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Uhde
ThyssenKrupp
Nitric acid
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Table of contents
Page
1. Company profile
10
12
14
16
18
19
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1. Company profile
With its highly specialised workforce of more than 4,500 employees and its
international network of subsidiaries and branch offices, Uhde, a Dortmund-based
engineering contractor, has, to date, successfully completed over 2,000 projects
throughout the world.
Uhdes international reputation has been built on the successful application of
its motto Engineering with ideas to yield cost-effective high-tech solutions for its
customers. The ever-increasing demands placed upon process and application
technology in the fields of chemical processing, energy and environmental protection
are met through a combination of specialist know-how, comprehensive service
packages, top-quality engineering and impeccable punctuality.
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BP Kln,
Cologne, Germany
Capacity: 1,500 mtpd HNO3 (100%)
Air
Compression
Air
Ammonia
Combustion
NO gas
NO gas
Energy recovery
Tail gas
Excess energy
NO gas
Gas cooling
NO gas
+ Acid condensate
Process
water
Absorption
Tail gas
Block diagram of
nitric acid process
Tail gas
Nitric acid
The oxidation of ammonia over a platinum catalyst to nitrogen oxides, and their absorption in
water to form nitric acid was first carried out in
1838 by C.F. Kuhlmann. However, this discovery
was not then commercialised as ammonia was
too expensive compared with the Chile saltpetre
used to manufacture nitric acid in those days.
The Birkeland-Eyde process,
invented at the beginning of
the 20th century, which
involves the direct combination
of atmospheric oxygen and
nitrogen in an electric arc, was
also of limited application due
to poor energy utilisation.
The history of the modern
nitric acid process really begins
in 1901 when W. Ostwald established the ammonia oxidation
conditions necessary for high
nitrogen oxide yields. The first
plants using the Ostwald process
were started up in the first
decade of the 20th century.
Since then many improvements have been made by
various workers. Milestones
include the use of larger ammonia combustion units employing
flat platinum-rhodium gauzes
instead of Ostwalds rolled up platinum gauze
strip and the recovery of the heat of reaction for
steam raising or electricity generation. The
development of strong, affordable, corrosion
resistant stainless steel materials of construction
made feasible the absorption of the nitrogen
oxides in water under pressure, thus reducing the
size and cost of the absorption equipment, while
progress in turbo-machinery technology led to
the adoption of the more energy efficient dual
pressure process. From the 1920s onwards,
advances in the synthesis of ammonia from
hydrogen and atmospheric nitrogen by the
Haber-Bosch process have given the Ostwald
route to nitric acid an additional boost by lowering its feedstock costs. Nowadays practically all
nitric acid is manufactured by this process.
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3/2
1 mole
NH3
mole
1 mole
H 2O
H2O
Combustion
5/4
1 mole
mole
O2
3/4
NO
mole
3/2
O2
1/2
Oxidation
H2O
1/2
mole
mole
NO2
mole
NO
Absorption
1 mole
Stoichiometry of
nitric acid process
HNO3
Nitric acid
~ 20 % consumption
~ 80% consumption
Fertiliser
CN
Non-Fertiliser
AN
NP
CAN
UAN
AN (technical grade)
ASN
Caprolactam
Polyamide 6
Adipic
acid
Polyamide 6.6
Chemicals
Dinitrotoluene
Nitrobenzene
TDI
MDI
Polyurethane
Polyurethane
(flexible PU)
(rigid PU)
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Primary air
Tail gas
1
STH
Tail gas
turbine
WB
HP steam
HP
steam
2
NO gas
Steam
turbine
Tail gas
Ammonia (gas)
Process water
CW
Air
11
Condensate
Air
compr.
WB
9
LP steam
CW
10
AW
WB
BFW
BFW
CW
Ammonia (liquid)
CW
Secondary air
CW
CW
CW
5
7
Acid
condensate
Nitric acid
product
1 Reactor
2 Process gas cooler
3 Tail gas heater 3
4 Economizer
5 Cooler condenser & feedwater preheater
6 Absorption
7 Bleacher
8 Tail gas heater 1 & 2
9 Tail gas reactor
10 Ammonia evaporation & superheating
11 Turbine steam condenser
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The operating pressure required by such a process depends on the maximum permissible NOX
content in the tail gas. If the specified NOX limit is
below 200 ppm, a pressure of at least 7 bar abs.
must be considered, depending on the cooling
water temperature.
Lower NOX values of less than 50 ppm can be
achieved, if required, by integrating a catalytic
tail gas treatment process. Uhde also provides a
similar process without the ammonia evaporation
and heat recovery units for recovering acid from
the waste gas in, for example, adipic acid plants.
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11
Secondary air
Tail gas
1
Primary air
LP
steam
STH
Tail gas
turbine
WB
HP steam
HP
steam
Steam
turbine
2
8
NO gas
Tail gas
Ammonia (gas)
Process water
CW
Air
11
Condensate
3
CW
WB
Air
compr.
CW
12
WB
CW
LP steam
CW
CW
10
AW
Ammonia (liquid)
BFW
BFW
CW
CW
CW
5
7
Acid
condensate
Nitric acid
product
1 Reactor
2 Process gas cooler
3 Tail gas heater 3
4 Economizer
5 Cooler condenser & feedwater preheater
6 Absorption
7 Bleacher
8 Tail gas heater 1 & 2
9 Tail gas reactor
10 Ammonia evaporator & superheater
11 Turbine steam condenser
12 Air intercooler
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Secondary air
Primary air
STH
CW
WB
Air
compr.
Air
Tail gas
HP
steam
CW
2
NO gas
9
Tail gas
Tail gas
turbine
Process water
Steam
turbine
3
CW
Ammonia (gas)
NOx
compr.
HP steam
CW
14
Condensate
10
WB
Tail gas
LP steam
BFW
BFW
CW
CW
CW
LP steam
CW
11
Ammonia (liquid)
AW
12
CW
5
13
Nitric acid
product
Acid
condensate
1 Reactor
2 Process gas cooler
3 Tail gas heater 3
4 Economizer
5 Cooler condenser 1 & feedwater preheater
6 Tail gas heater 2
7 Cooler condenser 2
8 Absorption
9 Tail gas heater 1
10 Tail gas reactor
11 Ammonia evaporation & superheating
12 Ammonia evaporation
13 Bleacher
14 Turbine steam condenser
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Azeotropic nitric acid with an elevated concentration of 68% by weight can replace concentrated
nitric acid in some applications such as nitrations.
Due to increased market demand, Uhde has
developed an enhanced process for the reliable
production of azeotropic nitric acid without any
further weak nitric acid co-production. The basic
process design is mainly an extended dualpressure process.
BP Kln,
Cologne, Germany
Capacity: 1,500 mtpd HNO3 (100%)
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15
(optional)
Secondary air
Primary air
CW
15
STH
AW
CW
Tail gas
WB
Air
compr.
HP
steam
CW
2
NO gas
9
Tail gas
Tail gas
turbine
Ammonia (gas)
Process water
Air
HP steam
3
Steam
turbine
CW
CW
NOx
compr.
WB
14
Condensate
10
Tail gas
BFW
LP steam
CW
CW
BFW
CW
LP steam
CW
Ammonia (liquid)
11
12
CW
5
13
AW
Acid
condensate
1 Reactor
2 Process gas cooler
3 Tail gas heater 3
4 Economizer
5 Cooler condenser 1 & feedwater preheater
6 Tail gas heater 2
7 Cooler condenser 2
8 Absorption
9 Tail gas heater 1
10 Tail gas reactor
11 Ammonia evaporation & superheating
12 Ammonia evaporation
13 Bleacher
14 Turbine steam condenser
15 Air condenser (optional)
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N2 + 1/2 O2 + 82 kJ
4 N2 + 6 H2O + 1628 kJ
7/ N
2 2
+ 6 H2O + 1367 kJ
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Flowsheet of tail gas section of a nitric acid plant with EnviNOx reactor
Tail gas
2
Tail gas
Process water
Tail gas
turbine
CW
Ammonia (gas)
CW
NO gas
Nitric acid
Flowsheet of tail gas section of a nitric acid plant with EnviNOx reactor
(for lower temperature applications)
Tail gas
2
Ammonia (gas)
Tail gas
Hydrocarbon
Process water
Tail gas
turbine
EnviNOx
Uhde
reactor at AMI
Agrolinz Melamine International,
Linz, Austria
Capacity: 1,000 mtpd HNO3 (100%)
CW
NO gas
CW
1 Absorption
2 Tail gas heating
Nitric acid
3 EnviNOx reactor
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Plant type
Mediumpressure
process
Highpressure
process
Dualpressure
process
Operating
pressure pabs
5.8 bar
10.0 bar
4.6/12.0 bar
Ammonia
284.0 kg
286.0 kg
282.0 kg
Electric power
9.0 kWh
13.0 kWh
8.5 kWh
Platinum,
primary losses
0.15 g
0.26 g
0.13 g
with recovery
0.04 g
0.08 g
0.03 g
Cooling water
(t =10 K)
100 t
130 t
105 t
Process water
0.3 t
0.3 t
0.3 t
LP heating steam,
8 bar, saturated
0.05 t
0.20 t
0.05 t
HP excess steam,
40 bar, 450 C
0.76 t
0.55 t
0.65 t
including water
for steam turbine condenser
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15:48
Address 28.07.2010
16.08.10
2010-08-05_Nitric acid_Rev1.qxp
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