Single Pressure or Dual

Pressure Nitric Acid:

An Objective Comparison

The two methods are compared on the basis of chemistry, thermo-

dynamics, kinetics, and economics.

R.L Harvin
C and I Girdler, Inc.
Louisville, Kentucky

and

D.G. Leray, L.R. Roudier

Compagnie Française de l'Azote
Paris, France

For the past half century, the technologies of nitric acid
production in Europe and the USA have developed along two
different process schemes. Both involve ammonia oxidation
and absorption in water, but in Europe these are often carried
out at two different pressure levels, whereas in the USA one
pressure level is customarily used. Claims of efficiency and
economy are made for both processes, but it is interesting
that the barrier separating the areas in which each has reigned
supreme has seldom been breached.
The emphasis in Europe on energy .and ammonia effi-
ciency led to the development of absorption technology
which reduced the loss of valuable NOX to the atmosphere. In
the. USA, the processes were optimized with lower energy
costs and therefore lower ammonia conversion and higher
NOX losses were tolerated. In recent years, the US industry
*Due to space limitations, the complete text prepared tor
the 71st Annual Meeting of the AICHE in Miami cannot be
printed here. The deleted sections concern operational and
design features involved with process selection. Subjects
include catalyst composition, nitrous gas compression,
expanders and absorption of nitrous gas. The COFAZ math-
ematical model for nitric acid absorbers is discussed, and a
semi-empirical absorber design formula presented. Readers
interested in the full text should contact the AIChE.
has sought the more advanced absorption technology, de-
veloped in Europe, in order to cope with new pollution stan-
dards. Faced with increasing energy costs, US industry now
has an interest in re-evaluating the entire technology of the
dual pressure process as an alternate to the single pressure
process with improved absorption.
An objective comparison of these two nitric acid processes
logically begins by reviewing the similarity of the chemistry
involved, and the basic thermodynamic and kinetic prin-
ciples. Then, the process differences can be discussed in
relation to how these fundamentals are most advantageously
exploited.
The chemistry of the process for the production of weak
nitric acid (50-68% wt) appears deceivingly simple. It starts
with a single pure compound, plus air and water, and ends
with another pure compound in aqueous solution, with es-
sentially no byproducts. Chemical reactions and standard
heats of reaction appear in Table I. The single overall
reaction representing the process (Equation I) is basically
composed of three separate and distinct chemical steps: the
oxidation of ammonia to nitric oxide, the further oxidation to
nitrogen dioxide (tetroxide), and the reaction with water to
produce acid. Each step is carried out under different con-
ditions and in separate pieces of equipment.
The first step of the process is a heterogeneous, highly
exothermic, gas-phase, catalytic reaction of ammonia with

173
 Table 1. Chemical reactions and standard heats of reaction.

Source: Data from NBS Technical Note 270-3, Selected Values of Chemical Thermodynamic Properties, (January, 1962).

Heat of Reaction, 25°C

No. Reaction Joules/mol

1. . -436,918
2. . -226,523
3. . -316,832
4. . -275,780
5. . 4M/3 (g) + 6 NO (g) = 5 N2 (g) + 6H2O (g) -451,296
6. . - 90,309
7. . - 57,108
8. . - 28,617
9. . - 15,747
10. . - 58,672
11. . -144,334
12. . - 87,226
13. . - 58,609

oxygen (Equation 2). The primary oxidation of ammonia to gauze with the resultant reaction of ammonia with nitric
nitric oxide over a catalyst gauze of platinum-rhodium alloy oxide to yield nitrogen (Equation 5).
proceeds very rapidly through a fairly wide range of condi- The amount and condition of the catalyst are important
tions. Even though other reactions (Equations 3,4,5, and 6) influences of the efficiency of conversion. When the catalyst
yielding products such as N2 or N2O could be expected to is poisioned, or if the gas bypasses the catalyst, the oxidation
occur either simultaneously or consecutively, the efficiency to nitrogen becomes significant (Equation 3). As the catalyst
of conversion to nitric oxide is generally above 90%. ages and loses weight, the passage of unreacted ammonia
through the gauze can occur. This ammonis is subsequently
Gauze temperature a primary factor converted to nitrogen by reaction with nitric oxide (Equation
The primary factor affecting the conversion efficiency is 5). An excessive quantity of catalyst charged is useless, as it
gauze temperature. Generally, increased temperature will in- increases the likelyhood of converting nitric oxide to its
crease the efficiency to an optimum. The positive effect of elements. (Equation 6).
temperature is shown by the fact that the reaction producing The second step of the process (Equations 7 and 8) in-
nitric oxide is less exothermic than the other competing volves two reactions that occur sequentially. The reaction of
reactions. On the other hand, the destruction of nitric oxide to nitric oxide with additional oxygen to produce nitrogen
its elements (Equation 6) becomes significant around dioxide is followed by the dimerization reaction to produce
1,830°F(1,000°C). nitrogen tetroxide. The equilibrium mixture is called nitro-
To a lesser extent, pressure has a negative effect, on effi- gen peroxide. Both reactions are homogeneous, moderately
ciency but by proper selection of the gauze temperature, exothermic, gas-phase, non-catalytic reactions.
much of the effect of pressure can be offset. In practice, oper-
ating conditions can usually be selected which result in con-
version efficiencies between 94 and 98%. The information Table 2. Interrelationship of operating pressure, gauze
in Table 2, though subject to variation, shows a generally ac- temperature and conversion efficiency.
cepted interrelationship of operating pressure, gauze tem-
perature and conversion efficiency. Operating Gauze Conversion
The most prevalent side reactions competing for the Pressure Temperature Efficiency
nitrogen are the oxidation of ammonia to nitrogen and nitrous
oxide (Equations 3 and 4). These reactions proceed simul- 1 atm 790°C—850°C 97-98%
taneously with the reaction to nitric oxide and are functions 3.5 atm 870°C 96-97%
of the selectivity of the catalyst at the operating conditions. 8 atm 920°C 95-96%
Ammonia coming in contact with a hot metal surface prior to 10.5 atm 940°C 94-95%
reaching the catalyst may crack to yeild additional nitrogen.
Incomplete ammonia-air mixing and improper gas flow pat- Metric conversion:
terns can result in spot oxygen depletion within the catalyst 1 atm = 101.325 kPa

174
 The oxidation reaction is unique, in that it has a
measurably slow reaction rate, and also, that its rate has a
negative temperature coefficient; i.e., it proceeds more
rapidly at lower temperatures. Of particular importance is the
fact that the reaction rate is a cubic function of pressure.
The dimerization reaction is extremely rapid, so as to be
assumed to always be in equilibrium. The equilibrium com-
position is a direct function of pressure and an inverse
function of temperature. It is so temperature sensitive that
above 300°F (150°C), only nitrogen dioxide is significant;
whereas, at 100°F (38°C), the dimeric form predominates.
The third step:
condensing and advancing oxidation
The third step of the process involves cooling the reaction
gases below the dew point, with the subsequent formation of
a liquid phase of weak nitric acid. The purpose is to advance
the state of oxidation (Equation 7) and the state of dimeriza-
tion (Equation 8), and to remove water from the gas phase,
thus increasing the nitrogen peroxide partial pressure. It is
not the purpose to form weak nitric acid at this point, as this
would lower the nitrogen peroxide partial pressure.
The question arises as to the existence of a gas phase
reaction to form nitric acid, or whether water would be the
initial condensate. The subject has been debated by several
investigators, but the more detailed works by Carberry (I)
and Andrew and Hansen (2) conclude that the formation of
nitric acid is a liquid phase reaction, controlled by the solu-
tion of nitrogen tetroxide.
Nevertheless, the condensate formed will immediately
absorb nitrogen peroxide and become acidic. The conden-
sation follows the usual vapor pressure-temperature relation-
ships. The absorption of nitrogen peroxide and formation of
acid is a direct function of pressure, an inverse function of
temperature, and the amount of contact between the gas and
the liquid phases.
The fourth step in the process involves the formation of
nitric acid by the reaction of dissolved nitrogen peroxide with
water (Equations 9 and 10). The exact mechanism of the
reaction is uncertain. However, the most likely theories
support the absorption of nitrogen tetroxide by the liquid,
followed by its ionization and reaction with water (Equation
9). On this basis, the rate of absorption has been shown to
vary linearly with the partial pressure of the nitrogen
tetroxide. The reaction equilibrium exhibits an indepen-
dence of temperature, whereas correlations based on
nitrogen dioxide as the reactant (Equation 10) show an un-
usual negative temperature dependence. The temperature in-
dependence of the equilibrium (Equation 9) is probably the
result of compensating temperature dependencies of the
reaction rate, gas solubility coefficients, ionization con-
stants, and activity coefficients. However, the negative
effect of increased temperature is apparent by its reversal of
the dimerization equilibrium (Equation 8).
Regardless of which of the overall acid forming mech-
anisms apply, the formation of each mole of acid is accom-
panied by the formation of one-half mole of nitric oxide gas.
This is then reoxidized by the remaining oxygen in the gas
phase (Equation 7), and the acid forming process is repeated.
The conversion of nitrogen peroxide to nitric acid, therefore,
involves a step by step approach to completion, i.e., lower-
ing the residual nitrogen peroxide to its economic minimum.
It is of particular importance that the heat of reaction in
forming acid from nitrogen tetroxide (Equation 9) is 18,454
Btu/lb mole (42,925 J/mol) lower than from nitrogen dioxide
(Equation 10). Thus the greater state of dimerization prior to
acid formation results in a reduced heat effect during the step.
Nitric acid processes
The designers of nitric acid processes have generally ac-
cepted the chemical steps as outlined above and have con-
centrated their efforts on optimizing their designs within the
bounds of available equipment, materials of construction,
and economics. In recent years, several processes have been
developed for the direct production of high strength acid
using slight modifications to the basic chemical steps, but
these are beyond the scope of this paper.
The two important modern nitric acid processes which
have each been highly perfected are the dual pressure
process, developed and used principally in Europe; and the
single pressure process, originally developed by duPont and
used principally in North America. No attempt will be made
to review the historical development of the processes. It is
sufficient to state that, as presently developed, either process
is capable of highly efficient production of the same quality
of product, with the same limits on atmospheric pollution.
The Compagnie Française de L'Azote (COFAZ) dual
pressure process shown in Figure 1 was developed to take
advantage of two factors: (a) low pressure ammonia oxida-
tion, and (b) high pressure absorption or acid formation. In
addition to higher conversion, the lower gauze temperature
associated with the low pressure ammonia oxidation results
in a much lower rate of platinum deterioration. Both advan-
tages can be maximized at the lowest pressure. In contrast,
absorption is most advantageously carried out at the highest
pressure. In the COFAZ dual pressure process, the pressures
have been optimized at 50 psia (0.344 MPa) for ammonia
oxidation and 147 psia (1.014 MPa) for absorption.
The process begins with the vaporization of ammonia at 80
psia (0.55 MPa). 45°F (7°C) followed by superheating to
169°F (76°C), using heat from the compressed bleach air.
Filtered air, compressed in an axial compressor to 50.8 psia
(0.35 MPa) is mixed with the superheated ammonia vapor
(10-11% vol.) prior to entering the hot platinum gauze.
The gases leaving the gauze at 48 psia (0.331 MPa) and
1,590°F (865°C) flow through a series of heat exchangers for
recovery of energy, as either high pressure superheated
steam or shaft horsepower from expansion of hot tail gas.
Approximately 40% of the oxidation to nitrogen dioxide
occurs in the gas as it passes through the energy recovery
train and is cooled to 275°F ( 135°C) exit the tail gas preheat-
er. After further cooling in the medium pressure condenser to
113°F (45°C) and separation of 20% of the acid product as
30% strength nitric acid, the gas reaches a state of oxidation
to nitrogen peroxide of 50% with the dimerization being ap-
proximately 20%.
175
 The gas is combined with bleach air containing additional
nitrogen peroxide and is compressed in a centrifugal nitrous
gas compressor to 148.6 psia ( 1.025 MPa). The exit temper-
ature, of 435°F (224°C) results from the combined heat effects
of the compression, the further oxidation to 80% nitrogen
peroxide, and the virtual disappearance of the dimer. The
compressed gas flows through an empty oxidation chamber,
a high pressure boiler feed water economizer, and a low pres-
sure deionized water economizer, and thus cools to 204°F
(95°C). Residence time in the system, and the effect of
increased pressure result in at least 95% oxidation to nitrogen
peroxide, but the dimerization is only slight due to the tem-
perature level. The gas then is cooled to the approximate dew
point of 122°F (50°C), for entry into the absorber. The dimer-
ization increases to 48%, adding significantly to the heat
removed prior to the absorber.
immersed in the liquid. Deionized water or condensate is
added to the top tray, and weak acid from the low pressure
condenser is added at a tray corresponding to its strength.
Down-flowing acid and up-flowing gas alternately mix and
separate as the chemical steps of action formation and nitric
oxide oxidation take place with the liberation of heat. There
CONVERTER
STEAM SUPERHEATER
TAIL GAS TAIL GAS REHEATER
EXPANDER
Figure 1. Dual pressure nitric acid process.
176
are three operational zones in the absorber: the lower zone
cooled with plant cooling water, the middle zone cooled with
chilled water, and the upper zone which b essentially adi-
abatic. High efficiency of heat removal in the lower and
middle zones is of great importance for its effect on the
oxidation and dimerization reactions. jChilled water at 59°F
(15°C) is used and the outlet tail gas temperature is 64°F
(17.8°C). Refrigeration for the chilled water is provided by
the ammonia vaporizer which operates at 45°F (7.2°C).
Weak acid from the bottom of the absorber is let down to
48 psia (0.331 MPa) for bleaching with air from the axial
compressor. This air, with nitrogen peroxide stripped from
the acid, flows to the suction of the nitrous gas compressor
along with the main nitrous gas stream from the condenser.
Tail gas is reheated to 1,004°F (540°C) in two exchangers
in the low pressure section, and is expanded for recovery of
76% of the required compression power. The expanded tail
gas at 450°F (232°C) is exhausted to the atmosphere.
Single pressure process
The single pressure process shown in Figure 2 was devel-
oped to take full advantage of pressure to reduce the size
FIGURE 1
DUAL PRESSURE
NITRIC ACID PROCESS
of equipment throughout the process. Thus, a single com-
pression step is used to raise the pressure through the entire
process sufficiently to favor absorption. In the C & I/Girdler
Single Pressure Process, the air compressor discharge is at
157.7 psia ( 1.088 MPa) giving an absorber inlet pressure of
about 143 psia (0.986 MPa).
Increased consumption of ammonia due to the higher pres-
sure operation can be minimized by a higher ammonia
oxidation temperature and added emphasis on complete air
and ammonia mixing, and uniform flow distribution across
the gauze. The higher oxidation temperature results in in-
creased consumption of platinum and rhodium and the neces-
sity to rework the gauze every five to seven weeks. The
higher temperature and the favorable effect of pressure on
oxidation combine to make possible a greater recovery of
energy from the process.
In the US, the relatively low value of raw materials and
utilities and the methods of plant finance have combined to
make the trade-off between the aforemetioned factors opt in
favor of the single pressure process for plants built up to this
time.
REFRIGERATION
Figure 2. Single pressure nitric acid process.
The process begins by vaporization of ammonia at 180
psia (1.241 MPa) and 95°F (35°C), using process heat and
then steam for adding superheat to 350°F (177°C). Filtered
air is compressed in an axial compressor to an interstage level
and then, following cooling, in a centrifugal compressor to a
discharge pressure of 157.7 psia (1.088 MPa). A portion of
the air is diverted for acid bleaching and the balance, for
ammonia oxidation, is circulated through a jacket surround-
ing the tail gas reheater. The heated air and ammonia vapor
(10.3% vol.) are then mixed and passed through the
platinum-rhodium gauze, where the heat of reaction to nitric
oxide raise the temperature to 1,700-1,720°F (927-937°C).
The reaction gas flows through a series of heat exchangers
for recovery of energy either as high pressure superheated
steam, or shaft horsepower from expansion of hot tail gas.
Approximately 67% of the oxidation to nitrogen dioxide
occurs in the gas as it passed through the energy recovery
train and is cooled to 364°F ( 184°C). After further cooling to
145°F (63°C) in the primary cooler-condenser and then
separation of approximately one-third acid product as 42%
strength nitric acid, the gas reaches a state of oxidation to
CHILLED
WATER
ABSORBER
FIGURE 2
SINGLE PRESSURE
NITRIC ACID PROCESS
177
 nitrogen dioxide of 43%, with the dimerization being for ammonia vaporization, as previously noted, occurs at
approximately 20%. The gas is combined with bleach air 95°F (35°C) and is recovered from the secondary gas cooler.
containing additional nitrogen peroxide and passes through Both systems utilize circulating condensate as the energy
an empty oxidation vessel and the secondary cooler. In being transfer medium.
cooled to 150°F (66°C), the gas provides heat to a recirculat-
ing hot water system used for vaporizing the ammonia. The Gas compression
gas enters the absorber 95% oxidized to nitrogen peroxide The compressor terminal conditions and actual shaft
and 27% dimerized. power requirements for the single pressure process and dual
The absorber is essentially the same as described for the pressure process are compared in Table 3 for a 1,000 short
dual pressure process. Tower size and specific details may be (907 metric) t/d capacity plant. Both processes utilize axial/
optimized to design conditions and may vary considerably centrifugal combinations, although all axial or all centrifu-
with the temperature of the chilled water. For this design, gal may be preferred for some circumstances.
chilled water at45°F (7.2°C) is used, and the tail gas exit tem- In the single pressure process, the discharge temperature
perature is approximately 50°F ( 10°C). Acid from the bottom of the high pressure air compressor is arbitrarily set at 450°F
of the absorber is bleached at 147 psia (1.014 MPa), with (232°C) to provide the desired gas preheat to the ammonia
partially cooled compressed air. The bleach air, containing converter. More efficient compression with a lower
nitrogen peroxide stripped from the acid, then is added to the discharge temperature could be selected, and the heat
main gas stream before the oxidation vessel. The cold tail gas balance on the ammonia converter could be maintained by
is wanned by heat exchange with the hot compressed bleach separate air preheating and adjustment of the ammonia-air
air, and then heated to the expander inlet temperature of ratio within the safe limits.
1,150°F (621°C) in two exchangers in the energy recovery In the dual pressure process, the mass flow to the air com-
train. The expander recovers 80% of the required compressor pressor is slightly lower, due to the use of 2% excess oxygen
power. Expanded tail gas, at 565°F (296°C), flows through in the tail gas versus 2'/2% for the single pressure process.
an economizer, providing heat to high pressure boiler feed Also, the mass flow to the high pressure nitrous gas com-
water and low pressure deionized deareator make-up water. pressor is lower by 8.2%, due to condensation and separation
Subsequently, the tail gas at 150°F (66°C) is exhausted to the of weak acid at the lower pressure level. This accounts for a
atmosphere. lower total compression energy requirement for the dual
The 45°F (7.2°C) chilled water for the absorber is supplied pressure process.
by an absorption refrigeration unit, using heat recovered
The interesting feature of nitrous gas compression arises
from the compressor intercooler as the energy source. Heat
from the fact that it is a reacting system undergoing changes
of temperature and pressure, yet the temperature rise can be
the same as if an inert gas were compressed. Consider the
Table 3. Gas compression. effect of the compression on the chemical equilibria. Any
rise in temperature results in an instantaneous decrease in the
Low Pressure Unit Single Pressure Dual Pressure dimer content. Also, the nitric oxide, with a fresh supply of
Process Process oxygen and increasing pressure, will increase its state of
Type Compressor Axial Axial oxidation. In actual operating plants, it has been observed
InletGas Air Air that the heat effects of the two reactions tend to balance. In
Flow Quantity (kg/h) 189,116 184,512 certain instances with relatively less residence time, the
Suction Temperature, (°C) 37.8 37.8 observed net heat effect has been negative. For this design,
Suction Pressure, (Mpa) 0.0966 0.0966 the exact balancing is, of course, an arbitrary condition — it
Discharge Temperature, (°C).... 182 196 depends on the actual operating conditions and the compres-
Discharge Pressure, (MPa) 0.312 0.350 sor design.
Actual Shaft Power, (kJ/h) 27,515 30,719 Factors affecting the efficient conversion of ammonia to
nitric oxide for the single pressure process and the dual pres-
High Pressure Unit sure process have been discussed in other paragraphs. The
operating design parameters, for the comparative evaluation
Type Compressor Centrifugal.. Centrifugal are shown in Table 4.
InletGas Air Nitrous Gas In most existing nitric acid plants, the ammonia-air mix-
Flow Quantity, (kg/h) 189,116 173,633 ture entering the converter contains 10 to 11 % of ammonia by
Suction Temperature (°C) 46.1 52.2 volume. In the single pressure processes, the ammonia con-
Suction Pressure, (MPa).. 0.301 0.301 tent of the mixture should not exceed 10.5%, because of the
Discharge Temperature (°C).... 232 224 lower explosive limit. In the dual pressure processes, with
Discharge Pressure, (MPa) 1.088 1.025 the lower converter pressures, the explosive limit is higher,
Actual Shaft Power, (kJ/h) 35,845 30,830 giving additional operating flexibility.
Conversion efficiencies decrease gradually with time of
Total Compression Power, (kJ/h). 63,360 61,549 operation, and those shown reflect the generally accepted

178
 Table 4. Ammonia conversion.
Single Dual
Pressure Pressure
Process Process
Pressure(MPa) 1.056 0.336
Ammonia Concentration (vol. %) 10.3 10.0*
Temperature Air/Ammonia Mixture fC).... 249 190*
Temperature Nitrous Gas Leaving (&C) 937 866
Average Conversion Efficiency (%) 94.5 96.0
Number of Converters 1 2
Gauze Diameter (mm) 2032 4343
Weight of Gauze (kg) 62.2 62.2
*These values are based on air compressor inlet temperature
of 37.8°C. In practice, higher ammonia concentrations are
used in the dual pressure process with actual ambient tem-
peratures.
l'/2% differential for the two processes. Actual efficiencies
vary with the operational history of the gauzes, and a precise
value must be determined from integrated efficiency records.
The advantageous effect on the equipment size of the higher
ammonia conversion pressure used in the single pressure
process can be seen by comparing the converter dimensions
for a 1,000 short (907 metric) t/d plant. Not only is there a
smaller converter, but the single train layout is an advantage
as well.
Weight of the catalyst depends essentially on the produc-
tion capacity of the unit. Most plants have used 43 to 55 troy
oz/ton/hr (1.5 to 1.9 kg/metric t/h) of 100% acid, but the
number of layers of gauze has varied from four to more than
45 and increases with pressure. The weight of catalyst per
unit surface can thus vary from five to 55 troy oz/ft2 ( 1.7 to
18 kg/rn^).
Catalyst loss
During the course of the ammonia oxidation reaction,
platinum and rhodium are lost in the form of volatile oxide
vapors. The work of Handforth and Tilley (3) showed that the
rate of vaporization varies with temperature and the amount
of oxygen in the reacting gas mixture. According to Oele (4),
regardless of the catalyst thickness, the wire temperature
varies little from inlet to outlet of the catalyst pad. Thus, in
both single pressure and dual pressure plants, the entire
catalyst beds volatilize at rates corresponding to the exit gas
temperatures. Carefully conducted experimental work in-
dicates that the rate of catalyst loss per unit of reaction is
approximately three times more rapid at 1,718°F (973°C)
than at 1,590°F (866°C) (3), Other influences such as erosion
due to high velocity, uneven flow, hot spots, thermal shock,
etc. can affect the rate of catalyst loss.
In actual plant experience, the loss from a dual pressure
converter operating at 1,590°F (866°C) is estimated at about
2.9 x 10-3 troy oz/ton (0.10 g/metric t) of 100% acid and
from a single pressure converter operating at 1,718°F
(937°C) is estimated at about 11.2 x 10'3 troy oz/ton (0.384
g/metric t) of 100% acid. In single pressure plants, approxi-
mately 40 to 50% of the metal lost from the gauze can be re-
covered, reducing the permanently lost catalyst to about 6.8
x IQ'3 troy oz/ton (0.233 g/metric t) of 100% acid.
The high temperature level of available heat and the large
amount of compression energy leaving the process in the tail
gas have shaped the development of energy recovery
schemes of the modern nitric acid processes. Two options,
(a) high pressure steam and (b) heating tail gas for direct
power recovery by expansion, compete for the available
energy. In addition, other energy is recovered by heat inter-
change, making the processes highly integrated and energy
efficient.
For the process comparison, superheated steam is
produced at 580 psia (4.0 MPa) and 716°F (380°C), which is
the usual quality of the medium pressure steam in the large
ammonia plants. Deaerated boiler feed water is supplied at
sufficient pressure and 215°F (102°C). Make-up deionized
water is available at 104°F (40°C). A condensing steam
turbine with 3-4 in Hg abs. (10-14 kPa) back pressure is used
to supply the start-up and make-up power for compression.
The cold tail gas from the absorbers is the heat sink giving
the lower temperature limit in the high level energy recov-
ery train. Thus, in the single pressure process, considerations
of acid condensation and corrosion at the cold end of the tail
gas preheater, set the lowest nitrous gas temperature in the
train at 364°F ( 184°C). Similar reasoning in the dual pressure
process fixes the lowest nitrous gas temperature at 275°F
(135°C). Obviously, if corrosion could be avoided, some
lowering of these temperatures may be desirable.
Table 5 compares the high level heat energy available for
recovery in the two processes. The 10% greater available
heat energy of the single pressure process is largely the result
of the effect of pressure on the oxidation reaction.
Heat energy that can be transferred to the tail gas may be
converted directly to shaft energy at 36% efficiency. Heat
energy put in steam for use in the turbine is converted to shaft
Table 5. High level recoverable heat energy.
Single Dual
Pressure Pressure
Process Process
Temperature Limits
Upper-Exit Gauze (°C) 937 866
Lower-Exit Tail Gas
Preheater (°C) 184 135
Heat Energy Available
Sensible Heat (kJ/h) 157,946 150,253
Heat of Reaction (kJ/h) 22,115 13,327
Heat Loss (kJ/h) 529 529
Total Available (kJ/h) 179,532 163,051
179
energy at less than 25% efficiency. Thus, for either process, Table 6. Heat energy recovery as tail gas heating.
the highest practical temperature to the expander is desirable,
provided the heat available for boiler feed water preheating Single Pressure Dual Pressure
and steam generation are in an acceptable balance. The high- Tail Gas Exit Absorber Process Process
est temperature is limited also by the metallurgy of available
equipment. Although gas expanders are in operation at above Quantity (kg/h) 147,166 146,168
1,300°F (704°C), the highest temperatures used in nitric acid Temperature (°C). 10.0 17.8
plants have been around 1,250°F (677°C). Even so, some
companies prefer to limit the temperature to around 1,150°F Energy Recovery Source
(621°C). Nitrous Gas at 0.317 MPa
In the single pressure process, the final tail gas reheater 280°C-*135°C
is the first exchanger in the 1,718°F (972°C) nitrous gas Sensible Heat (kJ/h) 29,873
stream. However, a conservative tail gas reheat temperature Heat of Reaction (kJ/h) 6,847
of 1,150°F (621°C) is used, because of broad industry accep-
tance. The steam superheater and waste heat boiler which Nitrous Gas at 0.331 MPa
follow cool the nitrous gas to 533°F (278°C); the tail gas pre- 793°C-*560°C
heater cools it finally to 364°F (184°C). With this design, Sensible Heat (kJ/h) 44.338
50% of the available high level heat energy is used for tail gas Heat of Reaction (kJ/h) 792
reheat and 47% for steam generation. The balance is trans-
ferred to the incoming air, which flows through the jacket Bleach Air at 1.09 MPa
surrounding the high temperature equipment. 2320C-»79.4°C
In the dual pressure process, the large cross-sectional area Sensible Heat (kJ/h) 5,235
under the gauze is used, advantageously, as the location of
the steam superheater coils. Thus, the temperature of the LP Deionized Water
nitrous gas from the steam superheater is 1,460°F (793°C), 103~C->96.rC
and a tail gas reheat temperature of 1,004°F (540°C) results. Sensible Heat (kJ/h) 1,267
The waste heat boiler and the tail gas preheater cool the gas
to 536°F (280°C) and 275°F (135°C), respectively. This Nitrous Gas at 1.0 MPa
results in 50% of the available high level heat energy being 314UC^184°C
used in tail gas reheating and 50% for steam generation. Sensible Heat (kJ/h) 18,918
In the single pressure process, it is necessary to warm the Heat of Reaction (kJ/h)... 8,356
50°F ( 10°C) tail gas from the absorber to prevent corrosion on
the nitrous gas side in the tail gas preheater. Heat energy for Nitrous Gas at 1.034 MPa
the tail gas warming comes from exchange with hot com- 937-C-*643"C
pressed bleach air and low pressure deionized water from the Sensible Heat (kJ/h) 60,271
economizer. In the dual pressure process, no warming is re- Heat of Reaction (kJ/h)... 3,240
quired of the 64°F (17.8°C) tail gas.
A summary of the energy recovery as tail gas heating for Total Energy to Tail Gas 97,286 81,850
the two processes is shown in Table 6. (kJ/h)
In both processes, the compressors are on a single shaft, Tail Gas to Expander
with a direct connected tail gas expander turbine and a steam
turbine. Power, recovered from the hot tail gas by isentropic Pressure (MPa) 0.855 0.89
expansion through the reaction bladed turbine at 83-85% Temperature CQ 621 540
adiabatic efficiency, is a function of the expansion ratio and
is proportional to the absolute temperature.
A comparison of the power recovered from tail gas
expansion and the necessary make-up power from the steam
turbine is shown in Table 7. The higher compression require-
ment of the single pressure process is compensated by the Table 7. Summary of compression power (actual shaft
higher expander temperature with the result that steam power).
turbine make-up power is lower.
To gain maximal advantage from the high level heat Single Pressure Dual Pressure
energy available for steam generation, the boiler feed water Process Process
should be preheated to the fullest extent of available sources.
In the single pressure process, the tail gas, with a dew point Compressor Requirement (kJ/h) 63,360 61,524
of approximately 0°F (-17.8°C) at the stack pressure and low Power from Expander (kJ/h) 50,400 46,800
NOX content, provides an economic source of recoverable Steam Turbine Make-up (kJ/h) 12,960 14,724

180
heat energy. Thus, the expanded gas at 565°F (296°C) Table 8. Energy recovery as 3,999.1 kPa steam.
provides 23.64 MMBtu/hr (24,948 kJ/h) feed water preheat.
In the dual pressure process, cooling of the compressed Single Pressure Dual Pressure
nitrous gas following the oxidation vessel provides 15.0 Process (kJ/h) Process (kJ/h)
MMBtu/hr, (15,829 kJ/h) feed water preheat. The expanded
tail gas temperature of 450°F (232°C) is too low to provide HP Boiler Feedwater Heating
additional heating in the integrated process, but it could be Tail Gas at 0.102 MPa
used to generate 45 psig (0.31 MPa) steam for export. 296°C-»137°C
The assumption of deionized make-up water being avail- Sensible Heat 24,948...
able at 104°F (40°C) was to illustrate the ultimate in heat
energy recovery for the two processes. In the single pressure Nitrous Gas at 1.0 MPa
process, a make-up water heater follows the boiler feed water 224°C—> 140°C
heater in the expanded tail gas stream, and thus cools the tail Sensible Heat 8,082
gas to 150°F (65.6°C). Similarly, in the dual pressure Heat of Reaction 7,740
process, a make-up heater follows the boiler feed water
heater in the high pressure nitrous gas stream, recovering the Steam Vaporization and Superheat
required cooling duty as process heat. Nitrous Gas at 1.034 MPa
A comparison of the total energy recovery by the steam 643°C—>278°C
system for the two processes is shown in Table 8. The great- Sensible Heat 73,620
er steam recovery in the single pressure process results from Heat of Reaction 10,530
the combined effect of higher pressures and temperatures in
the ammonia oxidation area of the process. A tabulation of Nitrous Gas at 0.331 MPa
the disposition of the steam energy shows that each process 866°C—>280°C
requires about the same amount of energy, and this is 56-64% Sensible Heat 78,480
of the total recovered as steam. The net excess of recovered Heat of Reaction 2,736
steam energy is shown as export steam.
LP Deionized Water Heating
Tail Has at 0.102 MPa
Costs of production 137°C-»65.6°C
„ . of,. nitric
Costs . . acid., production
, .. for
,. the
., two
. processes are SensibleHeat 9,558
summarized in Table 9. The unit costs for ammonia and
i.1.„.
utilities ,. ,, for
are applicable f plants
, i in
• the
... USA
T ie A or Europe,
r- •
since Nitrous Gas at l.ü Mra
their prices tend to be relative to the world price of -uTo 7 s^n
petroleum. Platinum and rhodium are traded on the inter- J>ensibleHeat ,x>u
national markets and tend to cost the same wherever HeatotReaction 1.JI4
._, . .' ^ _ , -.M , _^ „_ ._. . . , , . . Total Energy
BJ to Steam Generation 118,656 105,912
Capital costs for a 1,000 short /n(907 metric) t/d single pres-
sure and dual pressure plants located in the USA have been ^. .. „„ ,_ . „
estimated» j at* $12,200,000
£ n inn nnn and A $13,800,000
a-n onn nnn respectively.
»• i Disposition
/ of Steam Energy
5J m Process
,A-,^A
TTU <ri /cnnnnn u- u » c *u A i
The $1,600,000 higher cost for the dual pressure process Make-up v Steam Turbine 12,960 „14,724
A~ A0n 0 --^
, from
results - i. larger
the i • ofc the
size i. vesselsi at the
u lower
i pres- Surf ace
„, Condenser
. . ._ , 42,480
' _. 48,276
,' .
A
c .. . ,, "u i » i * A • c
sure. Estimates for the plants located in Europe are similar, • -i AmmVaporization/Superheat
^ ' v 5,256 1,800
but the differential between the dual pressure process and the ^isc,e?l f^cms- —'—î J,'SU
. , pressure process is
single . only
. $1,200,000.
a-, onnnnn Total Used in Process 67,320 67,590
The dual pressure process is shown to have a $1.41 short „ „ 0 . . 0 ,„ _ 0 _.
. /tf-i cc . - ^ A * • A- > *u • t Excess as Export
r Steam 14,260 38,322
ton ($1.55 metric t) advantage in direct costs over the single ,. ... n ici noon
. . (K2/u) I/,Zjl IZ,oou
pressure process. This advantage is mainly due to the costs
associated with the catalyst. Costs of the other utilities and
ammonia offset each other. The higher ammonia
consumption of the single pressure process is more than com-
pensated by the higher steam credit. (This assumes that there Under indirect costs are maintenance, plant overhead, and
is a use for the excess steam.) It is reasonable to assume that insurance. These are related to the plant capital cost and are
future trends in the unit prices of ammonia and utilities will taken at 8% annually. It is also customary for single pres-
be parallel, and any change will not materially affect the sure plants to maintain a catalyst warehouse inventory of
direct cost balance. However, platinum and rhodium are less 150% of a full charge due to the frequency of catalyst change.
dependent on energy costs and are subject to variation based A much lower catalyst inventory (20% average) is required
on supply and demand. for the dual pressure plant. Interest paid on the catalyst

181
 Table 9. Production costs for nitric acid
Dual Pressure Single Pressure
Process Process
Unit Price Unit Quantity Cost/St. Quantity Cost/St.
Raw Material US$ Quantity Per St. US$ Per St. ys$
Ammonia.... 110.00 Short ton (ST)... 0.2866 31.526 ....0.2821 31.031

Operating Costs

CoolingWater 0.050 M gal 27.011 1.350 ...24.730 1.236

DeionizedWater 1.250 M gal 0.255 0.319 .... 0.279' 0.349
Condensed Steam 0.135 M Ib (0.700) (0.095) (1.215) (0.164)
SteamExported 4.000 M Ib (0.913) (3.652) (0.682) (2.726)
Power 0.020 kWh 6.84 0.137 4.30 0.086
Direct Labor (L) 8.00 HR 0.048 0.384 0.048 0.384

Catalyst
PlatinumMetal 230 Troy oz 6.026x10-3 ....1.386 2.717x10-3 ..'0.625
RhodiumMetal 511 Troy oz 0.845x10-3 0.432 0.204x10-3.. Q.104
Recovery, Refining, etc 0.736 0.184

Total Direct Costs. 32.523 ^31.109

(A= -1.414)
Indirect Costs

Supervision(S) 12.50 hr 0.024 0.300 0.024 0.300

Payroll Overheat® 100 (L + S) 0.684 0.684
Maint., Plant Overhead, etc. @
8% Investment 2.958 3.345

Interest on Catalyst Inventory® 10% 0.227 0.030

Total Indirect Costs (US A) 4.169 4.359

Total Production Costs (USA) 36.692 35.468

(A= -1.244)
Total Indirect Costs (Europe) 4.120 4.214

Total Production Costs (Europe) 36.643 35.323

(A= -1-32)
Metric conversions:
1 gal = 0.00378 m3
1 Ib = 0.4536 kg
1 ton = 0.907 metric t
l kWh = 3.6 kJ
1 oz = 0.0283 kg

investment is shown as an indirect cost. Using the total pro-
duction cost differential of $1.22/short ton ($1.35/metric t),
the payout before depreciation and taxes of the $1,600,000
extra cost of the dual pressure process in the US is four years.
In Europe, the total production cost differential is
$1.32/short ton ($1.46/metric t), and the $1,200,000 extra
cost of the dual pressure process is paid out in 2.75 years.
These payout times would not justify the higher investment
cost of the dual pressure process. However, a 20% increase
in catalyst related costs improves the payout to three years in
the USA and 2.1 years in Europe. In contrast, a 40% decrease
in the export steam unit value or a 70% increase in the price of
ammonia relative to the other items would be necessary for a
similar effect.

182
 The preceding sections have compared the single pres-
sure and dual pressure processes on the basis of chemistry,
thermodynamics, kinetics and economics. The dual pressure
process has a distinct advantage in lower ammonia consump-
tion and platinum-rhodium usage. The single pressure
process has a lower capital cost and is capable of greater
energy efficiency, in terms of more export high pressure
steam and less heat rejection to the surroundings.
The final result does not positively favor one process. Our
conclusion is that the two processes may be economically
competitive under a given set of circumstances. Selection of
a process may depend on other factors such as:
•Better utility integration with other plant facilities favors
one process.
•Limited space available may favor the single pressure
process.
•Capacities of 1,250 to 1,500 short (1,134 to 1,360
metric) t/d may favor the dual pressure process because of the
LERAY, D.G.
possibility of up to 225 psia (1.55 MPa) absorption.
•Capacities 300 to 600 short (272 to 544 metric) t/d may
favor the single pressure process since lower required con-
version pressure and temperature will lead to lower catalyst
consumption.
•Requirement of 60-65% acid strength may favor the dual
pressure process because of higher nitrous gas concentra-
tion to the absorber.
Literature cited
1. Carberry, J.J., Chem. Eng. Sei. 9, 189, (1959).
2. Andrew, S.P.S., and Hanson, D., 14, 105, (1961).
3. Handforth, S.L. and Tilley, J.N., Ind. Eng. Chem. 26,
1287, (1934).
4. Oele, A.P., Chem. Reaction Eng., 12th European Meet-
ing Fed. Chem. Eng., Amsterdam, 146, (1957).
ROUDIER, L.R.
183