em feature

by Mike Durilla

Mike Durilla is a
NOx and N2O
Product and Applications
Development Manager at
BASF - The Chemical
Control in Nitric Acid Plants
Company. Contact
mike.durilla@basf.com.
A Time to Review the Past and Look Ahead
The New Source Performance Standards (NSPS) for Nitric Acid Plants were last
updated in 1989.1 The standards address only opacity and nitrogen oxides
(NOx). The U.S. Environmental Protection Agency (EPA) is currently looking to
propose new standards; however, today the climate is much different than in
1989. Now there is a worldwide discussion regarding the reduction of green-
house gases. The nitric acid segment is the largest generator of nitrous oxide
(N2O), a greenhouse gas having 310 times the impact of carbon dioxide (CO2).
Today, there are technologies available which can significantly reduce N2O and
there has been a long successful history of NOx control in this segment. As new
standards are being considered, the time has come to once again review emission
controls for the nitric acid sector.

The Nitric Acid Process

The basic process to make nitric acid (HNO3) first
involves catalytically oxidizing ammonia (NH3) with
air to form nitric oxide (NO). Typically, the NO
yield is 9398%, but this depends on the operating
conditions in the reactor and the age of the catalyst.
Some N2O will also form.2,3,4
The mixture is cooled, which oxidizes the NO
forming nitrogen dioxide (NO2) and dinitrogen
tetroxide (N2O4). The temperature and pressure
will determine the distribution of NO2/N2O4 and
the residual amounts of NO and N2O.2,3,4
In the final step, the NO2 and N2O4 are absorbed
in water to form the desired HNO3. Absorber
constraints limit the amount of HNO3 that can be
absorbed. In addition, some NO will form as a
byproduct of the HNO3 formation reaction.2,3,4
Environmental Impacts
NOx has been the principal undesired byproduct
and is defined as NO + NO2. The NSPS specifies
a limit of 1.5 kg NOx (expressed as NO2) per ton
of HNO3 produced. In addition, NO2 has a char-
acteristic reddish brown color which, coupled with

6 em november 2009 Copyright 2009 Air & Waste Management Association awma.org
the stack diameter, determines opacity. The NSPS
specifies a maximum of 10% opacity.1
The NOx emissions exiting the absorber can be as
high as 2,000 to 5,000 parts per million (ppm).
There can be additional surges in NOx during start
up and shut down operations. The N2O emissions
can be 1,500 to 3,500 ppm. It should be empha-
sized that every nitric acid plant runs differently and
the actual emissions are dependent upon the par-
ticular operating conditions of each step.2,3,4
The current NSPS does not specify a limit for
N2O.1 Some nitric acid plants can control their
NOx emissions by upgrading the existing absorber
or adding a second absorber. Most installations
require supplemental NOx controls.2
NOx Control
Decolorization
Even before the Clean Air Act of 1970, nitric acid
plants were using catalytic combustors to improve
the energy balance in their process while at the
same time decolorizing their stacks.5,6 NO is
colorless, but NO2 is reddish brown. In the nitric
acid process, fuel was added to the exhaust to
increase the exhaust temperature thus increasing
the power recovery. If excess fuel was added, some
would react directly with NO2 and convert it to NO.
The increased temperature also resulted in a move-
ment on the NO/NO2 thermal equilibrium curve
to a point where the NO2 was further reduced. The
net effect was to decolorize the stack. The total NOx
level, however, remained unchanged.
Nonselective Catalytic Reduction (NSCR)
With the passage of the Clean Air Act, actual
reduction of the NOx level was required. The NSCR
process uses a fuel and a catalyst to burn out residual
oxygen (O2). Once the O2 is gone (O2 consumption
step), the fuel will react directly with NO2 (decolorizing
awma.org Copyright 2009 Air & Waste Management Association
step) to form NO and with NO (abatement step) to
form CO2, nitrogen (N2), and water. Waste heat
boilers are added to recoup energy from the high
temperatures inherent to the process. This technol-
ogy was widely used in new plants constructed
between 1971 and 1977. However, as fuel prices
rose, efforts shifted to enhancing the performance of
the absorption section of the process so as to reduce
the use of fuel while still meeting NOx limits.3,5,6
Selective Catalytic Reduction (SCR)
In the SCR process, NH3 reacts with NOx across a
catalyst in the presence of O2 to form N2 and water.
This process was of particular interest to the nitric acid
industry because it could be situated at a number of
locations within the process and did not have the high
temperature requirements associated with the NSCR
process. This also eliminated the cost for the waste
heat boilers often inherent to the NSCR process as
used in the nitric acid plant. SCR is a mature tech-
nology dating back to the 1950s and has been
applied to a number of applications. A number of cat-
alyst types and forms have been used in the nitric
acid industry. The selection is most often determined
by the temperature of the location in the process.
SCR control technologies are being used extensively
around the world in the nitric acid segment. About
80% of the nitric acid plants in the U.S. utilize SCR to
control NOx emissions. Whereas 8095% NOx
control was once considered a standard, more recent
installations have targeted 95% or higher.2,3,7
N2O Control
N2O control technologies are typically identified by
their location in the nitric acid manufacturing
process. The technologies are referred to as primary,
secondary, or tertiary control as shown in Figure 1.
Primary
Primary N2O control refers to reducing the N2O
emissions out the stack by reducing the amount of
november 2009 em 7

Figure 1. N2O Abatement in Nitric Acid Plants. Potential Locations to Place N2O Abatement
Technology within Nitric Acid Manufacturing Process. Graphic courtesy of Uhde Corp.
N2O formed in the NH3 oxidation step. Theoretically,
this can be done by modifying the catalyst used in
this step and/or modifying the operating conditions of
this step. However, to date nitric acid plants do not
use this approach to reduce N2O emissions.7
Secondary
Secondary N2O control refers to reducing the
N2O emissions out the stack by reducing the N2O
immediately after it is formed in the NH3 oxidation
step. In this approach, a specific catalyst is located
immediately downstream of the NH3 oxidation
catalyst. N2O is decomposed to N2 and O2 almost
instantaneously after it is formed.
This approach has the lowest capital cost because
the reactor that currently is required for the
ammonia oxidation catalyst is utilized with minimal
modifications. There are no additional operating
costs. Typically, up to 90% N 2O reduction is
targeted. There are greater than 60 nitric acid
plants worldwide implementing this technology.7
Tertiary
Tertiary N2O control refers to reducing the N2O
emissions out the stack by installing a catalytic
reactor at an appropriate location within the
process stream. Several different technologies are
available that look to combine with the existing
need for SCR NOx reduction. Each has different
performance capabilities and different operating
condition requirements.7
8 em november 2009 Copyright 2009 Air & Waste Management Association
When the monitoring of specific levels of N2O
reduction is required or is beneficial (as for emission
trading), tertiary control is the method that allows
the easiest access to make the required measure-
ments. However, tertiary control has the highest
capital cost and may require extensive engineering
costs in order to modify an existing reactor or add
an additional reactor to an already cramped
production facility. Tertiary N2O control simply may
not fit into every nitric acid plant. There are 10-15
installations currently being operated worldwide in
nitric acid plants.
One of the technologies operates best at ~430 C.
A first stage catalyst targets N2O. NH3 is then
added and a second stage catalyst targets NOx.
Up to 99% reduction of N2O is offered.
A second technology operates at ~330 C. NH3 is
added prior to the first stage which targets NOx.
Hydrocarbons are added to a second stage which
targets N2O. Up to 99+% reduction of N2O is
offered with this process.
A third technology reduces both NOx and N2O in
a single stage at temperatures as low as 300 C.
Only NH3 is added. The higher the temperature,
the higher the N2O reduction achieved. Simultane-
ous 90% N2O destruction and 90% NOx reduction
has been seen at 540 C.
When the concern about N2O emissions rose,
a close study of the operating NSCR units in a
number of nitric acid plants indicated that
those units were reducing N2O levels by approx-
imately 80%.8,9 While NSCR units are no longer
being installed on new installations, the question
has been raised as to how to account for their
potential 8090% N2O reduction benefit. In
scenarios where SCR is being considered as a
replacement of an existing NSCR unit in order to
improve NOx control, the N2O reduction from
the added SCR may be minimal. The new SCR
system might have lower NOx emissions, but
higher N2O emissions than the NSCR unit it
replaced. Installations that currently only have
to decolorize might also consider upgrading
to full NSCR to take advantage of increased N2O
reduction.
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The Effect of the Kyoto Protocol
Clean Development Mechanism countries under
the Kyoto Protocol allow N2O reduction products
to generate tradable carbon credits and financial
revenues. This has accelerated the implementation
of the N2O reduction technologies in a number of
industrial sectors including nitric acid.
A Final Thought
The ultimate approach to NOx and N2O control in
the nitric acid segment is based on an optimization
between the capital and operating costs of each
option being considered. The final solution may
well be a combination of several technologies. The
uncertainty of the future value of N2O reduction
has slowed the implementation of N2O reduction
techniques in the U.S. Nitric acid plants located in
countries under the Kyoto Protocol are already
considering and realizing the value of N 2O
reduction in their emission control strategies. em

References
1. Standards of Performance for Nitric Acid Plants, 40 CFR 60 Subpart G; available at http:/ecfr.gpoaccess.gov/cgi/t/text/text-
idx?c=ecfr&rgn=div6& view=text&node=40:6.0.1.1.1.18&idno=40.
2. Alternative Control Techniques Document: Nitric and Adipic Acid Manufacturing Plants, EPA-450/3-91-026, U.S. Environmental Protection Agency,
Research Triangle Park, NC, December, 1991; available at http://www.epa.gov/ttn/catc/dir1/nitric.pdf.
3. Best Available Techniques for Pollution Prevention and Control in the European Fertilizer Industry, European Fertilizer Manufacturers Association, Booklet No.
2 of 8: Production of Nitric Acid, Brussels: 2000; available at http://cms.efma.org/EPUB/easnet.dll/GetDoc?appl=18DAT_IM=000F76&DWD-booklet2.pdf.
4. Kuiper, J. High Temperature Catalytic Reduction Of Nitrous Oxide Emissions From Nitric Acid Production Plants, Report by the Dutch Ministry of Housing,
Spatial Planning and Environment, NOVEM Project Number 375001/0080, CE Ref. J-4586-02, Continental Engineering BV, Amsterdam, October 2001.
5. Adlhart, O.J.; Hindin, S.G.; and Kenson, R.E. Processing Nitric Acid Tail Gas, Chemical Engineering Progress, 1971, 67, 2.
6. Gillespie, G.R.; Boyum, A.A.; and Collins, M.F. Catalytic Purification of Nitric Acid Tail Gas: A New Approach. Presented at AIChE 64th Annual
Meeting, San Francisco, December 2, 1971.
7. Institute of Clean Air Companies (ICAC) Member Installation Lists.
8. Mainhardt, H. N2O Emissions from Adipic Acid and Nitric Acid Production in Background Papers: IPCC Experts Meetings on Good Practice Guidance and
Uncertainty Management in National Greenhouse Gas Inventories, 2002, 183-195; available at http://www.ipcc-nggip.iges.or.jp/public/gp/gpg-bgp.htm.
9. Nitrous Oxide Abatement Technologies for Nitric Acid Production, U.S. Climate Change Technology Program Technology Options for the near
and Long Term, November 2003,189-190; available at http://www.climatetechnology.gov/library/2003/tech-options/tech-options-4-4-1.pdf.

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