Proposed Manufacture of Monopotassium Phosphate at Green River, Wyo. I
General Survey; the Leniberg Reaction ROBERTD. PIKE,4069 Hollis St., Emeryville, Calif
The work covered by this series of articles was inspired by a desire on the part of Stockholders’ Syndicate of Los Angeles, owners of large deposits of phosphate rock in southeastern Idaho, to find means far economic manufacture and marketing of phosphoric acid from these deposits. The writer, therefore, made a survey of all available raw materials of the region which might have a bearing on the problem and finally came to the conclusion fhat its solution lay in effecting a combination of phosphoric acid with potash obtainable from the Wyomingite of the Leucite Hills of Wyoming. This solution potsesses lhe double adiantage of making use of raw
materials which are attailable in the general intermountain region in large quantity and in producing a fertilizer chemical of such high concentration thaf it can stand relatively high freight rates. The solution appears to possess considerable interest for the future because of the vast quantities of malerial available and because of the strategic location of Green River, the proposed point of manufacture, to u large part of the western United Slates, which it is anticipated may some day become a large eonsumer of commercial fertilizer. inferesting possibilities are also outlined for the production of compound7 of sodium as by-products.
HE Rocky Mountain region of the United States, Green River by pumping from shallow wells. This brine within convenient distance for freight haul from the bears an important role in the processes which have been town of Green River, Wyo., is a treasure house of developed. Vast supplies of common salt exist in the form those minerals and collateral resources for making concen- of a strong brine in the Great Salt Lake about 200 miles trated fertilizer chemicals which contain the principal ele- from Green River. Common salt can be produced very ments of plant food, and particularly monopotassium phos- cheaply at tho lake and shipped to Green River as au alternaphate. This conclusion follows from the close grouping of tive source of raw material to the Green River soda brine all of the necessary raw materials with cheap coal and natural in the processes to be described. By-pzoduct sulfuric arid gas and an inexhaustible supply of fresh water, together with is available a t Garfield, Utah, about 200 miles away, and large the avaihbility of practical processes to be described. supplies of native sulfur of commerciai grade occur in Utah The proposed industry naturally centers at the town of within practical distance. A good grade of l i e rock is Green River, which is on the Union Pacific Railroad about available within 120 miles. midway between Chicago and the Pacific, and on the magDuring 1926 and 1927 the writer undertook a research into nificent Green River. The elevation is about 6000 feet, methods for the manufacture of concentrated fertilizers and other c o m p o u n d s conand the situation is strategic taiuing phosphoric acid with from a freight viewpoint in that low rates exist on cona view to increasing the potential commercial value of t.he centrated f e r t i l i z e r s to the phosphate deposits of southPacific Coast for export; the e a s t e r n Idaho. As a result Green River is at the backof this work, m e t h o d s were door ofthegreat middle western developed f o r the low-cost plains where the demand for manufacture of commercial fertilizer is growing a n d is monopotassium p h o s p h a t e . d e s t i n e d to b e c o m e v e r y The source of p o t a s s i u m is great. Green River is ahout Wyomingite from the Leucite 40 miles f r o m the L e u c i t e ITis of Wyoming. It is the I l i of Wyoming (the source purpose of this paper to deof wyomingite), 15 miles from scribe the proposed processes large coal mines at R o c k which have been developed for Springs, 20 miles from two the commercial winning of potlarge n a t u r a l g a s reservoirs, ash from Wyomingite and the snd about 150 miles from the rnanufacture ou a tarye scale center, in southeastern Idaho, of commercial monopotaasiuni of what is probably the world’s phosphate. This latter coinlargest deposit of phosphate pound, containing as it does rock. A u n i q u e brine oona b o u t 80 p e r c e n t t o t a l t a i n i n g mostly sodium carbonate, some sodium chloride, FIGURE 1. EASTFACEOF ZIRKELMESA,SUPERIOR, a v a i l a b l e plant food (50 per cent P20 and 30 per cent &O) WYO., OCTOBER,1921 and little else. is available at 256
March, 1933
I h U U S T R I A I, A N D E N G I N EIS f l I N G C 11 E M I S T R Y
and being nonhygroscopic, is the most valuable of tile coiieeiitrated fertilizer chemicals.
257
ticularly as the leucite content reported hy Scliultz and Crossnamely, 26.1 per cent-does not account for the yield of actual potash (K&) from Wyomingite when subjected to base exchange with soda. The approximate mineral composition of Wyomingite as determined by a Wentworth micrometer stage is as follows:
EXTENTOF MATEnIAL RESoUnCES TnInuTArtY TO GREENRIVER . b y source of raw material to have interest in connectioii with these proposals must be g r a t i n extent. This criterion % bv naiume applies without question to the phosphate rock (If),the coal Leuoite so ( d ) , the fresh water of Green River (1, 17), the natural gss Pbloso i t a 15 Di0p& 12 (6), the salt of Great Salt Lake, the Wyomingite (14), and Katapborite 15 Glass and apatite tlie by-product sulfuric acid originating at Garfield Smelter, ___8 which results, in part, from the reduction of the concentrates roo of t,he Utah COOW The only p o t a s h Company. A test of bearing minerals an existing brine well f o u n d in the wycby t h e w r i t e r , torningite s t u d i e d are gether with a geologil e u c i t e and phlogocal r e p o r t by Boyle pite. T h e l e u c i t e (B), indicates a vast was a l t e r e d comsupply of the Green pletely to analcite by R i v e r soda b r i n e . the leaching process The same applies to to be described; hut the source of n a t i v e pblogopite appeared sulfur in Utah which to be unaltered by mas also examined leaching. and reported upon by Boyle (3, 8). Cheap The p r e s e n t - d a y n a t u r a l gas m a k e s p o t e n t i a l value of possible the cheap Wyomingite, as a prip r o d u c t i o n of mmary source of PO& P ~ W ~2.E om Q U A ~ R Y 01 LIBERTY PwrAan COMPANY. ZIRXBL MEAS, inonia. Thus, in this OCTOBER,1927 ash, d e p e n d s upon the fact that each 100 small region are resources potentially adequate to supply the entire Sorth pounds, when grouud to only a very moderate fineness, American continent with all the required plant food elementsquickly yields 8 pounds of K,O by base exchange with sodium i. e., phosphoric acid, potash, and nitrogen-in concentrated without the occurrence of side reactions, when leached under form for many centuries to come. pressure a t ZOOo C. Cheap and plentiful sodium compounds. particularly the carbonate, combined with cheap fuel will WYOMSWQITE yielrl vast quantities of potash from Wyomingite in the form The wvomineite dermsits of the Leucite Hills of Wvon~ini. of (,oncentrated fertilizer chemicals a t relativelv low cost. ape descGbed by Schiltz and Cross (14). The pliot&aphs OTHER METHODSO F EXTBACTSNO POTASH FROM shown in Figures 1 and 2 give sume idea of the extent of ihe WYOMINQITE deposit. All in sight is Wyomingite. The overburden is a superficial layer of soil only a f e inches ~ thick. The deThe writer (f0)has already described experiments for posit covers many thousand acres, and is probably more ntiliaing Wyomingite as a flux for volatilizing phosphoric than 100 feet thick on the average. The estimate by Bcliults acid in a blast furnace. Granting that the blast furnace and Cross of one billion tons of Wyomingite seems consema- at Green River utilizes the cheap solid carbonaceous fuel of tive. About half of all the known Wyomingite is in Zirkel the region (7),this would he an economic use which would Mesa, whose western edge is only about 2 d e s east of and produce considerable quantities of potash as a by-product about 2000 feet higher than the Superior hrancli of the in the form of potassium phosphate. tinion Pacific Railroad. Wliere a trani line would ent the A typical analysis of wyomingite from Zirkel Mesa follows: railroad is about 44 miles from Green River. Superficial % % % % samples taken by tlie writer from different points on the mesa K.0 13.80 CnO 5.00 801 0.43 11.57 .Ailor 0.75 CO, 0.20 FeO MgG 7.58 1.80 showed a uniform quality. All the material used in these Nap0 P*OI 2.20 He0 1.00 Si03 51.40 Fe*Oi 4.10 experiments was taken from the abandoned quarry of the The writer believes that processes which attempt a mass ill-fated Liberty Potash Company and was wyomingite of uniform composition and properties. l n spite of the size decomposition of the Wyomingite by dissolution with acids and uniformity of this deposit, were it not for certain unique or by decomposition with bases at high temperature are not properties of the mineral leucite, of which wyomingite is economically sound because of the large quantities of energy largely composed, its sole value, in the opinion of the writer and reagents required relative to the unit of potash produced. I n an endeavor to manufacture potassium phosphate would reside in its use a8 a flux in the volatilization of phosphorus in a blast furnaco (10)in which case its potash would directly, various experiments were tried with phosphoric be collected as a by-product in tlie manufacture of phos- acid as a leach at atmospheric boiling temperature, and at 200 pounds gage pressure (190" C. or 374" F.). Under phorns (7). Because the value of Wyomingite as a primary source of pressure the extraction of K,O is about 30 per cent and at potash does not reside in its potash content as such, but atmospheric pressure about 20 per cent, which extractions rather in its content of the mineral leucite, i t becomes de- are too low to have commercial signi6cance. It is reported that Italian leucite is decomposed by sulfur sirable to determine the actual mineral analysis of the rock. Schultz and Cross had inferred this from chemical analysis, dioxide (13). Sulfur dioxide was used in these experiments but a direct microscopic analysis was desirable, more par- under a pressure of about 50 pounds gage pressure, introduced
INDUSTRIAL AND ENGINEERIKG CHEMISTRY
258
VoI. 25, No. 3
into an autoclave, in which the fine ground ayomingite was River. The development a t Trail, British Columbia, can agitated in water. After 230 minutes the extraction of KzO market some 400 tons daily of fertilizer materials consistwas 3.1 per cent. Evidently the leucite in wyomingite, ing of various compounds derived from fixed nitrogen and unlike that in Italian leucite, is not soluble in sulfurous acid. phosphates. The phosphate rock has to be brought a long If the reader is interested in a number of other unsuccessful distance from Idaho. The sulfuric acid is a by-product, methods to extract potash from Wyomingite, he is referred and its utilization apparently furnished the reason for esto Wells (16). tablishing the industry rather than any inherent suitability for manufacturing fertilizers at that point. The same type LEMBERGREACTION of industry has been established at Anaconda, illont., and seemingly for the same reasons. On the other hand, no A key to the economic extraction of potash from leucite reason exists for establishing the proposed industry at Green was discovered by Lemberg in 1876 (9). Lemberg showed River except the economic desirability for it, all things conthat the mineral leucite, whose formula is given as KzO.- sidered. A120s~4SiOz, is altered by treatment a t 180" to 195" C. (356" Vast deposits of high-grade soluble potash have recently to 383" F.) for 18 hours with sodium chloride solution. The been opened up in New Mexico. These will produce, accordleucite is converted into the mineral analcite (analcime), ing t o recent reports, very cheap potassium chloride and in the formula of which is NazO&O&ioz 2H20. The equa- sufficient amount, if need be, to supply all of the domestic tion for the reaction may be written: demand, and more besides. I n view of this new development, it is almost self evident that potassium chloride should not mol. wt., 436.6 mol. wt.,440.4 marketed from Wyomingite at Green River. KzO .AlzOa. 4sioz -I- 2Na+ -I- 2H10 F? NalO~A110~~4SiOz~2HzO + 2K+ beYet there are certain features of this proposed enterprise Quoting from Eitel ( 5 ) who reviews Lemberg's work: "He which are unique and which will not allow it to be dismissed (Lemberg) was the first to observe the alteration of natural from the field of possible economic developments. These leucite into analcime (analcite) by treating the former with features all have to do with unusual advantages for making aqueous sodium chloride solution at 180" to 195" C. for 18 a commercial grade of monopotassium phosphate, a waterhours. The base exchange is completely reversible since soluble nonhygroscopic salt containing about 30 per cent the analcime-bearing tails react with potassium carbonate K20and 50 per cent P205, and, therefore, more of a phosphatic solution with quantitative restoration of the leucite. It than a potash compound. One advantage is the possible use is shown that the facility of the base exchange reaction de- of Rock Springs coal as a fuel in a blast furnace for volatilizing pends on the 'previous history' of the material; a natural phosphorus; another is the use of wyomingite as a flux in leucite which has been ignited undergoes the base exchange blast furnace, producing an acid containing as much as 0.20 reaction more slowly when treated with sodium chloride pound of by-product K20 per pound of PzOj, or a third of solution. The ions Mg" and Ca" (in chloride solution) the amount necessary to make the 30-50 monopotassium phosphate; finally, the remaining potash necessary for the only partially replace the monovalent bases." I n Part I1 of this paper, experiments will be described manufacture of monopotassium phosphate can be obtained designed to discover the engineering characteristics of the by base exchange from Wyomingite with cheaply available Lemberg reaction as applied to wyomingite-i. e., the effect sodium compounds, notably sodium carbonate. It would seem to be a fair presumption that monopotassium of time, temperature, fineness of grinding, strength of salt solution, and various anions associated with the sodium ion. phosphate made at Green River, as herein proposed, could Such data have hitherto not been published although the be marketed profitably on the Pacific Coast and in the Middle application of the Lemberg reaction to the extraction of West in competition with potash from New Mexico and with potash from Wyomingite has been proposed by Shoeld (12). phosphates from Trail, Anaconda, or Florida, even when These data will show that, when Wyomingite is dry-ground assuming that no premium will be paid for potash and phosto a moderate degree of fineness, it yields practically all of phoric acid in the form of monopotassium phosphate over its leucitic potash by the Lemberg reaction, but a t a far less concentrated forms a t point of delivery. A recently greater speed than that mentioned by Lemberg. A leaching published analysis by Thoenen (15) indicates that monopotime of 1 to 3 hours is sufficient to extract 8 pounds of K20 tassium phosphate made by processes proposed in these artiper hundred pounds of Wyomingite. There are no side reac- cles would be marketable a t a profit throughout the United tions, and the temperature which has to be achieved, 200" States. C. (392" F.), is moderate. Only that amount of sodium is LITERATURE CITED consumed which is actually exchanged for potassium. The Anonymous, U. S. Geol. Survey, Water S u p p l y PapeT 66, 173 availability of very cheap compounds of sodium with cheap (1902). fuel, together with wyomingite, which can be laid down at Boyle, A. C., private communication. Green River for $1.00 per ton or less, constitutes a sound Boyle, A. C., private communication. economic basis for the large-scale primary production of comCampbell, M. R., U. S. Geol. Survey, Professional Paper 100-A, 24 (1922). pounds of potassium. I n this statement is implied the proper Eitel, TV., P?-eisschift furst. jabl. Ges., 52, 13 (1925). design of pressure vessel for carrying out the Lemberg reacHall, E. B., private communication. tion. This has been investigated; suitable vessels for carryHignett and Royster, IND.ENQ.CHEW,23, 84 (1931). ing out this reaction are available, having a net capacity of Lee, 1%'. T., U. S. Geol. Survey, Bull. 315, 485-9 (1907). Lemberg, Z. deut. geol. Ges., 28,519-621 (1876). about 5000 cubic feet, and an estimated daily production Pike, R. D., IND.ENQ.CHEM.,22, 344 (1930). of 40 to 50 net tons of KzO. Richards, R. K., and Mansfield, G. R., U. S. Geol. Survey,
----
RELATIONOF PROPOSED INDUSTRY TO COMPETING SOURCES Since this work was completed there have been many important developments in the phosphate and potash industries in North America which ought to be given consideration in connection with the proposed industry a t Green
Bull. 577, 70 (1914). Schoeld, U. S. Patent 1,402,973 (1922). Schroeder, J., J. IND. ENQ.CHEM.,8, 779-80 (1916). Schults, A. H., and Cross, Whitman, U. S. Geol. Survey, Bull. 512, 35 (1912). Thoenen, J. R . , Bur. Mines, Rept. In~estigations3190 (1932). Wells, R . C.. Professional Paper 98-D,37-40 (1916). Wooley, R. R., U. S. Geol. Survey. Water Supply Paper 618, 11-13, 266-70 (1930).
