BASF: The right choice

for nitric acid plants

BASF supplies environmental catalysts and technologies
which reduce or destroy nitrous and nitric oxides emissions
from nitric acid plants. Tailor-made solutions combine
catalytic technology and project management services
for emission reduction projects.

Technical
Note

Figure 1: BASF catalysts for N2O decomposition (left) and NOx abatement (right)

The nitric acid (HNO3) industry is a utilized for emission removal in

major source of nitrogen oxide (NOx) numerous industrial applications,
emissions, including nitrous oxide (N2O) including off-gases from various sources.
or laughing gas. Nitrous oxide is 310 They can be used either individually or
times more effective than carbon dioxide in various combinations in relevant plant
(CO2) in trapping heat in the atmosphere. configurations, as shown in Figure 2.
BASF offers state‐of‐the‐art N2O These environmental solutions combine
decomposition and selective catalytic the strength of BASF ‐ The Chemical
reduction (SCR) DeNOx technologies Company with the expertise of its
(Figure 1) which reduce N2O and nitric chemists and engineers for innovations
oxides (NO and NO2). Both catalyst that meet regulatory compliance while
families, which were originally developed enhancing operations.
to reduce harmful impurities in nitric acid
and adipic acid plants, have been
 Absorption
Steam Heating Tower
Heat
Recovery/
NH3 Exchanger
Mixer
HNO3

Air BASF N2O

Decomposition BASF Reactor
180–450˚C
900˚C
3–12 bar
Compressor NH3
Converter Off-gas
Heater

Figure 2: BASF’s N2O decomposition and DeNOx abatement technologies in a nitric acid plant

N2O Decomposition & Climate Gas Selective Catalytic NOx Reduction (DeNOx)
Reduction BASF offers catalysts for the selective catalytic reduction of
BASF N2O decomposition technology supports the NOx from stationary source gases. The DeNOx process was
goals of the Kyoto Protocol including emission developed by BASF in the 60s and the V2O5 catalysts were
trading certificates. N2O decomposition technology developed in the 70s.
destroys N2O emissions up to 100%. The The catalysts are used for, but not limited to, the following
decomposition of 1 ton of N2O has the same effect applications:
as saving 310 tons of CO2 emissions.
m N
 itric acid plants
The catalysts are used for, but not limited to, the
following worldwide industrial N2O emission sources, m P
 ower plants (coal, oil, gas, biomass)
such as: m G
 as turbines
m Nitric acid plants m G
 as and diesel engines
m Adipic acid plants with referring m S
 hip diesel
license and design
m R
 ailroad engines
m Caprolactam plants
m G
 lass trough
m F
 CC units in refineries
m S
 team crackers
m S
 teel mills
m C
 alcination plants
m C
 ement plants
m W
 aste incineration plants (municipal waste,
hazardous waste, clinical waste)

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BASF’s Long History of A major issue requiring attention was the pressure drop over
Outstanding Climate Protection the catalyst. To analyze this, BASF initially operated their own
plants with ARF reactors, taking into consideration the capital
With its impressive background in chemical technologies and expenditures (CAPEX) and operating expenditures (OPEX) of
strong desire to improve the atmosphere, BASF was designing the plants even in these early years of the SCR on
and installing solutions for the environment before regulatory a production scale level. Many niche applications of this
limits on harmful emissions were even established. Since the technology followed. With continuous efforts to develop and
1960s, BASF’s DeNOx abatement techniques have been in optimize its high‐performing SCR technology, BASF created
place in BASF plants. This technology was expanded to third a DeNOx catalyst that combines low pressure drop, high NOx
party plants worldwide in the 1970s. Starting in the 1990s, conversion and selectivity, very low NH3 slip, and close to zero
innovations for the abatement of nitrous off-gases in nitric acid ppmv generation of N2O over the entire DeNOx system.
and adipic acid plants have been employed.
The N2O decomposition catalyst followed a similar
In the 1970s, the basic configuration for the SCR process developmental process. The philosophy was to scale up the
consisted of a promoted vanadium/titanium oxide catalyst that initial catalytic technologies for use in BASF plants. This was
catalyzed the reaction of ammonia (NH3) with NOx. Different followed in the early 2000s by a transfer of this technical
operating temperatures and pressures were investigated for expertise to third party plants. BASF currently provides the
the initial catalyst generations. In the early 2000s, a “one size highest N2O efficiency with a possibility of greater than
fits all” system was launched and showed outstanding 90% reduction.
properties that met the regulatory policies of global authorities.
The complete single‐stage system consisted of an axial radial
flow (ARF) reactor, NH3 dosing mechanism, and control and
measuring unit equipment. Successful multi‐stage systems
have also been implemented.

Compressed Air NO2

Ammonia NO Nitric Oxide Gas Mixture
Absorption HNO3
Oxidation Gas Oxidation +
Acid
NH3 Condensation

Figure 3: Process diagram of nitric acid production Tailgas

Tailgas Treatment

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Nitric Acid Production As seen in equation 2, the liquid dimer, nitrogen tetroxide
(N2O4) is also generated. Low temperature and high pressure
Nitric acid plants are often part of a larger production facility, operations promote maximum NO2 production.
such as fertilizer or explosives manufacturing. This creates
significantly different operational environments. Diluted HNO3 Absorption: The nitric oxide mixture is pumped into an
with a concentration range from 30–70% is produced via absorption tower and then absorbed into H2O. Oxidation
ammonia oxidation, nitric oxide oxidation, and absorption, takes place in the free space between the trays, while
as shown in Figure 3. absorption occurs on the sieve or bubble cap trays.
Ammonia Oxidation: The initial step involves The chemical reaction in the tower is:
oxidizing ammonia over a platinum (Pt)/rhodium (Rh)
gauze catalyst to produce nitric oxide and water. 3NO2 + H2O Š 2HNO3 +NO (3)
This exothermal reaction uses approximately 900 kJ/mole
of heat and is given by: This reaction is exothermic and continuous cooling is required
within the absorber. A secondary air stream HNO3 is pumped
4NH3 + 5O2 Š 4NO + 6H2O (1) into the tower to re‐oxidize the NO and remove NO2 from the
HNO3. The concentration of the HNO3 produced depends on
Air for this process is compressed, filtered, and preheated by a the number of absorption stages as well as the concentration
heat exchanger. The heated air is then mixed with vaporized of the NO2 entering the absorber.
ammonia. The ammonia‐air mixture is passed to a converter
where it is catalytically converted to nitric oxide and excess air. Controlling Harmful Emissions
The temperature of the catalyst affects the output of the the Catalytic Way
converter. Higher catalyst temperatures cause a greater
selectivity towards NO production, while lower catalyst A major source of NOx emission is the tailgas from the
temperatures result in creation of N2 and N2O. absorption tower. This continuous emission is heavily
dependent on the process and increases can occur with:
Nitric Oxide Oxidation: The NO formed during ammonia
oxidation must now be oxidized. The process stream passes m Insufficient air supply (Oxidation and absorption)
through a condenser and is cooled. The NO combines m Low pressure (Absorption)
m High temperature (Condensation and absorption)
non‐catalytically with residual oxygen to form NO2 via the
following reaction:
The output gases may vary within the following limits:
2NO + O2 Š 2NO2 D N2O4 (2)
NOx: 300–3,500 ppmv
N2O: 300–3,500 ppmv
O2: 1–4 vol %

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Various control mechanisms can be implemented throughout The amount of N2O formed depends on many factors,
the HNO3 plant. While extending the absorption process can including the combustion conditions in the oxidizing unit,
reduce tailgas NOx emissions, catalytic reduction allows catalyst compositions, catalyst age, and burner design.
operation over a wider range of pressures. SCR utilizes a
catalyst to react with the injected ammonia and chemically The N2O control mechanisms are defined by their location
reduce the NOx. Ammonia is injected before the catalyst layer within the production process. Primary controls are done for
at a temperature between 120°C and 450°C. This process is the oxidation process by either modifying the catalyst or
precisely controlled because an insufficient amount of NH3 optimizing the operating conditions. Secondary techniques
causes low NOx conversion rate, while too much NH3 results reduce the N2O immediately after it is formed in oxidation.
in a leakage of unconverted NH3 from the reactor. The NH3 is The preferred location for installation is directly after the gauze
absorbed onto an active site on the catalyst where it reacts in the reactor basket. Tertiary controls abate the N2O by
with the NOx to produce the harmless by‐products nitrogen installing a catalytic reactor either upstream or downstream
(N2) and water (H2O). of the tailgas expander after the oxidizer. In general, the
optimal location for this method is in the hottest position in
4NH3 + 4NO + O2 Š 4N2 + 6H2O (4) the stack gas stream. Secondary and tertiary methods can
4NH3 + 2NO + 2NO2 Š 4N2 + 6H2O (5) achieve greater than 90% reduction. Secondary N2O
decomposition catalyst can be substituted into the oxidation
8NH3 + 6NO2 Š 7N2 + 12H2O (6) stage without substantial costs through a slight increase of the
Raschig Ring bed diameter and/or height in new plants or by
However, unwanted N2O and other emissions are also exchange of the existing Raschig Ring bed.
generated by the ammonia oxidation step (Equations 7–11).

2NH3 + 2O2 Š N2O + 3H2O (7)

4NH3 + 4NO + 3O2 Š 4N2O + 6H2O (8)
4NH3 + 5O2 Š 4NO + 6H2O (9)
2NH3 + 2NO2 Š NH4NO3 + N2 + H2O (10)
NH3 + HNO3 Š NH4NO3 (11)

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 BASF N2O Decomposition Technology
Decomposition technology utilizes a catalyst to initiate
N2O breakdown to N2 and O2, as shown below.

2N2O Š 2N2 + O2

BASF utilizes a series of full, 100% active homogeneously

extruded catalysts (Figure 4) with a very thermally stable spinell
structure. A typical chemical composition is given by:

Typical Chemical Composition (wt%)

CuO 20
ZnO 16
Al2O3 + promoters 64
Table 1: Chemical composition of N 2O decomposition catalyst

They offer the highest temperature resistance and do not

leach into the nitric acid. They are available in various
geometries and sizes, including extrudates, ring tablets,
and honeycombs, as shown in Table 2. An N2O efficiency
of greater than 90% is possible. The choice of shape and
size depends on the plant’s operating condition and the
specifications that need to be met. The 3 mm catalyst offers
the highest N2O decomposition, while the 6 mm catalyst is
used when a lower pressure drop is required. Various
combinations that use the 3 mm, 6 mm, or both extrudates
generate a higher efficiency and ensure enhanced
performance for greater added-value. Honeycombs, which
are tailor‐made to fit the stiff catalyst bed, offer both high
efficiency and low pressure drop, while maintaining a
homogeneous flow. They are designed to compensate
thermal reactor expansion. The gap between the honeycombs
provides additional surface area for the catalytic process.

Figure 4: Examples of two BASF N2O decomposition catalysts

a. O3‐81 catalyst (top) b. O3‐85 catalyst (bottom)

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Figure 5: BASF N2O decomposition honeycomb catalysts a. O3‐88 catalyst (left) b. O3‐88 catalyst: close-up (right)

Used as secondary N2O tools, the catalysts are easy to time-consuming process and can typically be done during a
install since they can be “dropped-in” during regular platinum normal plant maintenance shutdown. The catalysts work with
(Pt) gauze exchange, as shown in Figure 6. They are poured all types of Pt gauzes and can be used in low, medium, high,
from drums into the burner basket directly under the gauze and dual pressure plants.
and then leveled off by raking. Catalyst installation is not a

Catalyst Shape Size, mm Density, kg/L Min. Operating Max. Operating

Temperature, °C Temperature, °C
O3-81 Star Extrudates 6 (diameter) 0.9 450 >800
O3-85 Star Extrudates 3, 6 (diameter) 0.9–1.0 750 >900
O3-88 Honeycomb 50–200 (length) 0.9 750 >900
(Extrudates)
70 (outer diameter)

Table 2: BASF N2O decomposition catalysts

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 During the ammonia oxidation stage, reactions at the Pt
gauze generate N2O. With the decomposition catalyst
located immediately downstream of the gauze, the N2O
is broken down into its natural components with a significant
impact on the climate. In some plants, N2O reduction of higher
than 90% can be achieved.

BASF SCR DeNOx Technology

The BASF DeNOx system provided as a complete system
together with our engineering partners is an “end‐of‐pipe”
solution, which can either be installed before the expander
or directly before the stack. The most advanced catalyst is
O4‐89 as an extrudate, but in some niche applications,
especially at ambient pressure, the monolithic catalyst O4-82
can also be used. The BASF catalyst O4‐89 has been
successfully applied for the removal of NOx from tailgas
derived from nitric acid plants, caprolactam units, gas turbines,
refinery furnaces, waste incinerators, power plants, and diesel
engines.

Figure 6: a. Installation of a BASF N2O decomposition catalyst (top)

b. Placing the Pt gauze over the decomposition catalyst (bottom)

Process Gas NOx NOx and NH3

Process Control

NH3 BASF
storage tank Axial
Radial
Injection Flow
Control (ARF)
NH3 evaporator Reactor
Air
N2 + H2O

Figure 7: Block diagram of BASF SCR DeNOx technology usage in nitric acid plants for process
off-gases (containing NOx)

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The BASF reactor system, which consists of the ARF reactor The BASF catalyst O4-89 (Table 3) is a very active and
(Figure 8), has a very low pressure drop (typically much less robust catalyst, which allows the installation within a wide
than 35 mbar, even with large off-gas volumes). The reactor temperature range. In nitric acid plants, the temperature
system is CAPEX/OPEX optimized, provides excellent fluid ranges typically between 180 and 450°C and temperatures
dynamic behavior, and is easy to fill and operate. The system as low as 130°C can be achieved in exceptional
fits easily in the existing “plot space” and is able to fit nearly all applications. The typical operating pressure window is
SCR reactor locations in various chemical plants. between 3 and 12 barg. For lower to ambient pressures,
the BASF catalyst O4-82 — a monolith concept — is the
preferred choice.

Physical Properties
Color Brown-Yellow
Geometry Extrudate
Diameter, mm Approx. 4.5
Active Composition V2O5 on metal oxide carrier
Load Density, kg/L Approx. 1,100
Crush Strength, kg Approx. 4

Table 3: Physical properties of BASF catalyst O4-89

Figure 8: BASF state-of-the-art design ARF reactor

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The pressure drop over the catalyst system is a major issue. Continuous Support is the Key to Success
With the BASF system, the pressure drop can be tailored to
the customers’ requirements. The pressure drop with the As part of our commitment to sustainability as well as
system ranges between 35 and as low as less than 10 mbar, customer satisfaction, BASF offers economic value by
depending on the operating conditions. Minimal pressure drop providing environmentally-friendly solutions and generating
can be obtained for both high- and low- flue gas temperatures trust through social responsibility. This creates the flexibility
through mechanical design of the reactor system. needed to ensure shorter start-up times and lower overall
costs. For the SCR DeNOx system, BASF supports its
The regulatory policies have increased the standards for NOx customers with:
emissions drastically, and the BASF catalyst is able to meet
the aspects with emissions less than 5 ppmv. The O4-89
m R
 efills
catalyst creates a state-of-the-art DeNOx system with m R
 evamps
extremely low NH3 (< 1 ppmv) slip along with a negligible N2O
m N
 ew turnkey solutions (with engineering partners)
formation. The cost difference for a 2000 ton/day worldscale
nitric acid plant with a NOx removal from 800 ppmv to 100 BASF has developed a Total Service Package to meet the
ppmv or for a NOx removal from 800 ppmv to <30 ppmv challenging demands of the Kyoto Protocol N2O emissions
is negligible. directives. The services offered in this package support the
sustainability of long-term Joint Implementation (JI)/Clean
Development Mechanism (CDM) projects, from initial feasibility
BASF DeNOx and N2O Technologies — studies to the issuance of offset credits. The services include:
Moving beyond BASF Plants m C
 atalyst Engineering and Supply
Since 1997, BASF has been employing its abatement • Full catalyst design based on process simulation
technologies on a commercial scale in plants worldwide.
Starting in 1960s, new technologies have been developed,
• Confidentiality license agreement
implemented, and optimized in BASF plants. Today, BASF • Supply of fresh catalyst/Disposal of spent catalyst
DeNOx and N2O decomposition technologies are used
m B
 asket & Reactor Design
globally in numerous nitric acid plants.
• Review of existing construction
• Two-way review of mutual experience
• Optimization strategies for basket’s engineering

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m Monitoring System The Right Choice
• Verification of monitoring/data processing requirements BASF is the right choice for the reduction of N2O and nitric
•  efinition and recommendation of the necessary
D oxides (NO and NO2) emissions in nitric acid plants. Since
analytical instrumentation 1997, BASF has been providing high N2O reduction efficiency.
BASF’s flexible solutions for N2O decomposition in nitric
•  upervision of delivery, implementation, and calibration of
S acid plants include easy handling capability, compatibility
the system with any Pt gauze, and minimal impact on quality of the
m Project Management HNO3 produced. The SCR DeNOx whether used alone or
in conjunction with the N2O system is an ideal solution for
• Documentation preparation handling tailgas. Along with its wide range of operating
• Verification and certification process assistance window for temperatures and pressures, it achieves high
NOx conversion in addition to low pressure drop and NH3
• Facilitation of offset credits slip. Both technologies are backed by reliable warranties
BASF also can provide support for voluntary emission and outstanding support and service that are associated
reduction projects. with BASF - The Chemical Company. At BASF, we
create chemistry for a sustainable future.

Figure 9: BASF provides technologically-advanced catalysts to meet the needs of nitric acid plants

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About Us Americas
BASF Corporation
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leading supplier of environmental Tel : +1-732-205-5000
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that drive customer success. 67056 Ludwigshafen, Germany
Tel: +49-621-60-21153
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Email: [email protected]

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www.catalysts.basf.com/enviro BF-9834 USL 06/12