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Ammonia’
Guy B. Taylor, Thomas H. Chilton, and Stanley L. Handforth
ExPB)LIMBN~AI. E. I ,
STATION, DU W I L X ~ N C T O NDEL.
Poar nld N B M v V R S AND COS~UANU. ,
YNTHETIC ammonia is rapidly becoming the primary As the products are cooled, the nitric oxide begins to react
large producer of nitric acid from Chilean nitrate for a great Part of the peroxides polymerizes,
many years, and has closely followed all work in the nitrogen-
2NOz Ns06 (3)
fixation field because of its obviously important bearing on
the manufacture of nitric acid. Since 1920 i t has appeared I n atmospBeric-pressure operation the gases then enter a
certain that nitric acid froni ammonia would supplant series of packed towers through which acid is circulated so
that from Chilean nitrate in America, so attention was rapidly that tlre strength is substantially constant from
directed to developing a process for ammonia oxidation. top to bottom in each tower but becomes weaker in each
succeeding tower. The reaction (4) taking place t.o form
acid in all the towers is
3N03 + HA1 =t 2HNOa + NO (4)
l‘lie nitric oxide prodiiced by &action 4 repeats Reaction 2
with tile excess oxygen preseiit in the packed tower.
Reaction 2 is irreversible at temperatures encouirtered
in absorption practice, hit is a termoleeular reaction with a
negative temperature coefficient (a, 3). Kcactions 3 and 4
involve equilibria ( I , 4, 7 , 8 ) favored by low temperature.
Calculations of plant pcrforniances are possible from fomrrlae
involving the rn,te constant of Renct.ion 2 and the equilibrium
Pressure Process
EXPERIMEXTAL PLAwr-Laboratory ex-
periments on the oxidation of ammonia nn-
der pressure were carried through to the
semi-works scale a t the Experimental Sta-
tion. Figure 6 is a diagrammatic sketch
of the semi-works plant, not drawn to scale,
which will also serve as a flow sheet of the
pressure process in general. Liquid am-
monia drawn from a cylinder was admitted
to a steam-jacketed pipe, where it wa?
gasified and superheated. The ammonia
gas was mixed with air which had been
preheated by interchange and filtered and
passed to the converter. The conversion
products from the heat-interchanger passed
through a coil submerged in a tank of
running water where acid, 35 to 55 per cent
"03, was condensed and trapped into an
appropriate plate of the absorption column.
The gas then passed through empty cast
chrome-iron vessels serving as oxidation
space, thence to the column.
Pipes and fittings handling the hot am-
monia-air mixture were made of nickel.
U All the acid section of the plant was con-
structed of chrome iron and gave not the
slightest trouble from corrosion.
The column, oxidation chamber, and pipe
fittings were all castings. Seamless drawn
tubing was used for the pipe lines. Valves
were made in the company's own shops
by machining bodily from forgings. When
this plant was built the art of working
chrome iron in this country was very little
advanced, S o one had succeeded in mak-
ing a riveted tank from plate. Cast screwed
elbows and the like were unsatisfactory
and these finally had to be machined from
solid bars. At the present time anything
may be had in this material that can be
made of ordinary steel.
The catalyst in this plant was a cylin-
der of platinum gauze 3 inches in diame-
ter, made of four layers in close contact.
The absorption column was 15 inches in
diameter, 14 to 16 plates, one 6-inch bub-
bler cap per plate. Both catalytic conver-
sion a n d t h e a b s o r p t i o n s t e p were
thoroughly studied over a range in ca-
pacity of 6 to 12 pounds ammonia per hour
and a t pressures of 50, 75, and 100 pounds
gage.
PILOT PLAm-On the basis of experience
gained with this experimental plant, a pilot
plant with fifteen times its nominal capacity
was built a t Repauno. The essential units
of both plants were the same.
In the pilot plant both the ammonia gas
and heated air were filtered. The cooler-
condenser was the return-bend type with
water trickling over a bank of tubes. The
column of twenty plates was provided
with two cooling sections, one between the
fifth and sixth and another between the
tenth and eleventh plates. It is necessary
f in large columns to cool both gas and
liquid. T h e c o n d e n s a t e was fed to
August, 1931 I'VD USTRIAL A N D ENGINEERING CHEMISTRY 863
water jackets. The amnionia was vaporized by steam capacity of the column, introduced many joints throough which
jackets on a large pipe just before mixing with heated air, leaks could occur int.0 the cooling watersithout being detected.
'rliis plant made 4 tons of nitric acid per day at 60 per ceiit Figure 12 shows on the right a column remodeled for the
strength in hot summer weather and 5 tons at 63 per cent improved cooling arrangement. The improved cooling
o r better during the winter mnont\%s. The yield from am- easily doubled its capacity with no increase in size.
omnia to nitric acid actually delivered approached 90 per
rent. Tiie loss out of the column as determined analytically . ~ -...-..
seldom ran as high as 2 per cent, and 1.5 per cent was normal.
Alkali scnihbing to recover this m a l l loss would pay only
iiiider special circumstances.
After this pilot plant served its original purbose, it was
rmoved to one of thc company's other plants and is still
in operation, with some later improvements, producing 6
tons or more per day.
CO.VMRI~CIAL P u N ~ T l i elower investment cost and
st,ronger acid resulting froni pressure operation more thaii
counterbalanced the increase in power for compressing air
and the lower conversion cfficieiicy obtained a t that time.
Tliese factors estnl~lislied by the pressure pilot plant led
Minitcdy in 19'28 to the adoption of this process for future
eqmision.
The largest of the pressure plants now in operation is
locat,ed a t Hepaiino. It consists of eight units wit.), a nominal
total cariacitv of 80 tons of nitric acid uer dav. Fimire 0
864 INDUSl'RIAL A N D ENGINBERIND CIIEMISTRY Vol. 23, No. 8
The result of the development to date is the adoption of an temperature raised 100' C . where the conversion is 98 per
operating unit consisting of a single converter about 2 cent this loss may he more than doubled. Yield, therefore,
feet in diameter delivering into a single column 5'/< feet in does not tell the whole story in costs. Catalyst replacement
diameter and 40 feet high capable of producing 25 tons of must be figured against ammonia costs for the most eco-
nitric acid in 24 hours, a capacity equal t o the whole low- nomical yield. With platinum-rhodium losses are approxi-
pressure plant shown in Figures 3 and 4. This standard mately halved. The loss per pound of ammonia burned
unit bas given an over-all soaleweight yield from ammonia is not affected by pressure. It seems to be a function of
to nitric acid of 93 per cent of theory a t an acid strength the weight of oxygen passing and the temperature.
of 61 per cent, with not more than 2 pcr cent loss in the spill The adsantages of pressure operation over operation at
gases. atmospheric pressure are (I) about half the initial investment
in plant, and (2) large increase in acid strength, reducing
Discussion of Alternative Processes both operating and investment costs of nitric acid concen-
tration by sulfuric acid.
The original spread in conversion efficiency of the pilot In operation a t atmospheric pressure, over-all plant yields
plants was 7 per cent in favor of low pressure when using better than 90 per cent of theory from ammonia to nitric
pure platinum as the catalyst. With platinum-I0 per cent acid can be ohtained. Operation a t 100 pounds gage, 7.8
rhodium (5) this spread under optimum conditions was atmospheres, will produce the same or better over-all yield
reduced to 4 per cent. The new design converter, besides at 8 to 10 per cent liigherktrengtli. The increase in strenCth
allowing an increase some five- fmni 50 per cent to 00 &r
fold in the pounds of ammonia cent means cutting by nearly
b u r n e d per ounce of metal one-half t h e c o s t of s u b -
per day, gives promise of sub- s e q u e n t concentration to 90
s t a n t i a l l y increasing yields per cent or higher. The only
nnder pressure. S y n t h e t i c operating item of the pressure
a m m o n i a contains traces of process significantly higher
oil and so does compressed air. than that of the atmospheric
For good conversions the most process is the cost of power. If
S C N ~ U ~ O U S care must be ex- in any p a r t i c u l a r l o c a t i o n
ercised to prevent oil from power rates are high, part of
reaching the catalyst. At any the power of compressing ajr
pressure coiiversion increases may be economically recovered
with rise of catalyst tempera- by use of an expansion engine
ture, but under pressure pre- on the gas exhausted from the
combustion may occur ahead columns.
of the rontact if the mixture is At one time in the develop
preheated much above350" C. ment when there was a sig-
The yield falls off slowly with nificant difference in conver-
increase in capacity above the sion between atmospheric and
optimum at all pressures. The piessnre operation, the alterna-
effect of running a 25 per cent tive of compressing after the
over rating is hardly detect- cata1,ytic step vas considered.
able on a commercial plant. This involved the construction
P l a t i n u m s t e a d i l y loses of a chromoiron compressor.
weight while in service. The Some experiments along this
loss amounts to 5 per cent per line were conducted bot cost
month under conditions giving studies indicatod that the ex-
95 per cent conversion a t at- pense of developing such a
mospheric pressure. With tho maebine was hardly warranted.
Thc latest typc converter gives such high yields that this local conditions determine whether in either case refngeration
course has been amply justified. There is certainly no ad- is justified.
vantage in compression after conversion.
Handling Anhydrous Ammonia
I n closing this article it is perhaps appropriate to say
a few words about handling anhydrous ammonia. Ammonia
is the most concentrated form in which nitrogen can be
shipped. For several years now i t has been shipped in tank
cars holding 50,000 pounds each. There is no difficulty
in unloading it int.0 storage tanks without loss or accident.
F i y r e 13 shows a row of storage tanks on an acid plant.
Each tank is hammer-welded steel and of tJie same size as a
tank car. Some of these tanks have been constantly under
pressures up to 150 pounds for years.
Acknowledgment
So many pcople have contributed to the development
described in this paper that proper acknowledgment to them
individually cannot be made here. Without a metal un-
Figure 13-Anhydrous Ammonla Sforaee Tanks attacked by nitric acid, a pressure operation would hardly
be practicable. This process owes much to the engineen of
Cooling an absorption system by refrigeration to tempera- both the du Pout Company and the steel manufacturers in
tures around 0” C., while it does materially decrease thc advancing the art of working chrome iron.
size of the system, is not nearly so effective &s a moderate Literature Cited
increase in pressure. Refrigeration as a method of cheapen-
ing plant costs is not very effective, because it reduces only (1) liodeustrin, L. Phyrih. Chom., 100, 68 (1922).
( 2 ) Uodlenririn,lhid.. 106, 105 (1922,.
the size of the absorptiori system, leaving all other units in (31 14iinei. I’feiRer, ond Malet. I.i h i m . phys., 21. 25 (1924)
the plant the same as without it. Pressure operation re- (4) Burdick and Freed, J. Am. Chem. Sor., IS, 518-30 (1921): Mass. Insf.
duces nearly all units in size. If refrigeration can he justified Technology, Thesis, 191X.
for an atmospireric pressure plant as a means of increasing ( 5 ) Ilavis, U. S. Patent 1,706,055 (Merch 19, 1929).
10) Perlcv. 1. INO. Euc. C N ~ M12.J-IB.
.. 119-120 118201
the capacity per cuhic foot of absorption volume, leas re-
frigeration would do proportionally even more in this di-
rection on a pressure plant. In the case of existing plants
NE of the most interesting aspects of the engineering sirable. Flint pebbles are imperfect, inany being fractured,
field is the almost overnight growth of fine grinding. cracked, chipped, and filled with holes, rendering them unfit
Materials and products which were formerly accept- for use with many products. The porcelain ball has made its
able a t 100 t o 130 mesh are now demanded 200-mesh fine; appearance as a more nearly perfect, and consequently a more
while products which were formerly thought very fine a t 200 desirable, grinding medium and is here t o stay. Its use
mesh are now commonplace a t 300 and there is a steady d e has heretofore bccn greatly FcJtrietod on account of its high
mand for products ground as fine as 350 mesh. cost, as balls have been made entirely by hand. Recently
Great strides have been made in the development of The Patterson Refractories Company, a snbaidiary of The
apparatus for fine grinding in the chemical, ceramic, metallur- Patterson Foundry & Machine Company, has developed an
gical, and mining fields. Pebble, ball, and tube mills occupy almost fully automatic method of manufacturing both por-
a prominent position in these fields because the amount of celain lining blocks and porcelain grinding balls. This method
grinding surface presented by the linings and by the freely and the plant in which i t is operated arc described in this
moving grinding mcdia is greater than in any other type of fine article.
bender. This accounts for the extremely fine products which A plant which makes a standardized product and turns
are now ground at very low cost with these machines. it out a t a fairly uniform rate, month in and montli out, is
Mills of these types are usually lined with Silex blocks susceptible to design of the straight-line production type and
imported from Belgium or with porcelain blocks most gener- t o automatic fabrication and handling of its produets, not
ally made in this country, while French flint pebbles possible in plants where many items are produced. The
havc been cornnionly used as a grinding mcdium. The Silex plant under discussion has been developed along these lines.
linings are reasonahly satisfactory for the grindiiig of rough
materials, but where higher priced products are being ground Preliminary Treatment of Materials
or where products are chdnged frequently and it becomes The principal materials consist of English and American
necessary to clean the mills, porcelain linings arc more de- ball clays, china clays, pulverized silica, and pulverized feld-
1 Received March 20, 1981. spar. The materials are unloaded from railroad cars directly