INDUSTRIAL ALVDEA'GILYEERIA'G CHEMISTRY
520
Vol. 21, N o . 6
I
I
American Potash a n d Chemical
The Trona Enterprise' Plant of the American Potash and Chemical Corporation at Searles Lake G. Ross Robertson U N I V E R S I T Y O P C A L I P O R N I A AT LOS
A
VISIT to the remarkable potash-borax plant a t Trona, Calif., leads one to suggest an inscription to be carved on its cornerstone-"Dedicated to the memory of Willard Gibbs." It would be hard t o find elsewhere a more striking example of the cash value of the phase rule. Even barring all question of engineering skill and ingenuity, the fact remains that physical chemistry has marked the difference between success and failure in the recovery of California's desert alkalies. For years various amateurs have steTved and evaporated the bitter waters of Searles Lake, out in the Nohave Desert. I n quest of alkali salts they crystallized, filtered, dissolved, and analyzed. Usually they got nowhere. One, the pioneer John Searles himself, coaxed a few hundredweight per year of crude borax out of marginal lake efflorescences. His product of forty years ago, transported with difficulty and sold a t fancy prices, could not even find a buyer today under modern purity standards. I n the new industry, however, a research staff revels in thermostats and salt-phase diagrams in two, four, or even six dimensions. The production manager, himself a n expert physical chemist, spends the day manipulating phases, components, temperatures, pressures, and concentrations. Of all these he has a-plenty. But when the whistle blows he counts 240 tons of potassium chloride, 130 tons of borax, and 10 tons of boric acid which weren't there the night before. Every pound of this daily output is white and dry as the driven snow in Dakota, and of top purity for its grade. The cornerstone may belong to the honored Gibbs, but the rest of the plant must be credited t o the intelligent and persistent experts who have fought a ten years' battle against a great variety of obstacles. T o these men first of all should go the thanks of a nation for demonstrating that there is a n American potash industry. Received April 8, 1929.
ANGELES,C A L I F .
Isolated Trona The town of Trona lies beside Searles Lake in a strange, desert sink about 180 miles in a northerly direction from Los Angeles. It is in a country which Providence seems to have forgotten. Both snowstorms and days a t 115" Fahrenheit are to be found in the records. It is a full three hours' trip from the settlements at Searles Lake via the company railway and the connecting Southern Pacific to the nearest human habitation-barring only the lonely station a t Searles junction. After one has journeyed through long stretches of sand and creosote bushes, punctuated by a few lizards, it is interesting to come upon a modern town of a thousand souls, with a splendid plant, offices, laboratories, store, school, open-air theater, fine residences, the latest dial-type telephone system, and the latest shade in silk hosiery. It is a little world by itself. Searles Lake Extensive geological and analytical reports, dealing with the inland alkali basins of Southern California,2 are already available. Summarizing briefly the geographical and economic situation: Apparently the original sources contributing t o Searles Lake have run heayily t o minerals such as soda and potash feldspars. Upon natural disintegration and carbonation from the air these have long ago thrown out the alkaline earths which would contaminate the normal stream flow. Sodium and potassium are therefore the only cations of importance present. Centuries of evaporation without drainage have caused so much crystalline precipitation in the lake that the crystal bed now stands a trifle above the level of the briny mother liquor. The occasional flooding and drying of the lake following a rainstorm have caused a cement-like crust to coat the surface, largely preventing evaporation of the brine 2
Gale, U. S Geol Survey, Bull 680-L (1914).
ISDCSTRIL4LA S D ESC7I:ISEERISG CHE-VISTRY
June, 1929
52 1
Corporation, T r o n a , California
beneath. The solid material a t the surface is almost' wholly common salt,, but in submerged layers there is a queer series of little-known double salts, precipitated from coniples Iirines a t various stages in recent geological history. So smooth, so level, and so compact is the crystal inass that a 2-ton automobile speeds with impunity at' 60 miles per hour over its 12 square miles of glittering surface. Tlie crystal bed is practically valueless; but the brine, itself of enormous volume, is the basis of the present industry. The latest analysis of Searles Lake Iirine is wggestive of complications: Per cen! by weight h-aCI Kia*SOi KCI NazCO3 Na2BaO; Na3POi NaBr LiCl h-aJS
As?&
16.33 6.96 4.75 4.74 1.31 0.15; 0.109 0.021 0.020 0.019
CaO FeiOa SHa h-a I
- AliOa
Sb?Os Organic Total solids approx. Water by difference
Per cenl b ) u'eighl 0.0022 0 0020 0.0018 0.0014 0.0006 0.006
34.65 65.35
These analytical values, with ion pairs coupled in conventional fashion, warrant a slight modification in the light of hydrogen-ion concentration. The p H of the brine is 9.48. Under such a condition it is seen that Iicarbonate, metaborate, and monohydrogen-phosphate ions exist in appreciable quantity, thus adding to the complexity. The total quantity of raw material in Searles Lake is stupendous. The industry removes nearly 400 tons of product daily, and throws back into the selfsame lake the rejected residue of 1500 tons of worthless salts. Owing to the low level of the plant site relative to blie surrounding country, there is no drainage to the outer world. There simply isn't anything else to do with the refuse. Despite the wholesale throwback, analysts have been uaable in ten years to measure a change in composition of the lake brine as great as the probable error of their determination. So why worry? Solar Evaporation The blazing sun of the Mohave Desert was the natural and obvious tool of most of the ill-fated amateurs mho dabbled in Searles Lake. It looked like good economy to throw up a few dikes, pen in a lot of brine, and let Old Sol drink up the water. Unfortunately the phase-solubility diagram for this brine does not permit the separation of any single salt of value a t natural outdoor temperatures. Moreover! it is difficult to construct a solar pond which will not
leak. It is also expensive to harvest and learh a solar, crystalline precipitate. Failure mas the inevitable result. Much to the credit of Doctor Teeple3 and his technical staff, the "obvious" has lieen rejected. The sun has been discharged from the job, and fuel oil hired. llatliematics has been substituted for liunclies. Details of the early phases of the enterprise may be seen in the papers of Teeple3s4and De Ropp.6 Why the Sunshine Failed
The fundamental principle which revolutionized the mode of attack on Searles Lake is best illustrated in phase diagrams. Of the hundreds constructed by the Trona research staff, two, shown in slightly abbreviated form in ~ is perhaps the most Figures 1 and 2 , ~villsuffice to s h o what important feature of the process. Figure 1 is a solubility-composition diagram for the principal components of interest in bearles Lake brine. The temperature is 20" C., taken roughly as a mean of desert lake temperatures, summer and winter, day and night. It therefore may be applied to a solar evaporation pond. For simplicity minor constituents are ignored. Moreover, since sodium chloride is present in gross excess in all such evaporations, the further assumption is made that the solution is always saturated with that compound. By such tricks the physical chemist gets rid of a threatening fourth or fifth dimension, and confines his geometry to three critical components, K-, Cod--, and SO4 --, without great error. Following con-\-entional phase-rule practice, any point Tvithin the equilateral triangle, such as A , marks the three equivalent concentrations of the ions in question; the nearness of the point to either vertex is the. measure of the relative concentration of that component. The point A represents Searles Lake brine-(approx.) 5 equivalents K-, 7 equivalents COa--, and 8 equivalents bo4-- per unit quantity. The point is located in a pentagonal geometric field marked "glaserite." Using customary phase-rule interpretation, this means that a brine of A composition evaporated a t 20" C. will begin deposition of that particular double salt. The product is of course worthless. Sobody has commercial use for both sodium and potassium sulfate in one preparation, especially if mixed with sodium chloride. At the same time, nevertheless, the h i n e is being robbed of valuable potash. 3
5
Teeple, I K D E A G CHEM, 19, 318 (1927). Teeple, I O t d , 13, 249 (1921). 1 4 , 787 (1922), 14, 904 (1922). De Ropp, C h e m .l.lel Eng , 19, 425 (1918).
ISBC;STRIAL A N D EhrGINEERIh’G CHEMISTRY As glaserite separates, the composition of the mother liquor shifts steadily from A in a direction appropriate to the loss of 3 K 2 Sod. When the point B is reached, the field of “burkeite” is encountered. In laboratory terms, this second and equally worthless salt now comes down in company with a continued separation of glaserite. The arrow, diverted by the new phenomenon, proceeds to C, where sodium carbonate heptahydrate joins the m U e . Another shift in direction, and finally a t D is reached the real product desired, the single salt potassium chloride. Unfortunately the brine is nearly gone, glaserite having
+
Vol. 21, KO.6
of the quantities of sodium chloride which accompany the glaserite, burkeite, and sodium carbonate a t all times. It would be natural to fear that this ever present substance would continue into the potassium chloride crystallization. When the temperature is reduced, however, the law of mass action, combined with two peculiar solubility curves, comes to the assistance of the process. Just before cooling starts, the solution is barely saturated with sodium and potassium chlorides. As the temperature falls, the solubility of potassium chloride falls faster than that of sodium chloride. Potassium chloride crystallizes first. The instant this happens, just so the effective concentration of chloride ion falls. Sodium chloride becomes more soluble, not less soluble, in the remaining liquor, in spite of falling temperature. The all-important result is that no more sodium chloride comes out in a place where it would contaminate the finished potash product. As the crystallization of potassium chloride continues, the solubility of sodium sulfate-a possible product-rises according to its well-known reversed solubility curve. It is accordingly not to be feared as a contaminating impurity. Thus the crystallization of potassium chloride may be prolonged for a n extended period with large yield. Eventually, of course, a t a certain concentration the process must stop, and the brine go back to the start. Construction of Graphs
Figure 1-Evaporation
of Searles Lake Brine a t 20“ C.
Dotted triangle indicates field of hanksite, KCI 2NazC03 9Na2SOa, which does not appear in rapid evaporation and may be ignored
The preparation of even so simple a diagram as that of Figure 1 comes only after long and patient laboratory research. Synthetic mixtures approximating Searles Lake brine had to be made, components entering one by one. The identity of each double salt must be detected a t the
taken most of the potash. D being the end point of crystallization, the system becomes monovariant and a mixed product of constant composition, consisting of four salts, runs out t o the end. The process is a complete failure. Phase Manipulation
Figure 2 shows the same components a t 100” C. Point d again marks the composition of the lake brine. The fields, while identical in composition and general arrangement, are widely different in size, owing to variations in the slopes of solubility curves. Plainly burkeite is the first salt to crystallize this time. Worthless, but a good riddance a t the outset. Its quantity is large-the larger the better. After a gross deposition of burkeite has taken place along the line of the downward arrow, at E this salt is joined by sodium carbonate monohydrate. More good riddance. Deposition of the two salts occurs u p t o F , where potassium chloride is then about to join the mixture. Failure is again imminent, but a t this strategic moment the physical chemist administers the coup de grace. H e suddenly lowers the temperature to 20°
c.
Graphically this move of course means a shift a t once back t o Figure 1, where point F is found far out in the field of pure potassium chloride. One substance and one alone may separate; and it does separate in quantity aided by the fall in temperature. As potassium chloride is being precipitated, the glaserite field will again be reached; but just before that misfortune occurs, the sludge of potassium chloride is filtered and the mother liquor sent back in cyclic flow t o the start of the process. Thus we get pure potash; but the change from Figure 1 to Figure 2 has tremendous significance in the engineering application to follow. I n the above discussion no formal notice has been taken
Figure 2-Evaporation
of Searles Lake Brine a t 100’ C.
instant of appearance, a difficult task when the mixture was continually agitated in a thermostat. S e w double salts were occasionally discovered, and in some cases named after members of the Trona family. It seems queer that so worthless a crystal as the carbonate-sulfate should be named after a really useful executive, Assistant Manager W. E. Burke. Space forbids more than mere mention of further graphic problems. Each single variation in temperature involves a complete repetition of one of the tasks. The manipulation of tetraborate and metaborate ions,-carbonate and bicarbonate ions, as components has alone given the staff plenty to do.
Rate of Crystallization
Most troublesome is the problem occasionally arising when a salt is due according to soluhility rilles but hangs back in supersaturatinti. The Trona laboratory is still nursing one solution which lias been working toward equilibrium for two years and still yields crystals. In fact, rate of crystallization promises to be a feature of critical importance iir t,he developmerit of new methods I I I J ~ Yin prospect. Plant Practice
The Searles Lake plant a t the outset follows iti modified technic the program cited with Figure 2. First the brine ir pumped through emergency storage to two colossal tripleeffect evaporators, which are tlie feature exhibit of the whole enterprise. In these evaporators, following tlie continuoris cyclic process, the brim is joined by other brine which has already rim the gauntlet of tlie plant, and has returned for anotlrer treatment. llic cvagorators, receiving steam from the power-house torIrini:s, operate it1 t,hrec stages of redttced pressitre. Tliw mal effjeieticg is attained hy int,roilucing the brine to the low-terripcra,turc, liigli-vacuum evaporator lirst, tlien. in turii to t.lie others. An effiaiency of 2.2 pounds of eraparated water to 1 pound nf stearn is attained. Iii this system the pipe removing vapor from the lowpressure evaporator is 6 feet. in diaineter--u. sizable calilier for a steam pipe. In tlic daily run of tliese evaporators over 1500 torts OS burkeitc and allied salts settle ant in eoticciitratcd sliidge and are sluiced back into the lake. Enongli liquor is ste:rdily wasted here t.o keep doivn the percentage of mitior compotielits, which would otherwise acenmulate ill a cyclia, closed m. At just tlie proper coricentratiori waste salts, is ready to yield bot,li pot alld borax upon cooling. Were one to judge by t l i e so1uhilit.y diagrams, the process shortly to follow would seem hopeless. llrifortuiiately potassium chloride and borax, the two product,s to c~iii is not suficient t o wvrant t h e inatmSarture of ailfnric a d on t.lic?ground.
,.
BWaX
The stage is set for the crystallization of borax. The liquor, passing itit.o tall cylir 1 crystallizers, is cooled in the presence nf a cliarge of c h e seed. Tire rrsttlt,ing crystals, already pure enough for technical use, are t,lien recrystallized to give a product, of exceptionally high degrce of purity. A continuous time and teinperiiture control regulat.es the crystal size neatly to suit commercial deomwl. The isolation, washing, and drying follow immediately. Just at present. the entire bomx output nf tlie world is coming from a small area adjacent to the Kcn,-San Bertiardirro County line, stretching from Tmna to Anrargo. Death Valley, the E’uiier:il Range, and its famed coleinanite
Plant of American Pofash nnd Chemical Cor oraflon, Shewing Searles Lake in B a c k a r o u n i
Other Products
C:ornmon salt is almost scorned at the Trona plant.
It is
liarilly worth lianling to 1,os Angeles, altl~ouglie n o r n i ~ ~ ~ ~ s quantities are to lit: had i~ few rods fronl thc railway ter-
minus. The rise of nieclianical refrigeration, and to a slight extent the use of solid carlniri dioxide, has depressed the w-esti:rii iriarket in salt. The rescareh department has its eye on the great waste of carbonates i n tlie present process. Several hundred tons of potential soda ash escapt: daily down the sewer, largely in the complex of impure burkeite. Under present conditions in tlie West soda ash is nearly as valuable as boras, particularly iii vitw of freight relatioris. A Wartime Resource
The Tmna project is now long past the purely experiinental and proniotioti stage. It sbartds as the Verdult fortress of the Amerioari potash industr)-the oirly real potash plant to survive the g(Jst-lVilr deflation. America need fear n o longer n war hlochde against 1:crrnan and Frertcli potash. If the Federal Government will furnish 30 to 40 millions-a couple of days’ outlay in a modern wvsr--Tronii will build a plant to supply the entire country routinnmx4y witliout restriction. Supply Problems
Tlriinks partly to tlic therrriodynnmios of turbines and evaporators conneettxt in ta~idcni,Trotia is able to generate electric power niuch MXP cheaply tlrarr it c:m buy hydro-
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I N D LrSTRIAL A N D EiVGIATEERlN(:CIIE.UISTRY
electric power at hightensionlinesa fewmiles to the west. Incidentally, it may be noted that the California hydro-electric companies are not a t present in danger of bankruptcy. The Trona plant operates a 440-volt motor service, using fuel oil. Despite tlie long desert liaul of fuel, costs are reasona.ble. Urinkirig water is a treasure. I i s u a l l y there is an adequate s u p p l y , curtailed slightly in dry seasons, for human consumption. This is ohtnincd from springs high up in the Argus mountains a t suine distance froin the town. From wclls near the plant a slightly brackish supply is available and finds teclinioal use in the plant. It also serves the coiiipaiiy swimmiiil: pool, a popular leature. The priiblem of the cooling of liquids is solved in various ways, in spitc of torrid weather, froin the spraying of exposed piping to vacuniii evaporat,ion and standard compressedammwiia reSrigerat,iim.
Vol. 21, No. 6
is hauled that can be s l u i c e d ; n o t h i n g is shoveled that can be dissolved, sucked, or blown in some manner suggestive of a fluid. As a result the company employs a mininuni of niuckers and a maximum of intelligent y o u n g f e 11o ws witli hands on valves aiitl eyes on ciironometric recorders. F i l t e r presses a r c avoided where possible. Instead, the sepi~ratioii uf crystdine matter is carried out in conical s e t t I i n g c ti a m he i s , wliicli arc washed hy comitercurrent brinc. The wash waters. or rather was11 brines, after doing duty, pads on tlirough tlie elaborate pipe system to such part oS the plant as may be appropriat,eto receive them and continue the cycle. Onaccount of limited water supply, saline solutiolis arc employed to the limit for washing purposes before fresh water is expciided. German Practice
The phase-rule chemist is not tho only one at Trona who looks askance at solar evaporation. Sun-dried salts would have t u he loosened, shoveled up into vehicles, aiid laboriously carried to storage or dump. Wherefore the engineering staff has adopted a gospel of pipe limes aiid pumps. Nothing
In spite of the obvious advantage of the Stassfurt potash industry from tlie wagc standpoint, B coinparison witli Troiiit bears closer analysis. The Htassiurt heds, deep beiieatli tlie earth, coiistitute a mining problem, riot amerrable to handling ivith a coilceiioii of pumps, evaporators, and pipe lirics alone. The desert operators, after having weathered the drop in the pricc of potassium chloride from 8155 per ton, t,en years ago, to S4.60 today, arc now confident that the Searies Lake iiidustry caii hold its owii indefiiiitely against any such competition. Chemically the Stassfurt problems do not compare wit11 those of Searles Lake. The (ierinan supply coli segregates of individual double salts wliicti can be dissolved by themselves and treated with relative simplicity. Ages ago Eature went through a complex seijuerice US solid-piiase depositions, roughly analogous to the processes wliich Trona must now do in a manufacturiii ilant. The comporients arc to be sure in a different ortment. At Stassfurt, therefore, s p a r a t e veiiis or beds lie ready for sciectim. I n contrast with Searies Lake, for illustratioii, it is u. simple matter to obtain potassium chloride froin the single, readymade nriiieral carnallite, KCI .hlgCll, G11,O. Trona's polyglot solution is another story. WCcaii therefore take our c i i o i c ~ n g i n e c r i n gbrains, pumps, and pipe lines, or pick, sbovel, sild lioiat. Arid tlrc desert industry is
