettes on this same basis; the so-called wet or dry briquettes. The wet briquettes are made by adding water to the lime before briquetting. 'This produces an extremely hard and tough briquette, which is also very porous after the water is driven off by preheating. C'sing pure dolomite and a perfect mixture, a production of 9.5 lb. of magnesium, at AND PLAKT 75 per cent silicon efficiency, is possible LABORATORY EXPERIMENTAL DEVELOPMENTS per cubic foot of briquettes. Dry briquettes This stage of development was on virgin are produced from dry lime, giving a comground in many ways. Very little really paratively fragile but compact briquette, conclusive information was available about from which a yield of 12.3 lb. of magnesium, the metal itself, especially as to its behavior a t 75 per cent silicon efficiency, is possihle under the proposed conditions. Reaction per cubic foot. The advantages of wet rates and temperatures under varying briquettes lie in their ability to resist conditions of vacua, heat capacities of the handling without excessive breakage, in reacting materials and the refractories, greater reaction rates, in higher ultimate under the high temperatures proposed, the efficicncies, and in reduced briquetting effects of magnesium vapor on the furnace pressures. On the other hand, dry briquettes materials, means of producing high vacua give a greater yield per cubic foot of retort rapidly, degassing of refractories, mcthods space, and in the Pidgeon retort process do of sealing the apparatus, and an infinite not require preheating for drying.

96

THE R E F R A C T O R Y OR " F ~ K E L E S S COOKER" SIETHOD O F P R O D U C I N G MAGNESIUM

REACTION RATES Prior to the laboratory for the fireless cooker method, nothing was known about reaction rates above 2100F. These

tom) portion could be held a t any tempcrature between 1 5 0 0 ~and ZIOOOF.,while the condensation (upper) part could be held a t about 13joOF. Magnesium was distilled

T i m e , minutes

hIagnesium charged, 2 1 Ib.; magnesium recovered, tests showed the rate to increase rapidly above this temperature, becoming a virtually instantaneous reaction a t 2360F., the rate being proportional to the number of silicon-vapor molrculrs per unit volume. The influence of silicon and of CaO in the reaction was also fount1 to be important in affecting the reaction rate and availability of the magnesium. The production of magnesium from pure MgO and pure ferrosilicon in which the yields mere poor confirmed the effect of CaO in the dolomite.

FIG. 2.-CONDEFSATION TEST

DATA.
20.9 Ib

Much higher production rates thus were to be expected in the refractory method than are obtained by the retort process, because of the much higher temperatures used. This immediately imposed the problem of properly designing a condenser to handle the production rate. T o arrive a t a condenser design, rates and temperatures of magnesium vaporization and condensation were determined in a two-zone retort or furnace (Fig. I). The distillation (bot-

and condensed in this retort a t various rates in vacuum under carefully controlled conditions. Magnesium distillation began a t a temperature of IIOOOF.Condensation was instantly indicated by an abrupt rise in temperature of the condensing unit and could be followed visibly through a sight glass in the side of the retort. Normal temperature recurred when condensation had been completerl. The amount of magnesium was then weighed and compared wit11 that originally introduced. The rate of condensation, the amount of heat abstracted per pound, and the rate of heat transfer per unit area through the wall of the condenser were thus all determined before the full-scale plant was designed and built. The curves on Fig. 2 give the results of these tests. Fig. 3 shows the experimental condenser (of 4-in. diameter) with a solid bsll of magnesium condensed upon it. The sodium impurities are condensed on the upper ant1 colder regions. At the right a ball that was

'

L
1IW\ I ~TLS. ;

1 11.. .I. -1: u.1,- C S J \ U ~ X : I i ) 115 lrrr,n ( : { ~ I > I From left to riplht: J. rz-lb. hall prnrluc~rl in I . 0.01-lh. hall produced i11 10-in. rlia. rt.tr>rt rfmcI! $-in, dia. rctort turcd thrnugh ;ixi:il @ane 2. a.,j-111,l~all produced in s l ~ n ~ v i n ~ mnjinrslum thc 4-in. din. rctnrt structusc) 3. 8-lb. hall p r n d u ~ d TO-in, in j. Ssmc a5 4, unfracturcd dia. retort

b. t

7-11>. ball produrcd in TO-in. dia. retort (cut tl~rnr~ah center and polisI18.d 7. 20-lb. ball produced in to-in. din. retort

98

THE REFRACTORY OR "FIRELESS COOKER" METHOD OF PRODUCING MAGNESIUM

condensed a t too low a temperature is shown. It exhibits a coarse crystal-like structure. Below the large ball is one of intermediate size condensed on smaller equipment. Fig. 4 shows a variety of balls from 0.1 to 2 0 Ib., condensed under various conditions by high condensation rates. Only pure magnesium is condensed if the temperature is above 5o0F. but below the

condensation temperature of approximately IIOOOF.

Because of its high heat content and great conductivity, Carborundum appeared to be the ideal refractory for use in the "fireless cooker." After a number of tests it was established that this refractory could

VACU~~M PYUP
ALLOV RLTOPI

COYWLCIIOII

CLLCTP~CU L L I I H ~ LLLMIHT

O?tl*~l*'.
tar

C"LI*O

Plcursrr buu

tscnrRet burro

E. G .

DE CORIOLIS

99

supply heat to the charge a t a sufficiently high rate, and that no deleterious reactions would occur between the refractory and the briquettes or the magnesium vapor a t high temperatures. I t was also established that the magnesium produced would be of a purity comparable with that of the magnesium obtained in the Pidgeon retort process.

During this period many other pertinent features of design, such as the vacuum system, the pump, and the closures, were worked out.

Work on the pilot plant, an addition to the pilot-plant building of the blagnesium Reduction Company's plant a t Luckey,

R E D U C R O N UNIT.

1 0 0

THE REFRACTORY OR "FIRELESS COOKER" METHOD OF PRODUCING MAGXESIUM

Ohio (division of National Lead Co.). was started toward the end of 1942.By January 1943 the work was completed. The unit contemplated the production of roo Ib. of magnesium per charge, with a n over-all cycle of approximately 2 hr., allowing 30 min. for production and condensation of the magnesium vapor. The expected rate of production was so much higher than contemplated in the laboratory that segregation of the function of magnesium condensation from that of reaction or production was considered desirable. As later events showed, coiltrol of the forrner was to be a real problem. By March of 1943 the plant was completed and ready for operation.

Fig, j shows schematically the o p e r ations involved in the process. The vacuumtight shell is fitted with four vacuum-tight hydraulically operated closures. The charge and discharge closures are a t the top and bottom of the unit. Burner and flue closurcs are a t the sides. The upper section of the unit contains an electrically heated chargeholding chamber in which thc preheat temperature of the charge of briquettes is maintained prior to dumping into the hightemperature reaction chambcr belorv. The briquettes are externally preheated to approximately I 250F. belore being placed in the upper or holding chamber. The reaction chamber is composed of a crossshaped Carborundum muffle. Surrounding this is an annular chamber of Carhorundum conused for heat storage. The nlag~lesiurn denser is suspended axially from thc top closure into the charge-holding chamber.

temperature is approximately 8ooF., obtained in hairpin U-shaped tubes suspended in an auxiliary furnace. Electric heating elements maintain a temperature of from 1 2 0 0 ~to r500F. in the upper chamber. During the firing period the bottom discharge closure is cleaned of all previous contamination and also made vacuum-tight. After a temperature of 2jooF. has been reached in the reaction chamber, firing is stopped, the briquettes are quickly charged, the burner and flue closures made vacuum-tight and the vacuum pump started. After the pressure in the reaction chamber has been reducrd to I in. Hg or less, the briquettes in the charge-holding chamber are dumped by an cxtcrnally, hydraulically operated valve. This part of the unit was completely revised subsequently, as described later. During the follorving magnesium reduction period the magnesium vapor passes into the upper chamber and condenses on the condenser. When the temperature in the reaction chamber has fallen to rzooF. the reaction is completed, air is allorved to re-enter the chamber, the top closure holding the condensed magnesium ball is raised above the chamber, the flue and burner closures are opened and firing is resumed. During the firing period the bottom closure is lowered and the spent briquettes allorved to fall into the spent briquette buggy. The cycle is then repeated. Addilionnl Fentz~res Design aud Operation of Because of frequent lack of factual data, i t was necessary to project laboratory results to the full-scale unit. This entailed the imposition of safety factors, which in some cases appreciably exceeded actual requirements. Approximately ro,ooo Ib. of Carborundurn refractory is used to provide the heat storage capacity between the temperatures of zjooO and zzooF. The bottom closure provides a double seal made by a tongue

O#eration The mode of operation is as follorvs: The unit is first hcatcd to a temperature of z700F. by burning natural gas with preheated air in the combustion space between the Carborundum muffle and the heatstorage Carborundum. The preheated air

and groove joint thrust home l ~ y the hydraulic cylinder. Water coolinr: i s provide<! to protrct all rlrhlltar ~ : ~ s k r tn ,tems perature of 150' bcinr: used to prcvrnt thr condensation of water vnljor frr>rt~ Iluv thc gases. The shell itself was d c s i ~ n c d opcrto

temperature of rgooDF. is low, so that the life of this retort would !x indefinitely long.
CofzJe~rser

Thc large condensers shown in Fig. 6 are the result of preliminary e x p e r i m e n ~ One .

. I I \ <, \: ate Iwtwccn tempcraturcs of 2 0 0 " znci 3mF. ( E x r ~ p tfor t h e contlenser anrt lop

FI(>. 6.-1<1

I!

I,

b\

\ 1-11

1:

,\.111\-1

'\

I"l1l:!~I~11s1).

is 14 in. and thc olhcr 16 in. in dianlctcr, similar in tle.;igr~to the lahoratnry unit. Rriqrrcllc Pre~rcalittg Prcheatitjg oE the briqurttcs prior to charging into the heaf-holding chamhcr was accompliqhed in two small convection furnaces. The briquettes wcrc placed in a cylin(1rical basket with a screen bottom I ~ c f o r c h c y \ e r e put into the furnace. Ret circulalrtl flue gases blown at high velocity through ~ h cfurnace r e r e found to k capalhu of hctiting th- t~riquettesto a uniform t ~ m l ~ r r a t u rregardl-s of the diamc ctcr of the basket. The temperature was cnwfullp cuntrctl'ted to prevcnt heatina above thc P C ~ ttmpcrature of the furnace.

clmurc shown, thc rlran-infi is accurate.) To provide heat-exchange capacity, thc Carlmrundum is arranpfrrl in an annular ring, so that i t is lltls~il~lc tran~fcrIhc to heat rapitlly r;trli:~tlnn. Since thcrr is no grcnt t hickncss of thc Carl)orurulurrl, thc material is quickly hrntcrl try thr cntnbustion gases, which n r r rnaintninrcl at n fiamc tcmpcraturc of 4;oo01:. In the chargc-hol(1i11g unilt a t ~ l i utop, a heat-misting alloy rrlorE of light jinrlge is utilized to prr\.etIt tliffu.;ion u i the magnesium vapor into the part of the unit that contains insulating firebrick. The holcling

02

THE REFRACTORY OR "F~RELESS COOKER" MUETIIOD PRODVCIXG MAGNESIUBI OF

Thc laboratory k s t s had shown that the briquettes couIc1 be hcatrd to the proper temperature without oxidizing the ferrcisilicon. and that either hydrated or com-

1048, thc plant was fired, and aftcr an initial suaking at 2goouF., to tlr!. thc brickwork, and so forth, it wa^s heatetl slowly to 2300F. Tests showed satiqfactory vacua

pletely anhydrous dolomitc coulrE Ile u<i=rl. ant1 control opcrtztiorl. Radiation lmses also Hanrllin~ot the briquettcs (rvliich wcrc were accorrIing to c:~lculations. furnished from the Magnesium Rctiuction J l n ~ ~ r c sm uProd t ~ e d i Company's plant near by) n=a<fncilitatrd Early it1 .4lltil r g q the first rnagnniuin by placing an automatic dump c1rutc in the 1 y this process was produccd-somc 40 to 1 bottom 01 rach preheat in^ haskct. 50 11,. in from 30 to 4; min. ITowevcr, thc conrltbnscr tcmperafurc had t ~ r c nhcld too Vacuum tcsts coiitluctcrl prior to initial Iniv aalld the metal was of thc untlesirahle f~ricg shorrcd that rcry satisfactory rrsults rrg~talstructure. During t h e owration of upereposzible. Thc. unit mas retlucerl from Ixcaking thc vacuum, thc mctal fell into and n= lost. atmmpheric pn.sGurc to 0.01 in. in S min. the furnacc, bccarnc i ~ n i t c d :s might be cry~ccturl, "playing safe" i The ultimatc prcsrurc of 0 . 0 0 2 5 in. was in the obtained in 2 2 min. These tcsts wcrc con- rcsult~d o v e ~ h o o t i n g condenscr tcmperature thc wcnn(l time the furnace was ducted prior to the bricking of thc shcll. After completion of the tests, in March charged, a few (lays later, and some m a p

nesium condensed in the upper part of the chambrr. I-lo~~ever, iorm and purity its were satiqfactory.

of the lower portion of the furnacc

at

lower tempera t u r s obviously rerluccd production of msgncsiurn. It also made

FIG. .

%:I

~d

9,.

'\I

i 1'

I '.I'

L ,

,\Lily.

, 7!:LlL2

IJL 1 ( , F JOE4TS.

Sln~1i)tp SroMrrn nurinr: thvw prrlimInar!* runs, a probIcm a r t w that was r\,holly unanticipated a n d was latrr to pmve serious. In the first run, nnt* of tht- rcmcnts used in the construction slaggrtl and drippet! out through thc Imttr)m hung, gluing the Carborundurn facr platr of thc t ~ u n g i t s clmcd position. in IT was also rlfscovcrcd that when anr rnollcn slag rxistcd in the furnace, it was prnctically impossible to obtain a high
vacuum.

control of condenser temperature much

more difificult. I n an attempt to eliminntc thc slag, thc cntire unit was raised to a tcmperaturc of ?RmF. and held at that tcmprraturp for an entire ivcch. Still thcre was no evidence that slagging had been e2imi naled T~ts were discon~intzurl thvrclorc until the cauFe of the slagging cnulrl be fountl.

Prnduction of magnesium during four sulisequent runs brought out a nurnkr of pnintrj. Thc briquettes could not be complc tcly degassed at the charge-hold in^ temperature of I 250' to r4wF. The rapid rate of heat transfer obtained from the storage refractory to the briqurttcs began t h e production of magnesium a t prrwurcs far in exccss of 0.2 in. HE.It was Iountl impwsible to eliminate the slaggirlg a t temperatures abox-e z400a1"., and operation

.4dislag~irr Tcsls rlrrd I I i ~ ~ d o p m c r r ~ s Since lahoralnry t-tc hail shown that purr silicon carhitlc (Carborundurn) docs not slag a t tcrnprratttrr< Pvrn al>n*ethe range of operation o thc turrlacc, it was f evident that eithrr t h r crmrnt or the rcfractory co~itaincrl s u l tancfi that did ~ slag untlrr the cnntlitic~ns of oprration. .Iko, sincc sonic s l a f i ~ i n had ocrurrcd ~ 'txfnre the trriqurtlw \vl.rrt. inrrotluccd. nci thcr thc dolnmitc nor thc m a g n ~ i u m vapor cr~ulrlIlc ~vhr>lly r~pnnsi1)lc. 1:xnminntinn crf tmt data from the six pruvious charges intlicatcr! that it rvas

not likely that the production of magnesium nor the vacuum was responsible for the slagging. Analyses revealed the various slags to be complex, containing silica, alumina in large proportions, iron oxide, calcium oxide and magnesium oxide. Examination of the spallac brick underneath the muffle revealed that the bulk of the slagging was coming from the combustion chamber. At no time during the operations had i t been possible to detect any slag running over the inside surfaces of the muffle. When the Carborundum muffle was removed and access to the heat-storage Carborundum was provided, it was quite apparent that the silicon carbide cement used to bond the heat-storage brick had melted out of most joints and slagged over most of the inside of the furnace (Figs. 7 and 8). Analysis of the cement used showed : Silicon dioxide. . . . . . . . . . . I I .8 Silicon carbide. . . . . . . . . . . 80.33 Iron oxide. . . . . . . . . . . . . 2 . 8 0 Aluminum oxide.. . . . . . . . 3.27 Calcium oxide.. . . . . . . . . . 0.51 Magnesium oxide. . . . . . . . o.5j Other impurities.. . . . . . . . 0.80
PER CENT

The slag that first glued the bottom of the bung was composed of: Silicon dioxide.. . . . . . . . . . Aluminum oxide. . . . . . . . . Calcium oxide. . . . . . . . . . Magnesium oxide.. . . . . . Other impurities. . . . . . . . .
PERCENT

jo.o j 23.22 I 7.60

9.01

o.I 2

Subsequent green glassy slags were found to contain: Silica.. . . . . . . . . . . . . . . . . . 61.56 Iron oxide. . . . . . . . . . . . . 3.57 Aluminum oxide.. . . . . . . . 24.80 Calcium oxide. . . . . . . . . . . 7.48 Magnesium oxide.. . . . . . . I . 25
PER CENT

Apparently the cement did not slag as a single compound but did so in a selective manner. I t appeared that the lowermelting-point substances melted out of the mixture first, followed by the others

a t successively higher melting tempcratures. The slagging material also seemed to become more refractory as the unit was operated. Subsequent tests indicated that the cement melted a t approximately 2570F. In all cases aluminum oxide was present in various amounts in the slags and in the peeled Carborundum. Since neither the dolomite nor the ferrosilicon contained appreciable amounts of this compound, i t must have been introduced by the cement. The investigations, which were continued for several months, showed conclusively that the " impurities," alumina and iron oxide, in the cement as a clay, were responsible for the low fusion point of the cement. I t was also shown that fusion would have occurred even if the furnace had never been exposed to vacuum a t the high temperatures of operation or to the attack of magnesium vapor. Cements free from these materials, also a number of zirconium silicate cements and refractories, were next tested. Unfortunately, the zircon cements, although quite satisfactory otherwise, showed evidence of attack by magnesium vapor. Hence their use was not possible. H o w ever, purified. silicon carbide cements were developed, which contained none of the clay ordinarily used as a binderi.e., less than 3 per cent impuritieswhereas the former cement had contained up to about 7 per cent. The interior of the unit was also rebuilt with entirely new Carborundum brick. Eventually a purified cement containing less than 2 . j per cent total aluminum and iron oxides was obtained and proved stable a t temperatures as high as 2850F. Tests on the effect of the briquettes on the silicon carbide cements, glasses and brick brought out a new point.. Although dolomite powder showed a tendency to fuse, it did not attack the unglazed brick, but it did attack the glazed brick. Also, it was noted that while the briquettes

E. G. DE CORIOLIS

15

did not attack the unglazed brick a t first, they did so when fusion of the ferrosilicon occurred. Attack on the purified cement was noted as well. Previous experience had demonstrated that the briquettes could not be fused in vacuum a t 2700F., but that if the ferrosilicon were oxidized the briquettes would fuse at that temperature. I t was, therefore, to be expected that if the ferrosilicon in the briquettes is kept from oxidizing in the unit, by discharging directly after the vacuum is broken, no rapid attack will occur.

progress and afforded a tool for comparing the production rate of the unit under a variety of operating conditions.

Revised Charging Method

I t had been found that the time required to evacuate the unit with the briquette? in the upper chamber was unduly long, requiring about 30 min. Furthermore, after reaching a comparatively low pressure before the charge was dumped, the rate of evolution of the gases from the charge into the reaction zone was so great that the pressure quickly rose to one inch after the charge was dumped. This indicated that the degassing accomplished in the upper chamber was not sufficient and actually of little value in shortening the time to attain high vacuum. Accordingly, the method of holding the charge in the upper "holding chamber," as originally developed, was eliminated and the charge dumped directly into the reaction zone a t atmospheric pressure. The revised method made i t possible to dump the charge quickly and to place the unit under vacuum within less than one minute after dumping.

Revisions to Condenser
Concurrent with the solution of the cement-slagging problem, work was conducted toward revising the condensing system. The new condenser was 8 in. in diameter instead of 14 and 16 as previously. Precautions also were taken to make sure that the vapor would be directed against the condensing surface. The top of the charge-holding chamber was necked down so that there was but 3-in. clearance between the condenser and wall of the chamber. The electric heating elements were relocated, to afford better heat control. The bottom bung was reconstructed, to avoid possible sticking.

"Production" Runs
Revisions were completed and the unit was refired in October 1943. By the middle of the following month some seven charges had been made in the unit. I n each the structure of the magnesium was good. Yields up to 60 per cent on the ferrosilicon basis were obtained. The magnesium production rate was carefully determined as a function of time. The condenser proved to be of correct size and under certain conditions operated satisfactorily. Up to this time and during these runs wet briquettes were used. The charges were dropped into the reaction chamber under atmospheric pressure, yet in all cases evacuation rates were more rapid than those previously obtained. The

Measurement of Magnesium Condensalion Rate

The previous method of observing the rate of magnesium condensation by means of a sight glass was far from adequate. In order to follow the condensation process more accurately, a heat exchanger was provided to measure the heat increment in the cooling water that was recirculated through the condenser, the heat in turn coming from the condensation of the magnesium vapor on the condenser surface. The system provided a reasonably accurate method of following reaction

106

THE REFRACTORY OR "EIKELESS COOKER" METHOD OF PKODUCING MAGNESIUM

ultimate vacuum obtained was considerably improved. No dificulty was experienced with slagging of either the cement or Carborundum brick.

until the vacuum is broken. The production efficiency of 41.5 per cent on the silicon basis was obtained after about 150 min. under vacuum. Although times up to 4 hr.

Wet versus Dry Briquettes Tests with Wet Briquettes.-The normal charges as previously used were composed of 650 lb. of wet briquettes mixed in the n~olecularratio of 1.1 MgO in the calcined dolomite to I Si in the 7 5 per cent ferrosilicon. Approximately I j o lb. of water vapor and other volatile matter was contained in each charge. The available magnesium per charge \\,as approximately 9 2 lb. After preheating in the convection furnace a t 12j0F., the briquettes were dumped directly into the reaction zone according to the revised method, the temperature of the furnace being 2650F. I n all, 16 charges were made. All were the same except that conditions of the condenser and upper chamber were varied in attempting to control the form of magnesium condensation and sodium separation. Fig. 9 shows a chart of the rate of n~agnesiun~ condensation and silicon efficiency as a function of time, using wet briquettes. Briefly, the curve indicates that magnesium condensation starts about 10min. after charging, reaches a maximum after 40 min. and then decreases slowly

under vacuum gave efficiencies as high as 60 per cent, a study of the heat input to the charge showed that much more than 40 per cent efficiency should have been obtained in the shorter period. The reason for the lower efficiency, therefore, was difficult to understand. During these runs i t was only when poor magnesium efficiencies were obtained. leaving unreactcd ferrosilicon in the charge, that difficulty in removing the spent briquettes was experienced. Under such conditions the silicon would burn when the vacuum was broken, generating excessively high temperatures, which tcnded to fuse the briquettes together. Efficiencies higher than 50 per cent gave no trouble. Diffusion of magnesium through the bottom alloy seal when the metal condensed on the bottom closure was also a minor problem. It was eliminated by proper adjustment of the spring holding the seal plates together. Natural gas was introduced in one a t t e m ~ tto eliminate this trouble, but was of doubtful success, although it did result in a slightly higher magnesium production per charge.

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108

THE

REFRACTORY OR '

F COOKER" ~ ~ METHOD OF ~ ~

PRODUCING MAGNESIUM ~ ~ ~

F ~ G . I I .--DRILLED 3-INCH-DIAMETER PIPE USED AS CORE FOR MAGNESIUM VENTING.

in. holes and made in three sections (Fig. 11) was used in the next test. By lowering this core into the furnace, then immediately dumping the charge around it, the tube was not exposed to oxidation until the vacuum was broken. I n the tests on coring the charge consisted of 525 Ib. of wet briquettes similar to those used previously, the charge now containing approximately 7 4 lb. of magnesium. The results proved the soundness of the theory. Magnesium production was well started a t the end of 10 min. The maximum rate of condensation of 111,ooo B.t.u. per hour was attained a t the end of 30 min., as compared with the previous maximum without the core of 87,000 B.t.u. per hour a t the end of 40 min. Furthermore, the silicon efficiency was increased from the previous value of 41.5 per cent without the core to 5 5 per cent with the core a t the end of 150 min. (Fig. 12). Since the question arose as to whether or not some increase in over-all efficiency might not have occurred because there was no necessity for transferring heat to the briquettes formerly occupying the space now taken up by the core, a subsequent test was made to check this possibility. The core pipe was replaced by one having twice as many holes but exactly similar otherwise. The results showed that magnesium production began a t the same time as with the former pipe core, but the maximum production rate obtained was 139,ooo B.t.u. per hour. Total production was also tremendously increased. At the end of 150 min., the efficiency was 7 0 per cent, an increase of 63 per cent over operations when no core was used and 27 per cent above that with the former steel core. Not only was it obvious that the briquettes formerly contained in the core could have no effect, but the cause of previous low was eliminated. Subsequently, larger cores were tried.

E G. DE CORIOLIS .

19

Dry briquettes were also used, with an increase in efficiency, but still not equal to that obtained with the wet briquettes. Figs. 13 and 14, corrected for differences

Repeatedly different amounts of heat per unit time had to be abstracted from the magnesium vapor by the condenser, and under such conditions control was difficult.

Time. minutes FIG. 12.-RATE OF MAGNESIUM CONDENSATION 4ND SILICON EFFICIENCY A S A FUNCTIOK O F TIME. Charge of wet briquettes using 3-inch-diameter pipe core with seventy M-inch holes. in charge size, summarize all results obtained in the coring tests. No further rise in efficiency was noted when using larger coring.
Condenser Tests

Although primary attention throughout the tests was paid to increasing efficiency and total capacity of the furnace, the condenser problem, while secondary, remained extremely troublesome. Nor was it completely solved a t the conclusion of the tests. While the quality of magnesium produced and the location of most of it on the condenser were quite satisfactory in numerous tests, there was frequently a deposition of the metal admixed with sodium on the colder part of the condenser. At times this was caused by the deposition of calcium salts on the inside of the condenser from the boiling of hard water. Two major factors contributed to the condenser difficulties. I n the period of development just ended remarkable changes in production rates were induced.

The other difficulty arose from the fact that production began so soon after the dumping of the charge. Because of this, magnesium condensation began a t a pressure of 0.4 in. Hg and a considerable amountwas condensed before the pressure had dropped to 0.08 in., 15 min. after the start of production. Under such conditions the velocity of gases past the condenser was so great that the magnesium vapor was carried past the part of the condenser on which i t would have condensed under diffusion-flow conditions. This gave rise to the admixture of sodium with magnesium on the upper part of the condenser, thus causing both a loss in production and a fire hazard. Various bailles were used to force the magnesium to condense on the proper part of the condenser, but although this worked very well a t first another condition soon developed that prevented the successful application of the principle. Magnesia and other foreign matter had gradually accumulated in the channels connecting the heat-storage chamber with the evacua-

o,
Frc. 13.-RATE
I. Charge, 2. Charge, 3 . Charge, 4 . Charge, j. Charge,

4
briquettes briquettes briquettes briquettes briquettes

Gb

Time.minutes
OF MAGNESIUM

ab

,oo

I$

I1 .

PRODUCTION AS A FUNCTION OF TIME.

wet wet dry wet dry

using 3-in. dia. pipe core with x.$o J6-in. holes. using 3-in. dia. pipe core with jo %-in. holes. using 3 - i n . dia. pipe core with 140 >i-i~i.holes. using n o core. using no core.

tion system, finally entirely closing them. From this time on all evacuation had to be accomplished through the condenser chamber. This slowed the rate of evacuation, but, more important, it caused a high-pressure condition a t the condenser when baffles were used. This condition gave rise to a very undesirable, crystalline structure of the magnesium. During this period the condensed magnesium was of such a form that part of i t very often fell from the condenser into the reaction zone. When this occurred the magnesium revaporized a t extremely high rates, thus making control of the condenser almost impossible. Furthermore, the vaporization was so rapid that local pressures as high as one half an atmosphere were generated. This is a sufficiently high pressure to produce molten magnesium and to cause it to come into contact with the Carborundum refractory. At times i t was necessary to break vacuum while the magnesium was still in the reaction retort. At these times local temperaturcs as high as 3oooF. were generated in the retort by the combusLion of the magnesium. I t was these occurrences that eventually weakened a small section of the reaction retort just a t the top of the charges. Finally, when the thirty-sixth charge was made, the briquettes broke through the weak section and made further operation impossible.

Although compelled to discontiilue the tests, a total of 34 completed runs assures that a number of facts were definitely established. Correlation of results of heattest records showcd that the heat available for the reaction was ample, about 77 per cent of the total used going into magnesium production. I n the design of the furnace it had been thought that the problem of heat transfer from the refractory to the briquettes would be a difficult one. Operation of the

furnace proved, however, that a factor of major importance might materially alter this assumption. When under vacuum and producing magnesium. the magnesium vapor particles apparently transfer heat a t an enormous rate compared with ordinary radiation and conduction. I t seems probable that the problem of heat transfer to the briqucttes is not such a major problem as was first thought. I vertical or large-diameter horizontal f retorts are employed, the problem may be only secondary to that of properly venting the charge. Venting is highly important. This incidentally leads to the question of whether or not the long, small-diameter retort used in the Pidgeon method is really concerned with heat transfer, or with the venting of the magnesium produced. When using a horizontal charge as in this process, there is always a space above the briquettes, which can serve as a channel for the vapor to escape. Hence, the distance the vapor must diffuse is less than the diameter of the retort. Very few difficulties were experienced with vacuum. Only if excessive dust accumulates during pouring, as with the dry briquettes, can the accumulated dust slow down the rate of evacuation. I n general, all vacuum seals, closures, and other parts were satisfactory. The work has demonstrated that pure, solid structures of good magnesium can be deposited a t pressures as high as 0.06 in. H g if the t e m p e r a t u r ~are held approximately right. Sufficient data have been accumulated to make i t possible to design a new condenser that urould provide the necessary characteristics. Certain conditions cause some slagging and corrosion on the inside of the retort. If the briquettes are allowed to remain in coiltact with silicon carbide a t tempcraturcs in excess of 2600F. while in contact with air, there is a tendency to melt the briquettes and make them flow over the refractory. The iron and silicon

IKER" METHOD OF PRODUCING MAGNESIUM

in the briquettes oxidize and form a compound that fuses in air a t about z600F. Little difficulty of this kind was noticed with the wet briquettes, howevcr. This caused no trouble with the type of bottom seal later used. The only severe corrosion occurred when magnesium dropped from the condenser and melted, as noted previously. The spent briquettes run freely out of the discharge bung when the production efficiency is 60 per cent or higher. The work carried out to date indicates that the time required to heat the furnace from the lower temperature to the higher, zzooO to z700F., is approximately 34 hr. Taking the reaction time for wet briquettcs as 236 hr., the total cycle would be 33d hr. With slightly more effective venting, it is reasonable to expect an increase in efficiency of 5 per cent, from 70 to 75 per cent, so that with a total production of IOO lb. of magnesium per charge, the hourly production would be 31 lb. While this is somewhat less than originally contemplated, i t is nevertheless quite satisfactory. This time is figured on the elimination of the preliminary degassing operation within the holding chamber, although degassing within the reaction chamber does have an effect upon the deposition of sodium on the condenser along with the magnesium. Although planned as a part of the original program, no tests were run using excessive amounts of ferrosilicon or with fluorspar as a catalyst. Since a strong possibility existed that either of these methods of increasing production might cause excessive slagging and ruin the muffle, their use was postponed in favor of other Iines of inquiry. Their use offers a possibility for future investigation.

or to estimate accurately its production capacity and cost of operation without further information concerning the factors in question, i t is possible to give the fundamental features of design that must be incorporated into such a furnace and make a rough estimate of the economics of the process. Assuming that the difficulties that still remain unsolved can be corrected in the future, i t should be practical to construct a furnace capable of producing between 500 and 1000 lb. of magnesium per charge. I t is conservative to expect that, when using wet briquettes of equimolecular mix, a silicon efficiency of 75 per cent can easily be attained. This would require 8300 lb. of wet charge containing 23 pcr cent water to produce 1000 lb. of magnesium. From previous operations, it is conservative to estimate that an efficiency of 75 per cent could be obtained in 4 hr. under vacuum, and that the furnace could be reheated to reaction temperatures in 2 hr., utilizing a t least IOOOOF. preheated air. The production capacity of the furnace, therefore, would be 1000 lb. of magnesium in 6 hr., or 4000 Ib. per 24-hr. day. This furnace, producing 1000 lb. per charge, would therefore be roughly equivalent in capacity to 40 alloy retorts of the type now used in the Pidgeon process. Obviously, i t is not possible to place too much confidence in estimated costs. However, it is felt that the estimates that have been made are conservative, and that they indicate that the refractorychamber method shows the potentiality of surviving competition with other processes for production of magnesium.

Although i t is not possible to design the details of a large commercial furnace,

The process was developed by Dr. J. J. Turin, now Ensign, U.S.N.R., with the collaboration of Jack Huebler. Design of the unit installed a t Luckey, Ohio, was by A. W. Peters.