Sept., 1919
T H E J O U R N A L OF I N D U S T R I A L A N D E N G I N E E R I N G C H E M I S T R Y
837
THE PRODUCTION OF NITROGENOUS COMPOUNDS SYNTHETICALLY IN THE UNITED STATES AND GERMANY ~
BY
ROBBRT
E. MCCONNELL, Late Lieutenant, U. S. Navy Received July 17, 1919
SUCCESS O F GERMAN T E C H N I S T S
Germany’s sustained resistance during hostilities depended directly upon her own supply of raw materials. Her economic isolation, accentuated when Italy a n d Roumania joined the Allies, was one of the remarkable features of t h e war. T h e blockade against importations produced t h e inevitable consequencesa revolution in technology. Nitrogenous compounds, which, in times of peace, are constituents so important t o industry and agriculture, became, during the mar, of prime necessity for t h e manufacture of munitions. I n 1913 Germany imported three quarters of a million tons of sodium nitrate f r o m t h e Chilean mines. A stock of half a million tons had been accumulated b u t this was insufficient for t h e production of munitions required by Germany on the western front in the year 1914. For t h e past t w e n t y years German technists have been active in deJeloping processes for t h e manufacture of nitrogenous products synthetically, which would render t h e German government independent of nitrate importations, in t h e event of hostilities. Considerable secrecy was attached t o these experiments, a n d since 1914 practically no information regarding the German developments had been obtainable. Through t h e Germans’ success in synthetic nitrate production, which has replaced Chilean nitrate importations, the blockade against munitions of war has been rendered ineffective. It is stated conservatively, t h a t without t h e product of these plants, Germany, through lack of munitions, would have been decisively defeated in 191 j. T h e production of nitrogenous products synthetically became of prime importance a n d the fact t h a t successful development of efficient synthetic nitrate plants h a d been accomplished b y t h e Germans could be stated conclusively in 191j upon t h e sole evidence of Germany’s sustained resistance. It is significant t h a t t h e assured success of German technists in t h e development of t h e Haber process for the manufacture of nitrogenous products synthetically was attended b y declaration of war. I n the perfection of their synthetic nitrate program German technists havegreatly depreciated the functional value of the huge a n d efficient British fleet. Great Britain is no longer able t o embarrass her enemy’s nitrogen supply b y sea blockade, providing such a n enemy is in possession of commercially successful synthetic nitrate plants or t h e ability and knowledge t o build such plants in a minimum time. U N I T E D STATES NITRATE P R O G R A M D U R I N G HOSTILITIES
During hostilities t h e United States a n d associated powers imported practically the entire o u t p u t of t h e Chilean nitrate mines for t h e manufacture of munitions of war. T h e United States consumed 60 per cent
of this world’s production in 1918,over 95 per cent of which was used in t h e manufacture of explosives a n d propellants. Notwithstanding this availability of t h e world’s supply, the United States a n d associated powers became greatly concerned over the sufficiency of nitrates for munitions manufacture, a n d on account of this apprehension coupled with the realization of t h e success of German synthetic nitrate plants, instituted extensive effort a n d large expenditure toward synthetic developments. A reasonably accurate forecast of military a n d naval methods a n d conditions which may prevail j t o I j years in t h e future, and provision of the means t o contend with such conditions, constitutes a prime function of our military and naval authorities. At this time, upon t h e conclusion of t h e world war, conjecture has become a n evident f a c t . T h e urgent importance of a comprehensive nitrate program appears clearly defined. Shortly after the declaration of war b y t h e United States, t h e President appointed a Nitrate Commission, t h e personnel of which included Rear Admiral Ralph Earle, Mr. Gano Dunn, Dr. Charles Parsons, Dr. A. A. Noyes, a n d Colonel Joyes. This Commission was delegated t o submit recommendations upon the type, size, number, a n d location of nitrate plants required t o insure an adequate supply of nitrogenous compounds for t h e manufacture of munitions of war. T h e problem which confronted t h e Commission involved the selection of the process best adapted t o fulfill t h e needs of t h e moment. There were no commercial nitrate plants in this country. Any process selected b y the Commission would have involved the solution of certain technical a n d mechanical problems which had not then been worked out in detail in this country. There existed two processes, however, which gave every reasonable assurance of dependable operation. These were known as t h e arc process a n d t h e cyanamide process, both of which required a n enormous supply of electric power. T h e former process utilizes the electric arc directly in the fixation of atmospheric nitrogen a n d has been developed t o a fair degree of success in Norway where electric power is very cheap. T h e cyanamide process makes use of t h e electric arc for making calcium carbide. T h e carbide is placed in an atmosphere of nitrogen, derived by the fractional distillation of liquid air, a n d under proper conditions will absorb a certain amount of nitrogen, forming a compound known as cyanamide. T h e cyanamide is then placed in immense vessels a n d steam is admitted which combines with the nitrogen, forming ammonia. T h e ammonia is then oxidized by passing over hot platinum screens and the oxides of nitrogen are absorbed in water, forming nitric acid. Of the two processes t h e cyanamide process requires less power. There also existed two other processes, as yet in
838
T E E J O U R N A L OF I N D U S T R I A L A N D E N G I N E E R I N G C H E M I S T R Y
the experimental stage, which gave promise of f a r greater economy of power and raw material requirements. These were known as t h e ammonia synthesis, or Haber process, and t h e cyanide process. It could not then have been positively stated, however, t h a t either of these experimental processes could be snccessfully and promptly perfected so as t o assure dependable large-scale production. Technists of the General Chemical Company’s staff had demonstrated their ability t o manufacture ammonia synthetically, in a more or less intermittent operation of their experimental plant on Long Island. It was known t h a t the German chemist, Haber, had successfully developed this process and t h a t large and efficient Haber plants had been constructed in Germany. T h e development involved the coordination of a great many very delicate and complicated mechanical details. T h e failure t o perfect any one of the several difficult steps in t h e process would mean t h e Failure of the whole scheme. The German scientists had been a t work on t h e problem for years and with the generous support of their government had finally developed a successful process. The Nitrate Commission, in view of the existing emergency, recommended t h a t a cyanamide plant be immediatefy constructed a t Sheffield, Alabama. It was realized that such a plant would require a large amount of pourer and t h a t after t h e war i t could not he expected t o operate in competition with importations of Chilean nitrates. The Commission also recommended a smaller plant, adopting the ammonia synthesis process, t o bc constructed a t Sheffield. A iargescale experimental plant for the cyanide process was built in North Carolina. I n 1y18 two more cyanamide plants werc started in Ohio b u t the work was discontinued upon the signing of t h e armistice. The cyanamide plant a t Sheffield was practically complete by November 1918. The first unit of the ammonia synthesis plant, embodying the General Chemical Company process, was finished in the summer of 1yr8 and several months were spent in experimental operation. These large-scale experiments demonstrated a great many serious faults in the process of t h e General Chemical Company, some of which have been successfully solved, b u t there remain other mechanical and chemical problems which have not been solved in this country. The American engineers and scientists are not t o blame for this. The men who struggled with this process, including the Army and Navy technists, the General Chemical Company’s staff, t h e engineers of the J . G. Wb;te Engineering Corporation’s staff, and a number of special investigators are no less able, and are f a r more resourceful, than the Germans who have perfected the process. Our Government asked the American engineers t o solve immediately exceedingly difficult technical problems which had taken the best talent in Germany years t o soivc. The German government has wisely aided and foste.red this work for a good many years, fully realizing the difficulties involved, b u t also fully appreciating the advantages that would attend the surcess of her scientists and engineers. The Navy Department has been cognizant for
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No. 9
the past 10 years of the probable nitrate developments, accentuated and emphasized in the war. I n the year 1909 the subject received attention. Rear Admiral Ralph Earle, a t t h a t time Inspector of Ordnance of the Naval Magazine, Philippine Islands, took up the study of this subject. During t h e war, as Chief of the Bureau of Ordnance, he was instrumental in securing the appropriation of $IO,OOO,OOO for t h e construction of the Navy nitrate plant to have been built a t the Naval Proving Grounds, near Indian Head, Maryland. This appropriation passed ConThe General Chemical Comgress in July 1918. pany placed their staff and processes a t the Navy’s disposal. Preliminary plant design was completed in August by the J. G. White Engineering Corporation, which had contracted t o undertake the design and construction of the plant. Upon t h e signing of the armistice a large portion of t h e equipment and machinery designed had been completed. Ground had been broken for the plant site and temporary buildings for housing construction workmen were nearing completion. On November 8, 1918, all work was discontinued, contracts were cancelled, and in December t h e officers of the section organized t o execute this work had been demobilized or assigned other duties.
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Shortly after the United States declared war the War Department organized a Nitrate Division, the main function of which became t h e construction of nitrate plants. Approximately two hundred million dollars were appropriated for the construction of four Army plants. On the date of the armistice one Army cyanamide plant and the Army General Chemical Company plant were practically completed. T h e War Department bad expended approximately one hundred and ten million dollars. T h e General Chemical Company plant was designed for adaptation of methods similar t o those It is this type of plant employed by the Germans. which t h e Germans have perfected and by means of which they are able t o produce large quantities of nitrogenous products a t comparatively small cost. As a result t h e Germans have become independent
Sept., 19x9
T E E J O U R N A L OF I N D U S T R I A L A N D E N G I N E E R I N G C E E M I S T R Y
of nitrogenous ra” material importations for muni tion manufacture, and I t is the only country in possession of the knowledge and experience prerequisite t o such independence.
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839
compel the German management t o operate the plant and divulge t h e secrets involved. It is reported the American delegates opposed such action on the grounds of injustice and held t h a t the plant products should not he considered of a military nature. T h e French strongly felt this t o he a mistaken attitude and were anxious t o convince the American peace delegates of the necessity of securing all the information possible. The French authorities in Paris were therefore pleased t o learn of t h e interest manifested by the Navy De-. partment, and authorization t o “visit” the plant was granted the writer by the Ministre de la Reconstitution Industrielle on March s ~ . The French felt t h a t little or no information of value could be obtained by an inspection of the idle plant, and were probably in hopes t h a t the Navy Department, in realizing this, might then discuss the subject oE operation with the American delegates. The writer immediately undertook the examination of the Oppau plant, fully appreciating and deeply regretting t h e possibilities of interference and emharrassment t o which such work could be subjected. Upon arrival at the plant the Germans displayed a polite h u t sullen attitude. They seemed willing t o f a cursory inspection, hut detailed examination. On the writer was informed t h a t his urce of serious objection and ere prolonged a formal come Peace Conference.
Following the completion, in the summer of 1918, of the United States Nitrate Plant No. I , a t Sheffield, Alabama, which employed t h e General Chemical Company process, a considerable array of talent and unstinted public expenditure was applied in t h e effort t o effect successful and dependable operation. A number of complex technical problems have not been solved. The correlating of mechanical details involved have not yet been perfected. Upon the conclusion of the armistice the importance of t h e work had not diminished. Provisions for protection in the event of an attack on this country demand the perfection of the processes, dependable operation of t h e plants, and construction of larger plants t o free us of dependence upon communication with Chile and further the mitigation of the Navy’s obligation t o maintain and hold this long and difficult ocean route during possible hostilities. A thorough knowledge of German methods appears preeminently desirable as a measure of protection. The precarious position which will be occupied by belligerents in the future without this knowledge is manifest. I n the zone of occupation held by the French army there exists a Haher nitrate plant a t Oppau, near Ludwigshafen, on the Rhine. T h e Army Nitrate Division requested permission of t h e Secretary of War t o send a commission of army officers t o inspect the plant. This permission was not granted promptly. Upon knowledge of this the Navy Department took immediate Fro. 3-Ar OPPAU. W I r B e Scnusesns $?OR RBUUVAL OP Cnaaon action t o procure data on t h e German methods and the Dro=os bf 25 ATNOSPBBRBS writer was instructed t o secure this information. Undoubtedly, a number of brief, superficial inspections T h e idle plant had proved a very valuable source of of this plant had been made immediately following highly desirable technical and mechanical d a t a and its the French occupation of t h a t territory. So far a s similarity t o the American plant, with which the writer known, however, a thorough a n d complete study had had been identified, enabled him t o secure valuable not been attempted by experienced technists. information in t h e time available. T h e examination It was stated in March 1919 t h a t t h e French had was by no means complete, however, and with great petitioned the Peace Commission for permission t o reluctance i t was decided rtnwise t o remain longer a t
T H E J O U R N A L OF I N D l r S T R I r l L A N D E N G I N E E R I N G C H E M I S T R Y
840
the plant, under the existing conditions, without further instructions.
IT, No. 9
w a r Frankfort, where i t is oxidized hy platinum catalyst converters. PRODUCTS "S
G E R M A N S Y N T H E T I C N I T R A T E PLANTS
CAPACITY---During t h e year ending November I , 1918,the Oppau plant of the R. A. S . F. Company produced go,ooo long tons of fixed nitrogen by the Haber process; t h a t is t o say, the capacity of this plant is equivalent t o approximately one-fifth the total of 3,000,000 tons of sodium nitrate furnished by Chile t o the entire world during the same period. This capacity is approximately t e n times the anticipated capacity of the United States Nitrate Plant No. I , a t Sheffield, Alabama, or two and one-half times t h a t of Plant No. 2 (cyanamide), a t Sheffield.
Vol.
oprnu
PLAY?
Tor= per Yr. A i n e m n i u m Nitrate.. ........ 10,000 .Sodium Mtrate . . . . . . . . . . . . . 130,000 100 percent Nitric Acid.. .... 40,000 i i ~ i~ d ~ ~........... ~ ~ 40,ouu ~ ~ i
T o n s ComIhined N per YE.
a
.
3,450 21,410 8.890 32.9S0
.
_ . _ _ 66,700 __ has been VBriously stated from .%z~,ooo,oooto $~o,ooo,ooo. It i s understood marks was a n
he following figures: Iignitc lor producer gas e n ~ i n e 3........................ . 1.isnite for sterm t o co catalyst.. ...................... 1,ignitc for steam powex plant.. .........................
Coke for rater ~ a producers.. r
.........................
Tons per I k y 400 1000 350
__
..
1750 5011
From t h e same source the following figures werc iihtained. (Assumptions are indicated by italics): On?R*7lNO
isno isliarus st $1.40..
Punhri
..................
300 chemists at $.7.50 1i.50 tons Iiwite at
.
.,.
5 0 0 tons coke st 8X.ll
52,11111
1.050
%11,037
4.00~
~11.noo
INTfiYBST
Iz(1 4-Ar
OPP
x50,lill0,00li ai 6 u n l . . .......................... .R 8.000 Meinlrrimce and remavdr at 10 per cent ............... I4.00U Oucrbnld, t l l C S , pensiionr. etc., " a y . ................... 10,000 ,~ 1 0 T A l . COST PRB D*"
It IS reno rated capacity of 125: year, has been constructed true Germany's total caps
ucts manufactured in Germany in the year i g r 6 contained 400,ooo tons of combined nitrogen. an amount which is equivalent t o z,jao,ooo tons of sodium nitrate, which is practically equivalent t o i.lie total tonnage annually mined in Chile for the markets of the entire world. Germany is now in position to export nitrogenous products in amounts approximating her normal consumption of three quarters of n million tons annually. The liquid ammonia has been shipped t o Hochst,
-...............$54.037
It was stated by the snperintendeut t h a t the plant had operated continuously, with t h e exception of one twenty-four hour shut-down which was caused by one of the numerous air raids, in which a gas tank was punctured by a bomb fragment. During the war i t is probable t h a t repairs, adjustments, and renewals were postponed as far as possihie and since the date of the armistice considerable of this work has been undertaken. I t seeins likely t h a t such a plant, operating in normal times would be shut down for repairs about 10 per cent of the total time. The total cost per day then becomes $58,337. go,ooo X 2240
f 36j = 553,000 Ihs. combined nitrogen per day. The cost per pound of combined nitrogen is then 58,337 + 553,000 = IO. jg cents per pound, equivalent t o NaNOa a t 7.74 cents per pound. If all the ammonia were converted t o 100 per cent nitric acid a t Oppau, it would be necessary t o increase the size of the oxidation, absorption, and concentra-
S e p t , 1919
T H E J O U R N A L OF I N D U S T R I A L A N D ENGINEERING C H E M I S T R Y
tion plants threefold. The cost per pound of combined nitrogen in 100 per cent nitric acid may then become 1 2 cents, instead of 10.55 cents, which is equivalent t o 2.68 cents per pound for loo per cent nitric acid. The above calculation is based upon figures which are: of necessity, very crude assumptions; however, it appears entirely probable t h a t lhis plnnl will be able l o produce concentrated nitric acid ol a cas1 ?tot in excess aJ throe ccrils pcr pauiid. I n normal times, before the war, the cost of nitric acid, manufactured from imported Chilean nitrate, was five or six cents per pound in this country. The increase in labor, material, and freight rates will no doubt set a higher price on imported nitrates in the future. I t seems improbable t h a t the old prices of nitrogenous products from Chilean nitrates will be reduced even assuming t h a t Chile will reduce or withdraw her export nitrate duties.
Germany can produce nitrates at one-half the cost of nitrates in this country which are manufacturedfrom the imported Chilean product Consider the consequences. The German farmer will be supplied with fertilizers, manufactured from synthetic nitrates, a t one-half the cost t o the American farmer. The advantage t o Germany will be stupendous. If Germany succeeds in monopolizing this industry she can export nitrates a t a price which would enable her to supply her farmers with fertilizers a t practically no cost or she could undercut the price of nitrogenous products t o such a point t h a t i t would be no longer profitable for Chile t o operate her nitrate mines. If these mines are ever abandoned it would take years t o reestablish the normal production. If this should happen and our Government were so short-sighted as t o permit a German monopoly of the nitrate industry, Germany wmld also indirectly control the world's production of explosives and propellants. Our huge fleet and standing army would, of course, be utterly helpless without nitrates necessary for munitions of war. Synthetic nitrate plants should be constructed and their success will grant assurance of our safety in times
841
of war, and in times of peace will provide the American farmer with fertilizer a t almost one-half its present cost. The program will require a high quality of scientific and engineering skill applied t o a difficult series of problems over a period of years. There is no question about the ability of our American engineers t o master the problems, the question is one of financial support and sane direction. The perfection of complicated mechanical devices and technical details is a slow evolution and requires patience and money as well as skill and ability, The very nature of the subject should place the program under strict government control. I n consideration of this subject attention is invited to the controversy arising over the proposed nitrogen monopoly, which was fathered by the German cyanamide industry and the Deutsche Bank, and presented to the Reichstag in March 191j. The German government appeared desirous of maintaining t h e new cyanamide industry in a healthy condition. These monopoly plans were t o have authorized a commercial monopoly on mineral as well as artificial, inorganic, nitrogenous compounds, t o be valid until March 31, 1 9 2 2 , and t o be extended beyond t h a t date by special law granting such authorization. Confident of its ability, through the perfection of the Habcr process, t o supply nitrogenous compounds a t prices far below those 01 the cyanamide industry, the N. A. S. F. people exerte fluence in objection t o t h e proposed monopol matter of fact, t h e e gradual reduction point has been demonstrat in market price of the nitrogenous compounds, made possible by the Haber plant productions, and the German government is probably convinced t h a t t h e necessity of a nitrogen monopoly is no longer apparent, t o the end t h a t t h e idea appears now t o have been abandoned. OUR FUTURE NITRATE YROGRAM
It is estimated by the writer t h a t a nominal expenditure i n the United States Nitrate Plant No. I , at Sheffield, would accomplish, under competent supervision, the necessary modifications of t h e General Chemical Company process and apparatus t o permit of successful, economical operation, and production. Using this plant as a test or pilot plant, other plants, should be constructed until a capacity in excess of 200,ooo tons per year of combined nitrogen has been reached in this country. I n peace times the farmers' supply of essential fertilizers would be increased a n d t h e price reduced. I n event of war our existence may be dependent upon such plants. In any event our security would be vastly increased, the burden of obligation carried by our fleet would be greatly reduced, and its functional, effective value doubled. Further emphasis upon t h e great importance of our future nitrate program seems unnecessary. LOBANOBLBS,C ~ ~ i ~ o a n r ~
