INDUSTRIAL AND ENGINEERING CHEMISTRY
May, 1930
ing details, plans and constructs the necessary equipment, handles all electrical and mechanical features, and studies any operating difficulties that may arise-in short, the Development Department carries the problem through the difficulties of semi-plant scale operation to the point where it can be turned over to the Operating Department for actual operation on a full plant scale basis. The Commercial Research Department is in many respects a technical sales department; it introduces and exploits new products and sees the new product safely through that period when it is no more than a marketable possibility. It makes market surveys, production studies, and investi-
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gates locations for new plants. It reports on the advisability of acquiring new processes or entering new manufacturing fields. The maintenance of a patent file, patent literature searches, and an oversight of the general business and economic situation are also duties of this department. The Commercial Research Department is similar to a foreign relations department. This brief record of achievement serves as an index to the attitude of the South toward industrial growth, and the era under discussion here marks the evolution and building anew of industry in this section. The New South has for its watchword-Progress.
Pressure-Synthesis Operations of the Du Pont Ammonia Corporation’ HORTLT after the World War the Ordnance Department of the Army estimated that the niaxii[iuni military consumption of nitrogen in time of war would be 12,000 tons per month, or approximately 500 tons of :ammonia per day. Ten years later, in 1930, thih country h:ts two major synthetic ammonia m r k s , with production capacity in excess of this military requirement. One of these plants, that of the Du Pont ilmnionia Corporation a t Belle, IT. T’a., is particularly well located for national defense purposeb, since it is far inland. In the future it is expected that the demand for cheap fertilizer nitrogen will further stimulate investment of large sums in extensions to these plants, with the result that the supposed need for government-owned nitrogen works will remain but a political ghdst.
S
Development of Organization
Organized originally to provide ammonia for use in nitric acid manufacture within the parent company (E. I. du Pont de Nemours & Co.), the Du Pont Ammonia Corporation is, in addition to satisfying this demand, now marketing large quantities of ammonia to the refrigeration, explosives, fertilizer, and various other industries. The original plant capacity of 25 tons anhydrous ammonia per day has been increased many fold. Furthermore, methanol, which was produced a t first only in small quantity as part of the gas-purification process, has now become a distinct and major part of manufacture a t Belle. Additional operations comprise sodium formate and aqua ammonia manufacture, both of which are logical subsidiary operations. In its brief existence the company has made connections and has experienced developments of considerable fundamental importance. Starting originally with a synthesis process based upon the designs and experience of L’Air Liquide, which developed the well-known Claude process, the company subsequently acquired exclusive American rights to the Casale ammonia process. This occurred a t the time the assets of the defunct Niagara Ammonia Company were purchased. Through arrangements effected by the parent du Pont organization, the Du Pont Ammonia Corporation acquired the Sational Ammonia Company, a long-established and wellknown manufacturer and distributor of anhydrous ammonia, aqua ammonia, and ammonium carbonate, together with its subsidiary, the Pacific Nitrogen Corporation, of Seattle, Wash. Thus the Du Pont Ammonia Corporation now comprises ammonia-synthesis works in Belle, W. Va., and Seattle, Wash., and the marketing organizations of the National 1
Received April 2, 1930
Ammonia Company and the Pacific Kitrogen Corporation in addition to its onn marketing facilities. Coincident with thePe various organization developments there has been carried out a vigorous program of technical development in the field of ammonia synthesis and alcohol synthesis. As a result the Du Pont Ammonia Corporation process has decidedly new and advantageous features and repreqents a radical departure from the original Claude process. Layout of Belle Works
The accompanying illustrations indicate fairly well the magnitude of present operations a t the Belle works. Figure 1 is a general view of the Kanawha Valley a t Belle, which is about ten miles up stream from Charleston on the Kanawha River. The Du Pont Ammonia Corporation property occupies the central part of the illustration. The coal-handling equipment, which is designed to receive barge shipments of coal, is distinguishable on the river bank. Proceeding from left to right in the group of factory structures are the mountain power-recovery system, coke storage, works office building, machine shop, experimental gas holder, coke-handling equipment, compressor and synthesis house, water-gas generator house, steam plant, gas holders, coal-handling equip ment, another compressor and synthesis house, alcohol storage, alcohol purification, and experimental synthesis plant. Farther to the right are the buildings of the Belle Alkali Works. In the foreground are the tracks of the Chesapeake & Ohio Railroad and on the far side of the ammonia plant are the tracks of the Kew York Central Railroad. The Kanawha River, a navigable tributary to the Ohio River, is plainly distinguishable in the middle distance. Water-Gas Generators and Compressors
Figure 2 shows the water-gas generator house. The generators have a total capacity of about 70 million feet of blue water gas per day. The coke used in the generators is obtained from near-by beehive ovens. Beginning next autumn, coke will be obtained from by-product ovens which are now being installed alongside the water-gas plant by the Du I’ont Ammonia Corporation. Coal will be delivered from the mines by barge. The coke-oven gas will not be used in hydrogen manufacture, but instead will be burned under boilers. Recently various writers in the technical press have advocated the use of surplus coke-oven gas for ammonia synthesis. Du Pont Ammonia Corporation experience shows that manufacture from coke water gas provides far cheaper hydrogen than can be obtained from coke-oven gas, even
Finme 3
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l'lic ram are f i l l d Froin stumge, nliirh his a total capacit,? of 8 million pminds of anhydroiis aiiiiiioriia. It is cornnion practice to store animonia as liqiior, or in !lie form of fertilizer salts, but, a t Jirllr: aiiliyOroris aiiiiiioiiia as made is stored in
1)" Pant AmmOllia Corpnmfiun Works i n Celltn
steel tanka each liolding 100 tons, at storage tenipcrature and scirri-workn iadities, tiie,se bcing largely Sur the m a l l (about 10" F.). The tanks are Iiouaed in an insulat.ed huild- rcale, more furdamcntal studies. The experimental plants are provided with separate office, ing, which resenihler; a huge refrigerator. Heavy-walled storage t,anks are not, needed, since tlie ammonia pressur[, iitboratory, and control facilities. They are iiianncrl by perDespite tlie large expense in equipinent~and opis maintained at. 25 pounds gage, at which pressure thc wstment nnquestionably ha,s been worth while. boil-off is vented. The boil-off is continuously compressed and coiideiised and is ret.urned to the anhydrous storage tanks. Operating Staff The Du Pont Aninionia Corporation owns a fleet of 1F5 It is, of course, riccessary to have a large staff of engineers, special Class V tank cars for anliydrous ammonia service and; in addition, about 40 tank cars for alcohol service. Tlic research men, and plant superintendents in connection witti investment in an ltdcquate tank-car fleet for anhydrous am- the Bellc operation. In order to provide adequate housing , the office Lidding shorvn in Figtire 0 nionia service amounts to a very large sum. The Du I'oiit Ammonia Carpiration originated the shipment of anliyilioii~~ in tanks, thus effeetiiin large savings in cost of tinhydrous ainnionia to qirantity constoners. Through the cohperation of the U. S. Bureau of Explosives t.he capacitp of anhydrous ammonix tank Pars has bern incrrased from 30,000 pounils to 50,nnO pounds. The Burcau of Explosives LIPm v e s particular credit for materially reducirip tiie cost of such cars by investigation? which 1 1 s ~ ~ I d to a reduction in shell t.hiekness from 11/4 f,o '/rinch. The present cars are heavily lagged witli cork. Experinrents are bcing carried out at I3elii, to determine t,he coiriparat.ive pressures attained in insulated and nniiisulated cars. In tliesc experiments, an uninsiiI;at,ed car and a stanilanl iiuulated car charged with asntnonia are being observed uiidcr actual shipment conditions, particiilarly h i lint weather. Experimental Plants
Fieurc 4-liypercumpccss0ra
for Mired Gas
It is obviously ne1 ary in connection with a c o n ~ p ~ a i ~ ~ . Manufacturing Operations lively new and rapidly developing industry to carry out teclinicnl expoirncntal vork on a large scale. For this p u r p w 'l'lic tccliiiicnl opmt,ions in~-olvcdin the miruuniu a i d atthe Dir l'ont Ainnionia Corpcmt.ion has invcstcd t,liree-quar- (I, ~ l i i i lsgntliesr~swill s~~~n~n:irizeiI biicfly. (!r,ke is c l n ~ i g ~irit,o l t,lie water-gas gcnorators, w-liicli tcrs of a million dollars in experirnrntal ~ilant,s. The exterior of tiie semi-works liigh-pressure plant is s l ~ o i v ~ini prorlucc n crude \niter gas liariiig the approxiinate coinFigure 7. 21 part of the equipment of this expcrinient,al plant position of 50 pcr writ hydrogen and 40 per cent carbon is shoini in Vipiire 8. This experiineiital plant is designed iuonoxide. Froin the water-gas generators the ga.s passcs to produce hydrogcit aiid ainmonia, and in addition there tu the primary scriibbcr.: and from there to tlin >rater-gas :ire fa.ciltirs for ttir: stricly of alcoliol aud other pressure synThese liolders feed the hydrogen manufacturing tli~srs. I u \Viiiiiington lliivc are arl&tional cupcrirnerit:tl opm:~,ion, frorn wl,icli isstirs thc corrrct synthrsic niixt,ure 1 x 2
I'vljrsTIiI:! I. 21 .vu EivGI,vEEltlAYG C"E.lllliTRY
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Vol. 22,
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cubic feet,, as against iiearly $10 per 1000 cubic feet for compressed hydrogen in cyliiiders. E'urtlrcrinore, the 117drogm contairicd in one 100-pound c,ylindrr is equivalent tu tlic liyilrogen eontaincd in approximately fifteen cylinders of compressed Iiydrogen, each having a capacity of 200 cubic feet. Of course, it is neccssary to have a cracking nilit iii connection with the liquid ariiiriorria supply, but the cost is negligible. SOliJC of the iiscs for cracked annnonia, whicli al~pcarto be promising, arc in tlic cutting and welding OY metals, in the reductioir of inct,allic ides, in the working of fused quartz; and for gciicral lalioratory and miacellancous manuixcturing purposes wlrcre relatively m a l l quantitics of hydrogen are wa.ntcd. Whilc the current price of amnionia in cylinders is about 15 cents per pound, it slioiild hc pointed out that co~isu~ners es can buy it at about 0 cents per pound ie methanol is now available in tank-car Iots at 40.5 cents per gahn. These low prices are due. to recent advances in largescale pressure synthesis and to econornioal methods of distribution.
Figure 5 -Mountain S y ~ t c mfor Power Recovery
Outstanding Characteristics in Pressure-Synthesis Industry
tion is effected in tlw riietlianul converter ill wliich tlrc contained ciarlion n i o n o x i d r is
TIN! cnpitai investinen: necrssary for the cxploitaticm of pressure synthesis is sxtrerndy h i g h . An ammonia plant of 300 tons per day capacity is probably the minimimi rwnorrric size if sufficicntly low costs are to bc obtained to make a satisfactory rate of ret u r n in t h i s liiglily c o m p e t i t i v e field. \\.Me lai.ge eap:n:ity diriouslg is rlesirablc frorri the standpoint of opes at,i 11I: overliead, there arc oilier factors not xi ob,vious in their effect o n economy. The size of sucii operating irnitu as coiripresTank Cars with Anhydrous Ammonia
aoinionia, wiiicli is drawn ufi to sturagc as a liquid. T l i e residiinl gas From the ainmonia converters is scriibhwl to recover unconilcninl ainnioiiia as a q i i : ~ ammonia. Steam condensate provides the a water for ~ & i ammonia maniifnctore. TVitIi good design and proper operating Fiewre 6-1,oading procedure tlic liazards in high-presstire syntl, appear to be loss tliaii in most, if not all, of the chemical operatiom of which we have knowledge. In fact, during the four years that t,he Belle works has operated tlierc has not been a fatality in connection with the manufacturing operations. Development of New Uses for Products
There is at any given time a fairly definite limit to the quantity of ammonia and alcoliol ahich can be marketed in the iisrral channcls. ll,rrt:forc, it is dcsirahlc to ile\-elop ncnibly large oiitlet,s for t,liese Iroduets and, in fact, for any ot,iier products that niay be priijectcd. For this purpose the 1111 I'ont Aniinonia Corporatioii has sct 1111. :is part of ita technical orzaiiiextion, a Sales I)evr4oImiciit 1)ivision, t l i e pliTpoCC of wliicli is to study iicw urns for iiiiiinmiiii and oilier produr.ts ii might bc intcrrsted in By way of iiliistnti would appear to be a use as fuel. A brief siirvey of tlic wiinoniics ~IIIJW that :t 100-pound cylinder of ainiiinnia will furnish aimit 3000 cubic feet of hydrogm, uvlikli at present cylinder prices For ammonia may be obtained a t a cost of about 8.5 per IOMi
snm i s .... md mnvcrt.ers .". ..
inereiliing far beyond earlier prodict,ions and this factor of unit size controls, to an iniportant drgrcr, the i i i i i i i i n ~ n i
Pisure 9--Du Pant Ammonia Corporation, Works Osee Building
Yxgure 8--Bxperimentsi Synthesis Plant for Study of HiahPre8e"le Pl'we*sea
and i n fact cannot do so nutil the pcrsoimel bas beon trained thorougbly in tliis liiglily spccialised industry and until all operating procedures have been standardized. While there have been many adverse coiulitions under which bidustrial pressure synthesis lias dcveloped in this count,ry, it would appear that the future success of the inilnstry is now asnurcd, and the prodocts ol t,his industry are being marketed on a rapidly increasing scale. Within t,he past five years this conntry has bccoine secure as regards suplilies of nitrogen for national defense and agriculture. Certairily the earlier fears, rral or imaginary, with respect to the adequacy of ilomest,ic nitrogen supplies are no longer justified.
Manufacture of Carbon Dioxide and Epsom Salts' W. P. Heath CaBnohic L ~ u o n z r o n uAILANT& GI
Carbon Dioxide Manufacture
AIWON dioxide, one of the most abundant gases in nature, is today manufact,ured, or collected, in several different ways. f3efore prohibition it was collected aiid compressed as a by-product of the fermentatiou of beer. Tile most recent method is to pipe it from wells. In CaliSornia prospectors drilling for oil ran into large pockets of carbon dioxide under pressure. Under government lease thesc p(1cket.s are now yielding tfieir store of carbon dioxide. >lost, of the gas thus collected is used in the manufacture of solidified carbon dioxide. Perhaps the most universally wed process today is the coke process, whereby carbon dioxide is collected as a product of the combustkin of coke tinder forced draft. 111 Atlanta, because of the proximity of raw materials, tlie Crystal Carbonic Laborntwy uses the wet process, with doloinit.e, sulfuric acid, aid water as raw ioaterials. 3Ia.~~nrALs-~l~oloniitc is mined at Cartersvillc, Ca., whore is located a very large limestolio quarry, operated to supply cnisl~odstone for concrete. The stonc ou tlie face uf this quarry varies in m i i l froiii a practically pure dolomite t o a very liiglily siliceous one. T h e purest dolomite is in a horiziintal vein layer 4 or 5 feet thick. I t is of very fine grain and light in color and can easily he selected from tlie impure grades. An average analysis of this stone is as follows:
C
*
Received Mrtch 12. l Y 3 U
54.00 45.00 0.06 0.06 0.50 89.00
l'liis stonc is most suitable on account of its freedom from excessive amounts of oxide of iron and alumina, carbonaceous matter, sulfides, and silica. It is sliipped to the factory in so-called "one-man" lumps. Tbe sulfuric acid is manufactured in Atlanta from brimstone, is 60" BaumO in strength, and is free from sulfur dioxide and nitrous oxide, ingredients which will cause trouble in the operation. I delivered in steel cars of 100,000 pounds capacity and ored in a lead-lined tank on the top OS the factory building ready for use. EQUIPMENT AND PRocEss-The stone is reduced to GO mesh by passing through Sturtevant Mill Company's e q u i p nient consisting of a jaw crusher and ring roll mill and air separator. The dolomite is received in hopper-bottom cars and discbarged by gravity into storage adjacent to the crusher. Tbe pulverizer, elevators, and dust separator are located in one bay of the building 22.5 feet square the entire height of the building and kept tightly closed to prevent dust from spreading oser the factory. The pulverized material is stored in a concrete hopperbottom bin on the top floor of the factory, from which it may be drawn out into a cart on scales. This cart runs on a
