Ammonium Nitrate

by the
Stengel Process
J. J. DORSEY, JR.l
Contnrerdol S d m b C-, SMIngtOn, Lo

I N THE summer of 1951, Commercial Solvents Corp. decided

to embark on a $ZO,Mhl,Mhl expansion of its Sterlington, La.,
plant. This expansion was to include increased production of
an important factor in the design of a solid ammonium nitrate
plant, since many of them are located in the Sonth where humid
weather conditions may seriously deet the output from the
ammonia and methanol and new facilities for producing solid dryers of a conventional plant. A brief comparison of the major
ammonium nitrate. Since a preliminary cost survey indicated components of the several processes is given in Table I.
that the Commercial Solvents ammonium nitrate process (8)
should result in the lowest investment and production cost, it was
necessary to obtain detailed design data from 8 pilot plant for
a large plant. Tentatively, June 1952 was the deadline for ob- Table I. Comparison of Ammonium Nitrate Processes
taining enough information on the process to allow a detailed en- commercis1
s01venta corp.
gineering comparison of the Commercial Solvents process with 0Lleration (stengel) Prilling OslolKryatal(6)
competitive processes and for at least a preliminary evaluation Preheatkg YeS NO NO
of the pilot plant product. Neutralization YeS YW Yea
The building, reaction equipment, and wster-cwled conveyor
installation were completed hy January 1952 By March 1952,
b$$E;
EvapO?StiOn

,sation
NO
NO
NO
Yes
Yes
NO
YB.
NO
YW
NO
NO
YeS
Flaking and aooling Ye. NO NO
it was apparent that additiond handling equipment would be Grinding Yea NO NO
necessary. Accordingly, two small dryers, product screens, Dniw NO YW Yea
Cwling NO Yea NO
and several conveyors were procured. A coating drum waa c1aasifioatlon Ye* YeS Ye*
Costing and bagging Yea Yea Ye8
fabricated, and a sewing machine for sewing filled bags was ob-
tained. Throughout April, May, and June of 1952, the complete
pilot plant wm operatad on a threeahift basis a t a production
rate of about 300 pounds per hour. The pilot plant waa operated In conventional prilling ammonium nitrate processes (7), the
in order to obtain additional information and to train production control of the particle size from the prilling tower is a function
personnel through May 1953. The required design information of the properties of the solution of ammonium nitrate such m
was obtained during 1952, to allow the construction of the plant concentration and temperature, the type of spraying equipment,
to proceed during 1953. The production plant waa completed and the characteristics of the tower. The final product moisture
in August, 1953, and has been operating since that time (3). level depends on the operation of two or three rotary vessels
functioning &B dryers and/or a cooler. The atmospheric condi-
In Stengel Process, Control of Producl tions, temperature, and humidity affect the capacity of the prill-
Moisture Is Independent of Climate ing tower and the dryers.
In the Commeroial Solvents process the control of the product
In this process, preheated ammonia and nitric acid react in a moisture o m be by the conditions maintained in the reaction sys-
packet reactor, as described for the patented Stengel reaction tem. This is a function of the preheating of the reactants and
system (8). The reactants are preheated ta a sufliciently higb
the operation of the stripper, which uses air to reduce further the
temperature that the molten ammonium nitrate leaving the reac- product moisture to the d&d level. This operation readily
tion system will be at the desired moisture level. This may be lends i h l f to automatic control. Since the moisture content of
as low as 0.1%. From the reactor, the mixture of steam and the ammonium nitrate is established in the reaction system, the
ammonium nitrate passes to a cyclone-type separator where a outside weather conditions have no effect on the product moisture.
separation of the molten ammonium nitrate and steam results.
The steam is taken to a total condenser and sewered. The molten
Pilot Plant Components A m
ammonium nitrate p " to ~ the stainless steel, water-bed con- Equipped for Automatic Control
veyor where it solid3ies aa a continuous sheet. This sheet of am-
monium nitrate is broken into about 5-mesh particles. This The pilot plant waa located about one-half mile from the am-
product is dried, cooled, and classilied into a -5 to +20 mesh monia plant, the nearest major production unit. Steam, water,
mixture before paesing on to coatmg and bagging equipment. power, and air were brought to the area from the plant supplies.
Provisions are incorporated for recovering fines from the screen Ammonia and nitric acid were brought to the pilot plant by
and other possible loasea in the process. portable trailers which were filled a t available facilities in the
The Commercial Solvents solid ammonium nitrate process production plant.
offem a simple method of producing a dry product without a The pilot plant building waa of prefabricated steel construction
prilling tower, crystalher, or dryers and coolers, thus d o r d i n g a placed on a concrete slab. No special Boor was supplied and
process that is essentially independent of the weather. This is attack on the concrete was negligible except where hot nitrate
frequently drained. The building was 20 feet wide by 48 feet
L h n t addrar. O h Mathiason Chemical Corp., New Haven. Conn. long, and the reaction equipment was housed in a special barricade.

I a n m 1955 INDUSTRIAL AND ENGINEERING CHEMISTRY u

ENGINEERING, DESIGN, AND PROCESS DEVELOPMENT

n
REACTOR SECTION Non
-Condensables
I
I
I I I -
G o ndenser
Vapor
R e a c t or Scrubber
Ammoniq
Heater NI-lqN03- 18.2 Ib./hr.
H20-274.51b./hr.

-0
i am

7-

Ammonia
- From T r a i l e r
' '-
NH NO
-
7
616.2 Ib./hr.
H20-2755 ib/hr. Separator
S c r u b b e r Pum

Nitric A c i d
-
P r e-
heater

FINISHING SECTION

90lb./hr. O v e r s i z e R e c y c l e
C o a t i n g Agent S c r e w F e e d e r

H 2 0 % 0.1- 0.4
A c i d i t y , 0.04 0.06-
S c r e e n Analysis %

-5, i - 2 0 72.0
N q N 0 3 - 6.18 tons/doy
- 20 , 14.2
-
T e m p e r a t u r e -OF.

-0 Pressure - inches H2 0

a pressure Pounds per. sq.ini

Figure 1. Process Flow Sheet for Pilot Plant Production of Ammonium N i t r a t e

12 I N D U S T R I A L A N D E N G I N E E R I N G CHEMISTRY Vol. 47, No. 1


Ammonia Storage, Metering, and Preheating. The ammonia
from a 1000-gallon trailer passed successively through a vapor-
izer, pressure controller, temperature controller, direct indicating
Flowrator, superheating equipment, and into the reactor (Figure
1).
The ammonia vaporizing and superheating equipment were of
standard carbon steel construction and were designed to use
available plant steam pressure of up t o 250 pounds per square inch
gage. While some tests were conducted utilizing ammonia
superheated to over 450' F. with electric heaters, this proved t o
be unnecessary, and for most of the operation preheating to
300" F. was adequate.
Nitric Acid Storage, Metering, and Preheating. The nitric
acid from a 2000-gallon stainless steel trailer passed either directly
t o the Ingersoll Rand Type s/4 MCS centrifugal pump or first
through a scale tank. From the pump the nitric acid flowed
through a direct indicating Flowrator and two acid heaters in
series t o the reactor.
Several types of nitric acid heaters were employed during the
pilot plant operation. Generally, two heaters were employed in
series, The first heater contained a number of coils of stainless
steel tubing within a carbon steel jacket. This heater was
operated a t less than 50 pounds per square inch gage steam pres-
sure and preheated the nitric acid to 250" F., if necessary. Prac-
tically no corrosion of the tubing inside the heater resulted, but
corrosion of the welds joining the two heaters was a continuing
problem, although not serious enough to prevent operation of the
pilot plant.
The second heater initially employed to preheat the nitric acid
above 260" F. was a Durco Series D4HF which is a standard
Duriron heater. I t s principal disadvantages were its small size
and low operating steam pressure limit of 75 pounds per square
inch gage. This heatcr was replaced with a straight, jacketed
section of 1-inch, Schedule 40, Type 304 stainless steel pipe.
This type of heater lasted over 1800 hours. In this equipment
corrosion also occurred primarily a t the zone adjacent to the weld-
of the top and bottom flanges. With this heater, acid preheat
temperatures as high as 320' F. were used for short periods.
Except for brief periods during the experimental program, it was
not necessary to have an acid preheat temperature much over
290" F. It is entirely probable that some vaporization of nitric
acid occurred at times.
Control of the nitric acid preheat temperature was by manual
adjustment of a steam pressure regulator for each acid heater to
give the desired reactor gradient or temperature.
Reactor, Separator, Stripper, and Scrubber. Two different
types of operation of the pilot plant were explored-the operation
leading t o the production of a n ammonium nitrate solution of 2
t o 3% water content which required a dryer and cooler for subse-
quent processing and, next, the operation to produce directly a
product of 0.2 to 0.4% water, thus eliminating the need for a dryer
or cooler. The major differences between these two types of
operation were the nitric acid preheat level and the use of a strip-
ping gas to dehydrate further the ammonium nitrate.
The reactor was fabricated from a 16-gage stainless steel tube,
2.5 inches in outside diameter by 8 feet long. Provisions were
made for entrance of the ammonia a t the side and nitric acid
directly at the top. The reactor was packed with various sized
packing to a packed height of up to 7 feet. A thermocouple well
extended through the center of the packing from the bottom.
Reactor temperatures were measured in this center thermowell.
The separator, of conventional cyclone-type design, was fab-
ricated at CSC's Sterlington shops. The separator was 8 inches
in outside diameter by 24 inches high. The steam-ammonium
nitrate mixture entered tangentially and the ammonium nitrate
flowed by gravity to the stripper below. The steam and non-
condensables left from the center discharge pipe and passed out
to the scrubber.
The stripper was fabricated from a piece of 3-inch, Schedule 40
January 1955 INDUSTRIAL AND ENGINEERING CHEMISTRY
PILOT PLANT
stainless steel pipe about 5 feet long. This stripper was packed
with various types of packing t o various levels. The piping a t
the bottom of the stripper allowed for entry of the heated strip-
ping air, and the discharge of the molten ammonium nitrate to
the Eastern Model D-11 centrifugal pump which pumped the
molten ammonium nitrate to the water-cooled conveyor where it
solidified.
The vapor scrubber was fabricated from a section of 8-inch
stainless steel pipe. The scrubber was designed to recover the
ammonium nitrate and ammonia which escaped from the separa-
tor and t o cool the steam leaving the scrubber. Normally a
packed height of 25 inches was employed. The scrubber a5-
sembly consisted of a circulating pump, a hot well controlled to a
constant level by condensate addition, and a flowmeter in the
pump discharge system. A side stream was taken off t o the acid
charge tank for recovery.
Also in the pilot plant reaction assembly was a surface con-
denser used t o condense all the steam from the vapor scrubber.
This condensate was weighed and analyzed to provide a measure
of the efficiency of the process.
Water-cooled Conveyor. From the bottom of the stripper,
the molten ammonium nitrate was pumped to the water-cooled
conveyor where solidification and cooling ocurred. The water-
cooled, stainless steel conveyor was a standard 20-inch-wide belt
with a cooling section 18 feet long. This conveyor belt was modi-
fied t o allow belt speed variations from 0 to 85 feet per minute.
For maximum water economy and heat transfer, water was cir-
culated through the two sections by a recycle pump until tht
water temperature reached a specified maximum. The cooled
sheet of ammonium nitrate was removed from the belt by a
scraper and fed t o the product breaker and grinder which were
located at the discharge end of the water-cooled conveyor.
Drying, Cooling, and Product Coating. It was initially thought
t h a t it might be necessary to have a t least one dryer and a cooler,
as in most conventional ammonium nitrate plants. I n this phase
of the pilot plant study, a General American Transportation
flight-type dryer, 12 inches in diameter by 9 feet long, and a
Link-Belt Model 207, Roto-louvre dryer were both evaluated.
The installation was so designed that the product passed first
through the flight-type dryer, and then into the Roto-louvre
dryer, or into either dryer separately. The Roto-louvre dryer
could be operated as a cooler, but generally sufficient cooling de-
veloped through the screens, and coating drum.
The product coating was accomplished by adding coating agent
and the classified ammonium nitrate to a rotating drum where
the tumbling coated the product. The coating agent was fed t o
the coating drum by a vibrating feeder or a screw feeder. The
feeder was adjusted to discharge continuously a t a fixed rate to
correspond to the known production rate. The product was
bagged in conventional six-ply, moisture resistant bags for stor-
age and field trials. All bags were sewn and overtaped.
Grinding to Size and Product Classification. The grinding of
ammonium nitrate to a product passed through 5 mesh and re-
tained on 20 mesh screen with a minimum of fines was extensively
studied. Many factors influence the characteristics of the am-
monium nitrate with regard to the production of fines. Among
these are temperature, sheet thickness, aging time, and moisture
content.
As part of this study of grinding ammonium nitrate the follow-
ing types of grinders were considered:
Corrugated roll, roller mill
Several types of hammer mills
Several types of granulators
Several types of so-called choppers
Generally, the best results were obtained with a hammer mill
or granulator, both of which are used in the production plant.
A vibrating screen was employed for classifying the product.
The screen was 2 feet wide by 3 feet long. This screen was modi-
13
ENGINEERING, DESIGN, AND PROCESS DEVELOPMENT
fied during later operation to incorporate an oversize w e e n , and
the oversize mas recycled to the primary grinder. The screens
were continuously blanketed with dry air to minimize blinding of
the 20-mesh product screen. The fines from the screening opera-
tion were returned with the acid to the reaction system RS shown
in Figure 1.
Development Program Includes Investigation
of Process Variables, Alternative Equipment
The program for pilot plant work was planned to obtain design
information for those components of the plant for which the
longest delivery time was indicated. Since it appeared that the
major item in t,his regard was the number, type, and size of
dryers and cooler, t,liisphase of the work was esplored first. Xext
in importance n - ~ the
s stainless steel, water-bed conveyors since
the length and number of t,hese, and the rotary diyer and cooler,
would dictate t o 3 large degree the size of the process building.
Concurrent with these studies, n.ork was
reaction system, grinding, coating, classification, bagging, and
recovering of fines from the grinding system.
Test8s on the small quantit>ieso i product available from the
laboratory studie? hnvc indicated that the product should store
and handle satisfactorily. Early in April and May of 1952 the
first product from t,he pilot piant was set aside under controlled
conditions for stomge stabilit
Aftel all of the above phase e well along, the possi-
bility of eliniinat ing rotary clryirig equipment came under inten-
sive study, and it was deterniined that the dryer and cooler
could be omitted in the commercial installation. During hIay
and June of 1953 the pilot plant as operated to train production
supervisors and operat,ors.
Operation of the reactor system t o produce molten a,mnionium
nitrate of about 0.3% moist'ure content resulted in a higher
ammonium nitrate temperature to the water-cooled conveyor.
The addition of ammonium nitrate fines to the moiten ammonium
nitrate was found desirable, since otherwise the higher t,empera-
tures put additional coo!ing loa,d on the stainless steel, water-
cooled conveyor. If necessary, the belt could be operated to
compensate for t,lie higher temperature, although the uniformity
of t.he sheet leaving the conveyor was not as good. Also, Kith
low moisture it was desirable to cool the product leaving the
water-cooled convpgor to a. lo-xer tempemtiire sirice the product,
passed very quickly LO t'he screens, the co:tting d r ~ i mand
, the bag.
When the tIyo dryere were eliminated from the pilot plant
building, t.he scrmis vere modified t,o allow the installation of an
oversize screen and t,lie recycle of the oversize material to the pri-
mary grinder. The pilot plant was operaied during most of the
first 6 months of 1953 without a dryer or cooler. During this
period it was possible t o obtain product moisture contents oon-
sistently less than 0.3%.
Any amount of fines greater than the quantity that could be
returned to the fines-dissolving system could be proportioned to
the nitric acid by means of anot>herscrew conveyor and passed
again through the reaction system. At the same time, the vapor
scrubber operation concentrated any fog loss from the system
to between 50 and 90% animonium nitrate; this concentrated
materia! was continually returned to the nitric acid for recycle
through the reaction system.
A stainless steeI suyface condenser condensed the water Irav-
ing the vapor scrubber. The weight and analysis of this water
gave an accurate picture of the losses and these data were neces-
sary for material balance calculatisns.
The molten amnionium nitrate was sampled as soon as it
reached the Sandvik belts. Changes based on the acidity and
moisture content of t,hese samples could be made t o bring this
phase of the operation t o the desired conditions.
A calibration was availahle for each reactant flowmeter as a
general means of controlling the ratio of ammonia t o nitric acid.
14 INDUSTRIAL AND ENGINEERING CHEMISTRY
In addition, the condensate from the total condenser located
after the vapor scrubber was passed through a pH cell, thus al-
lowing the continuous measurement of the p H of the condensate
after the recovery system In operation the fine control of a
slight excess of ammonia could best be done by referring to the
pIS recorder.
Start-up of Reaction Section. Normally, the finishing section
was started first since there was no point in Lhe process stream
where the product collected until i t reached the bag. The coat-
ing drum, screene, conveyors, grinder, and water-cooled conveyor
were started in that order. The reactant preheaters were ad-
justed to the desired steam pressure. The reactor, separator,
stripper, and connecting lines were steamed a t atmospheric
pressure.
The ammonia flow n-as started first and then the acid flow
was begun at a low rate until a rise in temperature in the reactor
as observed. M t c r this, the acid flow could be brought, rapidly
to the desired level. I s soon as the ternperat,ures of the molten
ammonium nitrate leached certain values, it mas possible t o
switch the flow froni the vapor scrubber sump t o the water-
cooled conveyor. 'rhe temperature at which this switch was
made depended on whet~lieror not a dryer was used.
After start,-up, a level T T ~ Sdeveloped in the scrubber sump and
the recovered ammonium nitrate soluthri was cireulat>edthrough
the scrubber. When t,he concentration of the solution in the
vapor scrubber reached a definite value, the solution was con-
tinuously removed to the acid charge tank for return through the
reactor. The level was maintained constant in the vapor scrub-
ber sump to control the concentration. To reduce entrainment
losses from the vapor scrubber, a,n entrainm.ent separator was in-
stalled. This proved highly beneficial since at times the scrubber
tended to carry over and this aininonium nitrate solution was re-
moved from the gas strrain and retnrned to the vapor xruhher
sump.
%'hen stripping air vtis ured, the stripper rvas started as soon
as the molten ammonium nitrate temperature reached about
400" F. The stripping air also passed through the separator
and vapor scrubber.
Water-Cooled Conveyor Operation. Depcnding on the pro-
duction rate and manner of operation, the make-up cold \-rater
was sent to the circulating -xater system of t'he water-bed con-
veyor, or added only io the first section. It is important to
solidify the molten ammonium nitrate as rapidly as possible to
keep the sheet of ammonium nit,rate as uniform as possible.
When the complete pilot plant was operated over extended
periods without shutdon-ns, the fines from below the vibrating
screens were continuously returned to a fines dissolving pot d i i c h
cont,ained an agitator. A thermocouple was located in the exit
line overflowing from the dissolving pot to the water-lxd con-
veyor. The amount of fines returned to the dissolving pot was
regulated to control the temperature of the molten ammonium
nitrate to t,he vater-bed conveyor to perhaps 30" F. above the
solidifying point of the ammonium nitrate. Returning the fines
to the production system in this manner resulted in cooling of the
ammonium nitrate and disposing of the fines. This reduc'ed the
water requirements to the mater-bed conveyor.
The control of the cooling through the water-bed convog'or was
based on the temperature of the solidified ammonium nitrate
pabesing over a Weston thermometer. TVhiIe this temperature
was not necessarily the true ieniperature of the ammonium ni-
trate, it did give a sufficiently reliable tempcrature for coiltrolling
belt operation.
Grinding, Drying, Cooling, Coating, and Bagging. From the
water-bed conveyor t h e product passed to the grinder which was
located directlyat theend of the belt. For most of the pilot platlt
work a n Art.hur Coltoii single rotor granulator was used. Vari-
ous screen sizes were tried as various sized products were made in
order to determine the ei7e most suitable. When the pilot plant
was operated with the two dryers, the material was conveged t o
Vol. 47, No. 1
 PILOT PLANT

January 1955 INDUSTRIAL A N D ENGINEERING CHEMISTRY 15

ENGINEERING, DESIGN, AND PROCESS DEVELOPMENT
the top of the flight-type dryer. After passing through this flight-
type dryer, the product discharged into a Koto-louvre dryer
direct'ly below. From the Roto-louvre dryer the product dis-
charged onto another conveyor which carried the product to the
screen. The screen cooled and also classified the product to a
plus 20 mesh size. From the screen the product, passed into the
coating drum where the proper amount of coating agent was ap-
plied. The product discharged directly from the coat,ing drum
into the bag, which was brought to the sewing machine and
sewed.
The operation of the flight-type dryer was tried with both
counter-current and concurrent flow of air and product. The
counter-current flow of air and product resulted in the best dry-
ing, although some difficulty was experienced with a carry-over
of the fines from the product into the air discharge duct from the
dryer.
In general, the drying conditions for the predryer were con-
trolled to keep the ammonium nitrate at about the same tem-
perature as it entered. Since it, was simple to control the amount
of cooling on the water-bed conveyor, it was possible for t h e prod-
uct to reach the predryer at a t,emperature anywhere between
130" and 190" F. The temperature of the inlet air and the quan-
tity of air were varied to give t,he desired product moisture con-
tent and product temperature at the discharge. Drying condi-
t,ions and, of course, capacities vere different when the t,wo
dryers Lvere used in series and when either dryer was used alone.
In general, if the temperature of the ammonium nitrat,e was in-
creased as it' went through the drycr, very little moisture reduc-
tion resulted. Most of the loss of moisture resulted if the tem-
perature of the ammonium nitrate was decreased in passing
through the dryer.
The Roto-louvre dryer employed \vas one of the smaller size
production dryers. Again it was possible to control the exit prod-
uct temperature and to sdme est,ent t'he moisture content, by
varying the air rate, air inlet temperatiire, speed of rotation of the
dryer, bed level, and retention time.
I t was found early in the course of the investigat,ion that under
humid conditions there was a t,enclency for thc vibrating screens
to blind. To minimize this blinding it was necessary to intro-
duce a small amount of conditioned air below the screens. This
air passed up through the screens and out through the top where
the product entered. Very little difficulty was experienced with
screen operation while conditioned air \vas employed, and the air
helped to cool the product.
It was difficult to obtain a uniformly coated product in the
pilot plant. A screw-type feeder arid a vibrating feeder were
tried for feeding coating agent to the coating drum at a steady
rate. Both of these types of feeders tended to stop feeding or to
feed erratically, primarily because t,he coating agent Tyould not,
flow steadily dawn to the feeder mechanisms. Since the amount
of coating agent used was only a few pounds per hour, it was pos-
sible to install the feeder on platform scales; thus the amount of
coating agent fed could be watched and recorded on an hourly
basis. 11-hilethis served to indicate the amount of coat,ing agent
used, it did not necessarily ensure that, the discharge of coating
agent was continuous. For selected storage stability tests, ma-
terial was prepared by charging 97 pounds of ammonium nitrate
a,nd 3 pounds of coating agent to a drum and rolling the drum
across the floor until thorough mixing resulted. In this manner
it was possible t o obtain data regarding the effect,ivenese of
vm.ious types of coating agents and various concentration levels
of coating agent.
Abnormal Reactor Operating Conditions
Are Intenlionally Included in Study
The decomposition of ammonium nitrate has been studied
extensively by many investigators. These investigations have
been sunimarized in many excellent bulletins issued by govern-
16 INDUSTRIAL AND ENGINEERING CHEMISTRY
ment agencies ( 1 , 2, 4, 6). l l a n y equations can be written for
XH&Os -
decomposition of ammonium nitrate-for example,
- KHS + HSOj
NzO + 2x20
(1)
-
SHaS03 (2)
PIIHIXOB N?$. ' / z 02 + 2H20 (3)
In the Stengel reactor equilibrium in Equation 1 is approached
from the right. At t,he normal operating temperatures of the
Commercial Solvents pilot plant, equilibrium is such that the
exit gases from the reactor contain comparatively small a,niounts
of ammonia and acid vapor, and these combine as the gases are
cooled and are largely recovered in the vapor scrubber. Under
normal operating conditions there should be even less decom-
position according to the reaction of Equation 2. Since the re-
action of Equation 3 proceeds at still higher temperatures, there
can be litt'le ammonium nitrate decomposition by t'his mechanism.
Based on operation of the pilot plant and commercial plant to
date, normal operat,ing temperatures after the separation of the
ammonium nitrate and st,eamwill be less than 400" F., and it is be-
lieved unnecessary t,oexceed a temperature of 430" F. Considering
that about a minute elapses between the time t,he ammonium
nit,rate leaves the separator until it reaches the individual water
cooled belts where cooling is very rapid, it is apparent that, there
can be little decomposition of the molten ammonium nitrate
beyond the reactor.
Khile temperatures higher than 460" F. may occur at times in
the reactor itself, the rcsidence time is normally only a small
fraction of a second and thus too short for significant deconi-
position. Under normal conditions of operation, Bemperaturea
in the reactor above 460' F. r$.ould not occur. During the
laboratory and pilot plant stages of this investigation, abnormal
reactor operating conditions were intentionally included on occa-
sion; for example, temperatures well above 600" F., extreme ratios
of reactants, and reactants contaminated v,-ith oil and other mate-
rials known to sensitize ammonium nitrate were studied. How-
ever, during all of the laboratory and pilot plant operat,ions no
uncontrollable conditions developed.
Yields €ram this process depend primarily on the mechanical
operation beyond the reaction system and on the efficiency of
the vapor scrubber recovery system. Yields across the reaction
system of 98% and better have been realized. Essentially the
only nonrecoverable material is that which decomposes.
A thermodynamic analysis of this process will be presented in
a subsequent papcr.
Pilot Plant Production Is Sufficient
to Allow Product Evaluation
During the pilot plant development of the process it was also
necessary to obtain information about desirable product char-
acteristics. It was known that a low product moisture was
desirable. It was expect,ed t,hat ahout, 3yo coating agent would
required. The major difference bet,ween the new product and
available fertilizer-grade ammonium nitrate was the shape and
size of the particles. Prills and crystal ammonium nitrate are
smooth of surface and rounded in shape.
The Commercial Solvents process product is irregular in shape
tending toward cubic, and can be sized as desired. Products of
several sizes were prepared for storage, field spreading, and mixing
tests in comparisons with existing products. The larger sized Coni-
mercial Solvents process particles showed the least tendency to
clog conventional-type spreaders, but smaller particles wcre
more readily distributed in mixed fertilizers. A - 5 to +20
mesh product T ~ selectedS as the most satisfact,ory product for
all users.
In April and hlay of 1952 some of the first pilot plant produc-
tion was put aside for storage stabi1it)y evaluation. Some of
this mRt,erial is still in storage and is still satisfactory. Some of
Vol. 47, No. 1
 ENGINEERING, DESIGN, AND PROCESS DEVELOPMENT
this early pilot plant production and later production was also
tested by Mississippi State College, and Louisiana State Univer-
sity. Satisfactory storage stability has been demonstrated with
products made with all of the process variables discussed.
Summary
Extensive pilot plant work preceeded the commercial develop-
ment of a new process (the Stengel process) for manufacturing
ammonium nitrate. This process is now in commercial operation
at Commercial Solvents Corp., Sterlington, La. The process
offers significant investment savings and lower operating costs
through reduced personnel and utilities requirements. Since
the control of the product moisture is in the reaction equipment,
the process is essentially independent of climatic conditions.
Acknowledgment
The author wishes to express sincere appreciation to Commer-
cia1 Solvents for permission to present this information. Credit
is due t o all Commercial Solvents personnel who were associated
Thermal Calculations for
Sugar Process Engineers
HOWARD E. HIGBIE'
Deparfmenf of Chemirfry, University o f Piffsburgh, Piffsburgh, Pa.
T HERMAL properties of gas mixtures have been frequently
tabulated as the enthalpies of the individual components (9).
Then the total enthalpy or heat content of the mixture is com-
puted by summing, for all components, the product of the
enthalpy of the pure component times the fraction of the com-
ponent present. This procedure is justified x h e n the heat of
mixing is negligible; otherwise, the heat contents of the mixtures
are not additive.
The volume, enthalpy, and free energy changes on forming
liquid solutions from their components are not negligible in
general, hence workers in the field of theory of solutions have
expressed the solution properties in terms of partial quantities
(6)-for example, partial molal volume, relative partial molal
heat content, and chemical potential. These quantities are de-
fined to be additive so that the specific volume of a solution, for
example, is the sum of the products of the mole fractions times the
partial molal volumes of the components. The partial quantities
are intensive properties of the solution and depend on the
composition of the solution as well as on the other variables which
determine the value of the total property.
The partial enthalpies of water and sucrose in solution provide
a convenient basis for engineering calculations of the thermal
effects attending changes in these solutions. These changes,
which occur in the sugar refining and processing industries, may
involve the gain or loss of either component from the solution.
A tabulation of the partial enthalpies of water and sucrose is
presented in Tables I and 11, for the concentration range from 0
t o 65 weight % sucrose and the temperature range from 32" to
200" F. An enthalpy table for crystalline sucrose has been pre-
pared to cover the same temperature range (Table IV) and an
enthalpy table for water vapor over this temperature range
(Table 111) has been included for convenience in making computa-
1 Present address, 7813 Maple Ridge Rd , Bethesda 14, Md.
January 1955 INDUSTRIAL AND ENGINEERING CHEMISTRY
with this project, in particular t o W. 0. Bell, Jr., J. D. Kramer,
A. P. Miller, L. A. Stengel, and R. S. Egly.
Literature Cited
Burns, J. J., and associates, U. S. Bur. Mines, Rept. Invest.
4944.
Elliot, Martin A , Ibid., 4244.
Hester, A. S., Dorsey, J. J., and Kaufman, J. T., IND.ENG.
CHEM.,46,622(1954).
Grant, It. L., and Scott, G. S., U. S.Bur. Mines, Infor. Ciro.
7463,June 1948.
AIiller, Phillip, and Saeman, W. C., Chcm. Eng. Progr., 43, 667
(1947).
Rous, W.H., and associatee, U. S.Dept. Agr., Tech. Bull. 912,
J u n e 1946.
Shearon, W.H.,Jr., and Dmwoody, W. B., IND. ENG.CHEM.,
45,496 (1953).
Stengel, L. A. (to Commercial Solvents Corp.), U. S. Patent
2,568,901 (September 25, 1951).
RscBIvEn for review July 30, 1954. ACCEPTED October 29, 1964.
presented at the Regional Meeting of the American Institute of Chemical
Engineers, Washington, D. C., March 1954.
tions. In the following sections a method of preparing these
tables is outlined and methods of using the tables for the calcula-
tion of the heat effects attending several types of changes are
described.
The justification for presenting the thermal properties of
sucrose solutions as two tables of partial enthalpies rather than aa
a single table of the total enthalpy or of the apparent enthalpy can
be seen in the relationships between the heat effects and solution
changes. The thermal equations can be stated by inspection and
the calculations are straightforward. The solution partial
enthalpies can be used in conjunction with existing enthalpy
tabulations-e.g., the steam tables.
A recent communication from Lyle points out that he derived
an empirical equation for the enthalpy of sucrose solutions in
terms of concentration and temperature (6). Although it wm
written without the benefit of more recent heat of dilution and
solution data, the equation agrees well with the present tabula-
tion. The Lyle equation does not express the partial enthalpies
explicitly so that the calculation of the heat effects accompanying
solution, precipitation, and vaporization processes is less con-
venient than with t h e present tabluation.
Development Is Based on Relationships between
Partial Quantities and Measurable Quantities
The partial enthalpies of Tables I and I1 as well as the partial
specific heats used in their evaluation are defined similarly to the
well-known partial molal properties of solutions (6, page 33)
except that they have been put on a unit weight rather than a
unit mole basis. Thus, the partial enthalpies of water and
sucrose in solution are defined by
17