Robert Perry: US Patent 4,731,231 -- Nox Reduction by
Cyanuric Acid


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**[rexresearch.com](../index.htm)**

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**Robert
PERRY**

**NOx Reduction by Cyanuric Acid**

---

  

**[C. Petit: San Francisco Chronicle (Dec
18, 1986); "Smog-Fighting Process Discovered"](#sfchron)**   
**[R. Perry: US Patent # 4,731,231; "NO
reduction using sublimation of cyanuric acid"](#4731)**   
**[R. Perry: US Patent # 4,800 068; "NO
reduction using sublimation of cyanuric acid"](#4800)**   
**[R. Perry: US Patent # 4,886 650;  "NO
reduction using sublimation of cyanuric acid"](#4886)**   
**[R. Perry: US Patent # 4,908,193;  "NO
reduction using sublimation of cyanuric acid"](#4908)**

---

***San Francisco Chronicle* (Thurs., Dec. 18, 1986) ~**

**"Smog-Fighting Process Discovered"**

**Charles Petit**

A chemical commonly used in swimming pools could eliminate a
major component of smog from the exhaust of vehicles and
industrial power plants, a Livermore researcher said yesterday.

The chemical is cyanuric acid, which is used to stabilize
chlorine in swimming pools. When heated, the solid chemical
produces a gas -- isocyanic acid -- which can be combined with
the exhaust of an internal-combustion engine to neutralize the
oxides of nitrogen produced by the burning of the fuel.

The result is water vapor, nitrogen, carbon dioxide and certain
other relatively benign gases.

The discovery, being published today in the British journal
Nature, was revealed by Robert A. Perry, a 33-year old chemist
at the Combustion Research Facility operated by Sandia National
Laboratories in Livermore. Sandia is a privately operated, but
government financed, facility across the street from the
Lawrence Livermore National Laboratory.

Perry and his colleagues said that isocyanuric acid introduced
into the exhaust of a small diesel engine in their laboratory
cleaned essentially all oxides of nitrogen from the exhaust of
the engine.

As advance word of the discovery began to circulate, officials
at agencies charged with regulating air pollution showed intense
but cautious interest. "A laboratory experiment is one thing",
said one official. "Making it work in the real world is
something else."

Oxides of nitrogen, usually identified by the shorthand term
Nox, pour into the air over the US at a rate of 27 million tons
per year. Scientists blame Nox emissions for most of the
eye-smarting ozone and the brownish air discoloration that is
characteristic of smog.

The oxides also are a significant source of nitric acid in acid
rain, although most acid rain is blamed on sulfur compounds not
affected by the process revealed yesterday.

Perrys report appears to mark a major success for the 5-year
old combustion research lab, established specifically to find
ways to increase efficiency and to reduce pollution from engines
and industrial combustion.

Yesterdays disclosure marked the end of several years of
experimental work for Perry and his colleagues, who were testing
a number of compounds for neutralizing exhaust when they
discovered that isocyanuric acid worked in 1985.

Isocyanuric acid is released when cyanuric acid, is heated
above about 625 degrees F. That is well below the exhaust
temperatures typical of gasoline and diesel engines and the
types of stationary power plants fueled by fossil fuels.

If the cyanuric acid is introduced as it leaves the engine, the
heat of the exhaust vaporizes the powder into isocyanuric acid.
The isocyanuric acid then neutralizes the oxides of nitrogen
that are an ordinary byproduct of combustion.

"The reaction takes just a few milliseconds", Perry said.

Perry bought the cyanuric acid first used in his lab at a
swimming-pool supply house in Dublin, not far from his home. In
swimming pools, it stabilizes the activity of chlorine compounds
that disinfect and clarify the water.

It is ideal for massive use in air pollution control, he said,
because it is nontoxic and fairly cheap -- about $1 per pound.
If used in an automobile, that amount should be enough to clean
up about 500 miles worth of exhaust, he said.

However, the main use for the process is not expected to be in
privately owned autos, from which more than 90 per cent of NOx
is already removed by catalytic converters, but rather in
trucks diesel engines or at large stationary power plants.

Because Sandia does not conduct applied research, the Dept. of
Energy has awarded Perry exclusive rights to the patent on the
process in exchange for retaining the right to use it without
paying license fees. He now plans to quit Sandia and form a
commercial company, called Technor, to market it.

Perrys discovery comes at a time when increasingly stringent
air pollution regulations are  being adopted by the US EPA,
the California Air Resources Board and local pollution-control
districts.

The most urgent need for NOx control in California is in the LA
basin, although severe problems also exist elsewhere. In Kern
County, for instance, oilfield equipment is a major source of
oxides of nitrogen.

In the  Bay Area, "Our priority really is not on the NOx",
said Lew Robinson, director of planning at the Bay Area Air
Quality Control Management District. "We are mainly worried
about hydrocarbons, but I can see that this could be
tremendously valuable in other parts of the country."

---



**US Patent # 4,731,231**

**NO Reduction using Sublimation of Cyanuric
Acid**

**Robert Perry**

March 15, 1988 ~ US Cl. 423/231

**Abstract ~** An arrangement for reducing the NO content
of a gas stream comprises contacting the gas stream with HNCO at
a temperature effective for heat induced decomposition of HNCO
and for resultant lowering of the NO content of the gas stream.
Preferably, the HNCO is generated by sublimation of cyanuric
acid.

**Other References ~**   
Back et al., "Photolysis of HNCO Vapor in the Presence of NO and
O.sub.2 ", Canadian Journal of Chemistry, 46, 531 (1968).   
Perry, "Kinetics of the Reactions of NCO Radicals with H.sub.2
and NO Using Laser Photolysis-Laser Induced Fluorescence", Jour.
of Chemical Physics, 82, 5485 (1985).

*Primary Examiner:* Heller; Gregory A.   
*Attorney, Agent or Firm:* Millen & White   
***Goverment Interests:*** The U.S. Government has
rights in this invention pursuant to Contract No.
DE-AC04-76DP-00789 between the U.S. Department of Energy and
AT&T Technologies, Inc.

***Description ~*** BACKGROUND OF THE INVENTION

This invention relates to a new method and device for removing
NO.sub.x from gaseous material, e.g., from exhaust gas streams.

The recent emphasis on ecological and environmental concerns,
especially air pollution, acid rain, photochemical smog, etc.,
has engendered a wide variety of proposed methods for removing
NO.sub.x especially NO from gas streams.

Certain proposed techniques involve a great deal of capital
outlay and require major consumption of additives, scrubbers,
etc. For example, U.S. Pat. No. 3,894,141 proposes a reaction
with a liquid hydrocarbon; U.S. Pat. No. 4,405,587 proposes very
high temperature burning with a hydrocarbon; U.S. Pat. No.
4,448,899 proposes reaction with an iron chelate; and U.S. Pat.
No. 3,262,751 reacts NO with a conjugated diolefin. Other
methods utilize reactions with nitriles (U.S. Pat. No.
4,080,425), organic N-compounds (e.g., amines or amides) (DE No.
33 24 668) or pyridine (J57190638). Application of these
reactions imposes organic pollutant disposal problems along with
the attendant problems of toxicity and malodorous environments.
In addition, they require the presence of oxygen and are
relatively expensive.

Other systems are based on urea reactions. For example, U.S.
Pat. No. 4,119,702 uses a combination of urea and an oxidizing
agent which decomposes it, e.g., ozone, nitric acid, inter alia;
U.S. Pat. No. 4,325,924 utilizes urea in a high temperature
reducing atmosphere; and U.S. Pat. No. 3,900,554 (the
thermodenox system) utilizes a combination of ammonia and oxygen
to react with nitric oxide. All of these methods must deal with
the problem of the odor of ammonia and its disposal. All require
oxygen or other oxidizing agents. These methods also suffer from
the drawback of requiring controlled environments which make
them difficult to use in mobile vehicles or smaller stationary
devices.

Japanese Publication No. J55051-420 does not relate to the
removal of nitric oxide from gaseous systems, at least as
reported in Derwent Abstract No. 38871C/22. It utilizes
halocyanuric acid to remove malodorous fumes, e.g., mercaptans,
sulfides, disulfides, ammonia or amines from gases by contact
therewith followed by contact with activated carbon.
Temperatures are reported as less than 80.degree. C.; classical
acid/base interactions appear to be involved (not pyrolysis
decomposition products of the halocyanuric acid).

Back et al, Can. J. Chem. 46, 531 (1968), discusses the effect
of NO on the photolysis of HNCO, the decomposition product of
cyanuric acid. An increase of nitrogen concentration in the
presence of large amounts of nitric oxide (torr levels) was
observed utilizing a medium pressure mercury lamp for photolysis
of HNCO. High temperature reactions were neither addressed nor
involved; similarly, the effect, if any, of HNCO under any
conditions on low amounts of NO (e.g., in the < torr to ppm
range) was also not addressed. In fact, the increased
concentration of nitrogen was associated by the authors with
high NO levels. Their theorized reactions explaining the results
would be important only at high NO levels.

Furthermore, use of cyanuric acid as a source of isocyanic acid
(HNCO) for purposes of studying various properties of the latter
or its subsequent degradation products is also known. See, e.g.,
Okabe, J. Chem. Phys., 53, 3507 (1970) and Perry, J. Chem.
Phys., 82, 5485 (1985). However, heretofore it was never
suggested that cyanuric acid could be useful in the removal of
NO from gas streams.

As a result, there continues to be a need for a simple,
relatively inexpensive, non-polluting, non-toxic, non-malodorous
and regenerable system, method and device for removing nitric
oxide from gas streams.

**SUMMARY OF THE INVENTION**

Accordingly, it is an object of this invention to provide such
a system, method and device.

It is another object of this invention to provide such a
method, system and device which is applicable to small
stationary devices, mobile vehicles, as well as to larger
applications, including smokestacks from plants, furnaces,
manufacturing factories, kilns, vehicles, and essentially any
other source of exhaust gas containing NO, particularly
industrial gases.

Upon further study of the specification and appended claims,
further objects and advantages of this invention will become
apparent to those skilled in the art.

These objects have been attained by this invention by providing
a method of reducing the NO content of a gas stream comprising
contacting the gas stream with HNCO at a temperature effective
for heat induced decomposition of HNCO and for resultant
lowering of the NO content of the gas stream. It is preferred
that the HNCO be generated by sublimation of cyanuric acid.

In another aspect, these objects have been achieved by
providing a device useful for reducing the NO content of a gas
stream comprising:

means for storing a compound which upon sublimation generates
HNCO;

means for subliming said compound in operation;

means for contacting said NO-containing gas stream with said
generated HNCO; and

means for raising the temperature of said gas contacted with
HNCO to a level effective for heat induced decomposition of HNCO
and resultant lowering of the NO content of the gas stream.

In yet another aspect, these objects have been achieved by
providing in a conduit means for an effluent gas stream
containing NO, the improvement wherein the conduit means further
comprises device means for lowering the NO content of said gas,
said device means comprising:

compartment means for storing a compound which upon sublimation
generates HNCO;

means for heating said compound to a temperature at which it
sublimes;

means for contacting said NO-containing gas stream with said
generated HNCO; and

means for raising the temperature of said HNCO-contacted gas
stream to a level effective for heat induced decomposition of
HNCO and resultant lowering of the NO content of the gas stream.

**BRIEF DESCRIPTION OF THE DRAWINGS**

Various other objects, features and attendant advantages of the
present invention will be more fully appreciated as the same
becomes better understood when considered in connection with the
accompanying drawings, in which like reference characters
designate the same or similar parts throughout the several
views, and wherein:

FIG. 1 schematically illustrates one possible configuration for
carrying out the method of this invention and for configuring
the device and/or improved conduit of this invention.

![](peryusp.jpg)

**DETAILED DISCUSSION**

This invention provides many significant advantages over other
theoretical and/or commercially available NO reducers. It is
generically applicable to all industrial gas effluent streams,
e.g., those mentioned in the references discussed above. It is
very simple, inexpensive and portable. It does not require the
use of catalysts and/or co-agents. In addition, when the
preferred source of HNCO (cyanuric acid) is spent during
operation, it can be simply and inexpensively replaced. It
provides heretofore unachievable convenience and efficiency in
reducing NO. Its non-toxicity is another major advantage as its
ready availability and low cost.

As opposed to many of the other systems now available, that of
this invention imposes minimal changes in otherwise preferred
operating conditions for the engine, plant, factory, etc., which
generates the effluent gas stream being purified. For example,
as opposed to presently utilized catalytic converters, this
invention does not impose a requirement that a vehicular engine
be run rich with resultant undesirable lower compression ratios.
In addition, the requirement for use of unleaded gas in order to
avoid catalyst poisoning also does not apply. Overall, the
efficacy of the system of this invention in lowering NO contents
is extremely high.

Within the broadest scope of this invention, any source and/or
means of generating HNCO and admixing it with the effluent
stream can be used. For a variety of reasons including those
discussed above, in the preferred embodiment, sublimation of
cyanuric acid will be utilized: ##STR1##

Isocyanuric acid is a tautomer of cyanuric acid. For purposes
of this invention, the two are equivalent. The sublimation of
cyanuric acid in accordance with the following equation,
##STR2## can be conducted at any temperature effective to cause
a volatilization of sufficient HNCO for the desired purpose. In
general, temperatures greater than 300.degree. C. will be
utilized since sublimation rates at lower temperatures are
generally too low. Preferably, temperatures greater than
320.degree. C. will be used, especially greater than 350.degree.
C. There is no preferred upper limit on temperature; but
generally a temperature less than about 800.degree. C. will be
employed. The precise temperature for a given application can be
routinely selected, perhaps with a few orientation experiments,
in conjunction with considerations of the volume to be filled,
the flow rate of the gas, the resultant residence time of the
admixture of HNCO and NO in the effluent gas stream, the surface
area of the HNCO source which is being sublimed and the
sublimation rate which ensues in a given system upon selection
of the given temperature. For example, for 50 g of a cyanuric
acid sample having a surface area of about 20 cm.sup.2, the
sublimation rate achieved at a temperature of 450.degree. C. is
sufficient to reduce the NO level from a 50 l/m gas stream from
1000 ppm to essentially 0 ppm.

While cyanuric acid itself is the preferred source of HNCO,
other sublimable solids can also be used for its generation.
These include other compounds which are typical impurities in
samples of cyanuric acid, including ammelide and ammeline
##STR3## In general, cyanuric acid wherein the OH groups are
replaced by 1-3 NH.sub.2, alkyl, NH-alkyl or N-alkyl.sub.2
groups, are utilizable. Such alkyl groups typically will have
1-4 carbon atoms.

Also utilizable are oligomers of HNCO which are linear rather
than cyclic as in cyanuric acid. For example, cyamelide is
particularly noteworthy. Also utilizable are the known
halocyanuric acids such as the mono-, di- or tri-chloro, bromo,
fluoro or iodo acids or other various mixed-halo substituted
acids.

Any means or technique which results in admixture of HNCO with
the NO-containing gas is included within the scope of this
invention. For example, if the effluent gas stream itself is at
a sufficiently elevated temperature, it can be directly passed
over a solid sample of the HNCO source to effect sublimation and
instantaneous admixture. It is also possible to incorporate the
solid HNCO source into a solvent therefor, most preferably hot
water, and conventionally spray or inject the solution into the
effluent gas stream. Of course, it is also possible to use
conventional heating means (e.g., conductive, inductive, etc.)
to heat the sublimable source of HNCO and then to conventionally
conduct the resultant HNCO gas into admixture with the effluent
stream. Steam injection preceded by passage of the steam over,
through, etc., the HNCO source such as cyanuric acid can, of
course, also be utilized.

It is also possible to indirectly admix the HNCO with the
effluent gas stream. For example, if the HNCO is injected into
the combustion chamber which produces the effluent gas stream or
if the sublimable source such as cyanuric acid is so injected,
the HNCO will be incorporated into the effluent gas stream at
its point of generation. As long as the necessary reaction
conditions are maintained for subsequent interaction of the HNCO
with the NO in the gas stream, the NO reduction method of this
invention will be accomplished. The latter option pertains to
any system which generates an NO-containing stream, including
vehicular engines (wherein the injection of cyanuric acid or
HNCO can be accomplished via the conventional valves), furnaces,
plants, etc. Alternatively, the admixture can be effected
directly either downstream from the point of generation of the
effluent gas or directly near or at this point, e.g., right at
the head of the vehicular engine where the heat generated by the
latter can be utilized, not only for sublimation of the solid
source of HNCO, but also for effecting the NO reducing reactions
based on the presence of HNCO.

The NO content of the effluent streams into which the HNCO has
been admixed will be lowered as long as the temperature of the
effluent stream is raised to a level at which HNCO thermally
decomposes into products which result in lowering of the NO
content. The precise elevated temperature reached is not
critical and will be routinely selected, perhaps in conjunction
with preliminary orientation experiments, in dependence on the
relative amounts of NO and HNCO and especially the residence
time produced by the volumes and flow rates involved. Generally,
temperatures on the order of about 400.degree. C. will suffice
where residence times are greater than or equal to about one
second. Higher temperatures can also be utilized, e.g., about
400.degree. to 800.degree. C.; however, there will be an upper
limit where the nature of the dominant reactions will change. In
the regime of 450.degree.-700.degree. C. free radical reactions
produce NO in the presence of oxygen. At elevated temperatures
i.e., greater than 1200.degree. C., the presence of oxygen will
make the production of nitric oxide unacceptable.

Pressure is typically not a critical variable under all
realistic applications. Thus, pressures in the range from about
0.1-10 atmospheres as well as lower or higher values are
employable.

The relative amounts of NO and HNCO are not critical.
Typically, the system will be designed so that stoichiometric
amounts are employed. Of course, excesses of either ingredient
can be designed where desirable. In many applications, it will
be desired to utilize very slight, environmentally acceptable
excesses of NO in order to avoid excesses of HNCO. The latter is
an acid which might recyclize to cyanuric acid at the low
temperatures ensuing after the reaction has run its course.
Thus, since the excess of NO can be chosen to be benignly low in
view of the great efficacy of this invention in reducing NO
contents, and since the products of the overall NO-reduction
reactions are nitrogen, carbon dioxide, water and carbon
monoxide (with a minor component of CO), the resultant system
containing benign amounts of NO will cause no environmental
concerns. Of course, where otherwise desirable, the system can
also be run with slight excesses of HNCO. Where excesses are
employed of either ingredient, these can, e.g., be in the range
of about 1.01 to about 1.1 or more on a stoichiometric basis.

In a preferred mode of operation of this invention, the NO
reduction reactions will be conducted in the presence of
surfaces which act as a catalyst for the free radical reactions
which effect the NO reduction. The nature of the surface is not
critical as long as it is catalytically effective, metallic or
otherwise. All those surfaces well known to catalyze related
free radical reactions will be employable, e.g., metallic
surfaces, oxides, etc. For metallic systems, preferably, the
metal component will be iron which will typically be provided by
the steel, stainless steel, or other iron-based surfaces
utilized in plants, vehicles, factories, etc., and especially
utilized in the conduits containing effluent gas streams, e.g.,
mufflers, smokestacks, etc. Other typical metals include the
usual transition metals, e.g., the noble metals, including
platinum, palladium, rhodium, silver, gold, etc. as well as
nickel, cobalt, chromium, manganese, vanadium, titanium, etc. In
a further preferred embodiment, the reaction will be conducted
in a chamber containing particles of such catalytic surfaces,
e.g., pellets, beads, granules, etc. The particle sizes and
distributions are not critical. As usual, the greater the
surface area, the more efficient this effect will be. Where
catalytic surfaces are utilized, residence times can be shorter
and temperatures can be lower under otherwise identical
conditions. Without wishing to be bound by theory, it is felt
that the catalytic effect is primarily exerted in initiating the
generation of free radicals triggering chain reactions necessary
for the NO reduction.

Other components may also be present in the NO-containing
stream without adversely impacting this invention. For example,
where NO.sub.2 is involved, it also will be removed by this
invention. However, under the normal conditions where NO is a
problem, NO.sub.2 often is not a problem. The amount of NO in
the effluent gas stream also is not critical. Typically, the
amounts will be 1 ppm or more, e.g., 1-10,000 ppm or 10-5,000
ppm, typically 100-1,000 ppm, etc. By routine, judicious
selection of reaction conditions as described above, the amount
of NO after admixture with HNCO can be reduced to any desired
low level, including 0 ppm within limits of detection. Greater
reductions in NO contents in a given system can be achieved by
utilizing longer residence times and higher temperatures.

FIG. 1 illustrates one embodiment of a system of this
invention. The overall "device" 1 simply comprises means such as
chamber 2 for holding the sublimable compound; means for heating
the latter to its sublimation temperature, e.g., in FIG. 1 the
means simply being the input gas stream 3 which is at an
elevated temperature; means for contacting the resultant HNCO
with the input stream, which here simply comprises the adjoining
conduits whereby the input stream heats the cyanuric acid and
the resultant HNCO is instantaneously mixed with the input
stream; and means for conducting the reaction, here illustrated
by furnace 4. Many other equivalents will be very clear to
skilled workers. For example, one or both of the storage chamber
and the furnace can be inductively, conductively, radiatively,
etc., heated using external sources other than the input stream
itself. One or both of storage chamber and furnace region can be
located anywhere along the path of the effluent stream, e.g.,
they can be located right at the head of an engine or the
exhaust outlet of a furnace or plant. As discussed above, it is
even possible for the storage means to be located upstream of
the chamber which produces the effluent stream where this is
practical. Conventional heat exchange means can also be
incorporated into the system wherever desirable. In FIG. 1, the
heat exchange means is the input gas itself.

Without wishing to be bound by theory, the following is a
proposed mechanism for the NO reduction system: ##STR4##

As can be seen, free radicals are generated which cause chain
reactions to ensue. This explains both the speed and high
efficiency of the system in removing NO from the gas stream. The
reaction mechanism is highly surprising since the weakest bond
in the HNCO molecule has a strength of about 60 kcal whereupon
it would have been expected that a much higher temperature than
those in the range of 400.degree.-800.degree. C. would be
necessary for a significant effect based on decomposition of
HNCO.

This mode of action also serves to further clarify the
distinction between this invention and the more conventional
chemistry known for HNCO, e.g., that is described in Back et
al., supra. In the latter, no elevated temperatures were used;
only a purely photolytic decomposition of HNCO was effected. In
addition, the lower of NO content mentioned in this reference
related only to relatively high pressures of NO in the several
torr range.

Without further elaboration, it is believed that one skilled in
the art can, using the preceding description, utilize the
present invention to its fullest extent. The following preferred
specific embodiments are, therefore, to be construed as merely
illustrative, and not limitative of the remainder of the
disclosure in any way whatsoever.

In the preceding text and the following examples, all
temperatures are set forth uncorrected in degrees Celsius and
all parts and percentages are by weight; unless otherwise
indicated.

**EXAMPLE 1**

A 7.2 horsepower Onan diesel engine was utilized for the
experiment. Its exhaust had a flow-rate of 100 l/m. A 2 l/m
sample was introduced into a cyanuric acid sublimation chamber.
The latter contained 50 g of cyanuric acid and the sublimation
occurred at 350.degree. C. Thereafter, the mixture of HNCO and
exhaust gas was passed through a furnace region packed with a
bed of steel ball bearings. The temperature in the furnace
region was maintained at a temperature equal to or greater than
450.degree. C. utilizing a conventional heater. The effluent
from the furnace region was passed into a NO.sub.x analyzer. The
residence time in the furnace was about 1 second.

The exhaust gas from the diesel engine included the usual soot,
water, oxygen and CO.sub.2. Its 500 ppm NO content was reduced
to less than 1 ppm (i.e., to the sensitivity level of the
NO.sub.x analyzer). The load on the engine varied from 0.23 to
0.8 with no effect observed on the process.

**EXAMPLE 2**

Under the conditions of Example 1, 5 pounds of cyanuric acid
(2.27 kg) is loaded into the holding chamber. This provides
enough active ingredient (53 moles of HNCO) to remove
approximately 50 moles of NO. At a typical NO concentration in a
vehicle exhaust of 500 ppm, 2.5.times.10.sup.7 liters of gas can
be scrubbed. This is sufficient to remove NO from the exhaust
gas of automobiles for a driving range of approximately 1,500
miles.

The preceding examples can be repeated with similar success by
substituting the generically or specifically described reactants
and/or operating conditions of this invention for those used in
the preceding examples.

From the foregoing description, one skilled in the art can
easily ascertain the essential characteristics of this
invention, and without departing from the spirit and scope
thereof, can make various changes and modifications of the
invention to adapt it to various usages and conditions.

---

**US Patent # 4, 800,068**

**System for NO reduction using sublimation
of cyanuric acid**

**Robert Perry**

**Abstract ~** An arrangement for reducing the NO content
of a gas stream comprises contacting the gas stream with HNCO at
a temperature effective for heat induced decomposition of HNCO
and for resultant lowering of the NO content of the gas stream.
Preferably, the HNCO is generated by sublimation of cyanuric
acid.

**Description ~ BACKGROUND OF THE INVENTION**

This invention relates to a new device for removing NO.sub.x
from gaseous material, e.g., from exhaust gas streams.

The recent emphasis on ecological and environmental concerns,
especially air pollution, acid rain, photochemical smog, etc.,
has engendered a wide variety of proposed methods for removing
especially NO from gas streams.

Certain proposed techniques involve a great deal of capital
outlay and require major consumption of additives, scrubbers,
etc. For example, USP 3,894,141 proposes a reaction with a
liquid hydrocarbon; USP 4,405,587 proposes very high temperature
burning with a hydrocarbon; USP 4,448,899 proposes reaction with
an iron chelate; and USP 3,262,751 reacts NO with a conjugated
diolefin. Other methods utilize reactions with nitriles (USP
4,080,425), organic N-compounds (e.g., amines or amides) (DE 33
24 668) or pyridine (J57190638). Application of these reactions
imposes organic pollutant disposal problems along with the
attendant problems of toxicity and malodorous environments. In
addition, they require the presence of oxygen and are relatively
expensive.

Other systems are based on urea reactions. For example, USP
4,119,702 uses a combination of urea and an oxidizing agent
which decomposes it, e.g., ozone, nitric acid, inter alia; USP
4,325,924 utilizes urea in a high temperature reducing
atmosphere; and USP 3,900,554 (the thermodenox system) utilizes
a combination of ammonia and oxygen to react with nitric oxide.
All of these methods must deal with the problem of the odor of
ammonia and its disposal. All require oxygen or other oxidizing
agents. These methods also suffer from the drawback of requiring
controlled environments which make them difficult to use in
mobile vehicles or smaller stationary devices.

Japanese Publication J55-51-420 does not relate to the removal
of nitric oxide from gaseous systems, at least as reported in
Derwent Abstract 38871C/22. It utilizes halocyanuric acid to
remove malodorous fumes, e.g., mercaptans, sulfides, disulfides,
ammonia or amines from gases by contact therewith followed by
contact with activated carbon. Temperatures are reported as less
than 80.degree. C.; classical acid/base interactions appear to
be involved (not pyrolysis decomposition products of the
halocyanuric acid).

Back et al. Can. J. Chem. 46, 531 (1968), discusses the effect
of NO on the photolysis of HNCO, the decomposition product of
cyanuric acid. An increase of nitrogen concentration in the
presence of large amounts of nitric oxide (torr levels) was
observed utilizing a medium pressure mercury lamp for photolysis
of HNCO. High temperature reactions were neither addressed nor
involved; similarly, the effect, if any, of HNCO under any
conditions on low amounts of NO (e.g., in the<torr to ppm
range) was also not addressed. In fact, the increased
concentration of nitrogen was associated by the authors with
high NO levels. Their theorized reactions explaining the results
would be important only at high NO levels.

Furthermore, use of cyanuric acid as a source of isocyanic acid
(HNCO) for purposes of studying various properties of the latter
or its subsequent degradation products is also known. See, e.g.,
Okabe, J. Chem. Phys., 53, 3507 (1970) and Perry, J. Chem.
Phys., 82, 5485 (1985). However, heretofore it was never
suggested that cyanuric acid could be useful in the removal of
NO from gas streams.

As a result, there continues to be a need for a simple,
relatively inexpensive, non-polluting, non-toxic non-malodorous
and regenerable system, and device for removing nitric oxide
from gas streams.

**SUMMARY OF THE INVENTION**

Accordingly, it is an object of this invention to provide such
a system, and device.

It is another object of this invention to provide such a system
and device which is applicable to small stationary devices,
mobile vehicles, as well as to larger applications, including
smokestacks from plants, furnaces, manufacturing factories,
kilns, vehicles, and essentially any other source of exhaust gas
containing NO, particularly industrial gases.

Upon further study of the specification and appended claims,
further objects and advantages of this invention will become
apparent to those skilled in the art.

These objects have been attained by this invention by providing
a system of reducing the NO content of a gas stream comprising
contacting the gas stream with HNCO at a temperature effective
for heat induced decomposition of HNCO and for resultant
lowering of the NO content of the gas stream. It is preferred
that the HNCO be generated by sublimation of cyanuric acid.

In another aspect, these objects have been achieved by
providing a device useful for reducing the NO content of a gas
stream comprising:

means for storing a compound which upon sublimation generates
HNCO;

means for subliming said compound in operation;

means for contacting said NO-containing gas stream with said
generated HNCO; and

means for raising the temperature of said gas contacted with
HNCO to a level effective for heat induced decomposition of HNCO
and resultant lowering of the NO content of the gas stream.

In yet another aspect, these objects have been achieved by
providing in a conduit means for an effluent gas stream
containing NO, the improvement wherein the conduit means further
comprises device means for lowering the NO content of said gas,
said device means comprising:

compartment means for storing a compound which upon sublimation
generates HNCO;

means for heating said compound to a temperature at which it
sublimes;

means for contacting said NO-containing gas stream with said
generated HNCO; and

means for raising the temperature of said HNCO-contacted gas
stream to a level effective for heat induced decomposition of
HNCO and resultant lowering of the NO content of the gas stream.

**BRIEF DESCRIPTION OF THE DRAWINGS**

Various other objects, features and attendant advantages of the
present invention will be more fully appreciated as the same
becomes better understood when considered in connection with the
accompanying drawings, in which like reference characters
designate the same or similar parts throughout the several
views, and wherein:

FIG. 1 schematically illustrates one possible configuration for
carrying out the method of this invention and for configuring
the device and/or improved conduit of this invention.

**DETAILED DISCUSSION**

This invention provides many significant advantages over other
theoretical and/or commercially available NO reducers. It is
generically applicable to all industrial gas effluent streams,
e.g., those mentioned in the references discussed above. It is
very simple, inexpensive and portable. It does not require the
use of catalysts and/or co-agents. In addition, when the
preferred source of HNCO (cyanuric acid) is spend during
operation, it can be simply and inexpensively replaced. It
provides heretofore unachievable convenience and efficiency in
reducing NO. Its non-toxicity is another major advantage as its
ready availability and low cost.

As opposed to many of the other systems now available, that of
this invention imposes minimal changes in otherwise preferred
operating conditions for the engine, plant, factory, etc., which
generates the effluent gas stream being purified. For example,
as opposed to presently utilized catalytic converters, this
invention does not impose a requirement that a vehicular engine
be run rich with resultant undesirable lower compression ratios.
In addition, the requirement for use of unleaded gas in order to
avoid catalyst poisoning also does not apply. Overall, the
efficacy of the system of this invention in lowering NO contents
is extremely high.

Within the broadest scope of this invention, any source and/or
means of generating HNCO and admixing it with the effluent
stream can be used. For a variety of reasons including those
discussed above, in the preferred embodiment, sublimation of
cyanuric acid will be utilized: ##STR1##

Isocyanuric acid is a tautomer of cyanuric acid. For purposes
of this invention, the two are equivalent. The sublimation of
cyanuric acid in accordance with the following equation,
##STR2## can be conducted at any temperature effective to cause
a volatilization of sufficient HNCO for the desired purpose. In
general, temperatures greater than 300.degree. C. will be
utilized since sublimation rates at lower temperatures are
generally too low. Preferably, temperatures greater than
320.degree. C. will be used, especially greater than 250.degree.
C. There is no preferred upper limit on temperature; but
generally a temperature less than about 800.degree. C. will be
employed. The precise temperature for a given application can be
routinely selected, perhaps with a few orientation experiments,
in conjunction with considerations of the volume to be filled,
the flow rate of the gas, the resultant residence time of the
admixture of HNCO and NO in the effluent gas stream, the surface
area of the HNCO source which is being sublimed and the
sublimation rate which ensues in a given system upon selection
of the given temperature. For example, for 50 g of a cyanuric
acid sample having a surface area of about 20 cm.sup. 2, the
sublimation rate achieved at a temperature of 450.degree. C. is
sufficient to r3educe the NO level from a 50 l/m gas stream from
1000 ppm to essentially 0 ppm.

While cyanuric acid itself is the preferred source of HNCO,
other sublimable solids can also be used for its generation.
These include other compounds which are typical impurities in
samples of cyanuric acid, including ammelide and ammeline
##STR3## In general, cyanuric acid wherein the OH groups are
replaced by 1-3 NH.sub.2 , alkyl, NH-alkyl or N-alkyl.sub.2
groups, are utilizable. Such alkyl groups typically will have
1-4 carbon atoms.

Also utilizable are oligomers of HNCO which are linear rather
than cyclic as in cyanuric acid. For example, cyamelide is
particularly noteworthy. Also utilizable are the known
halocyanuric acids such as the mono-, di- or tri-chloro, bromo,
fluoro or iodo acids or other various mixed-halo substituted
acids.

Any means or technique which results in admixture of HNCO with
the NO-contianing gas is included within the scope of this
invention. For example, if the effluent gas stream itself is at
a sufficiently elevated temperature, it can be directly passed
over a solid sample of the HNCO source to effect sublimation and
instantaneous admixture. It is also possible to incorporate the
solid HNCO source into a solvent therefor, most preferably hot
water, and conventionally spray or inject the solution into the
effluent gas stream. Of course, it is also possible to use
conventional heating means (e.g., conductive, inductive, etc.)
to heat the sublimable source of HNCO and then to conventionally
conduct the resultant HNCO gas into admixture with the effluent
stream. Steam injection preceded by passage of the steam over,
through, etc., the HNCO source such as cyanuric acid can, of
course, also be utilized.

It is also possible to indirectly admix the HNCO with the
effluent gas stream. For example, if the HNCO is injected into
the combustion chamber which produces the effluent gas stream or
if the sublimable source such as cyanuric acid is so injected,
the HNCO will be incorporated into the effluent gas stream at
its point of generation. As long as the necessary reaction
conditions are maintained for subsequent interaction of the HNCO
with the NO in the gas stream, the NO reduction method of this
invention will be accomplished. The latter option pertains to
any system which generates an NO-containing stream, including
vehicular engines (wherein the injection of cyanuric acid or
HNCO can be accomplished via the conventional valves), furnaces,
plants, etc. Alternatively, the admixture can be effected
directly either downstream from the point of generation of the
effluent gas or directly near or at this point, e.g., right at
the head of the vehicular engine where the heat generated by the
latter can be utilized, not only for sublimation of the solid
source of HNCO, but also for effecting the NO reducing reactions
based on the presence of HNCO.

The NO content of the effluent streams into which the HNCO has
been admixed will be lowered as long as the temperature of the
effluent stream is raised to a level at which HNCO thermally
decomposes into products which result in lowering of the NO
content. The precise elevated temperature reached is not
critical and will be routinely selected, perhaps in conjunction
with preliminary orientation experiments, in dependence on the
relative amounts of NO and HNCO and especially the residence
time produced by the volumes and flow rates involved. Generally,
temperatures on the order of about 400.degree. C. will suffice
where residence times are greater than or equal to about one
second. Higher temperatures can also be utilized, e.g., about
400 to 800.degree. C.; however, there will be an upper limit
where the nature of the dominant reactions will change. In the
regime of 450.degree.-700.degree. C. free radical reactions
produce NO in the presence of oxygen. This effect can be
controlled by the addition of oxygen scavengers or increased
concentrations of HNCO to consume the nitric oxide produced. At
elevated temperatures, however, i.e., greater than 1200.degree.
C., the presence of oxygen will make the production of nitric
oxide unacceptable.

Pressure is typically not a critical variable under all
realistic applications. Thus, pressures in the range from abou
0.1-10 atmospheres as well as lower or higher values are
employable.

The relative amounts of NO and HNCO are not critical.
Typically, the system will be designed so that stoichiometric
amounts are employed. Of course, excesses of either ingredient
can be designed where desirable. In many applications, it will
be desired to utilize very slight, environmentally acceptable
excesses of NO in order to avoid excesses of HNCO. The latter is
an acid which might recyclize to cyanuric acid at the low
temperatures ensuing after the reaction has run its course.
Thus, since the excess of NO can be chosen to be benignly low in
view of the great efficacy of this invention in reducing NO
contents, and since the products of the overall NO-reduction
reactions are nitrogen, carbon dioxide, water and carbon
monoxide (with a minor component of CO), the resultant system
containing benign amounts of NO will cause no environmental
concerns. Of course, where otherwise desirable, the system can
also be run with slight excesses of HNCO. Where excesses are
employed of either ingredient, these can, e.g., be in the range
of about 1.01 to abou 1.1 or more on a stoichiometric basis.

In a preferred mode of operation of this invention, the NO
reduction reactions will be conducted in the presence of
surfaces which act as a catalyst for the free radical reactions
which effect the NO reduction. The nature of the surface is not
critical as long as it is catalytically effective, metallic or
otherwise. All those surfaces well known to catalyze related
free radical reactions will be employable, e.g., metallic
surfaces, oxides, etc. For metallic systems, preferably, the
metal component will be iron which will typically be provided by
the steel, stainless steel, or other iron-based surfaces
utilized in plants, vehicles, factories, etc., and especially
utilized in the conduits containing effluent gas streams, e.g.,
mufflers, smokestacks, etc. Other typical metals include the
usual transition metals, e.g., the nobel metals, including
platinum, palladium, rhodium, silver, gold, etc. as well as
nickel, cobalt, chromium, manganese, vanadium, titanium, etc. In
a further preferred embodiment, the reaction will be conducted
in a chamber containing particles of such catalytic surfaces,
e.g., pellets, beads, granules, etc. The particle sizes and
distributions are not critical. As usual, the greater the
surface area, the more efficient this effect will be. Where
catalytic surfaces are utilized, residence times can be shorter
and temperatures can be lower under otherwise identical
conditions. Without wishing to be bound by theory, it is felt
that the catalytic effect is primarily exerted in initiating the
generation of free radicals triggering chain reactions necessary
for the NO reduction.

Other components may also be present in the NO-containing
stream without adversely impacting this invention. For example,
where NO.sub.2 is involved, it also will be removed by this
invention. However, under the normal conditions where NO is a
problem, NO.sub.2 often is not a problem. The amount of NO in
the effluent gas stream also is not critical. Typically, the
amounts will be 1 ppm or more, e.g., 1-10,000 ppm or 10-5,000
ppm, typically 100-1,000 ppm, etc. By routine, judicious
selection of reaction conditions as described above, the amount
of NO after admixture with HNCO can be reduced to any desired
low level, including 0 ppm within limits of detection. Greater
reductions in NO contents in a given system can be achieved by
utilizing longer residence times and higher temperatures.

FIG. 1 illustrates one embodiment of a system of this
invention. The overall "device" 1 simply comprises means such as
chamber 2 for holding the sublimable compound; means for heating
the latter to its sublimation temperature, e.g., in FIG. 1 the
means simply being the input gas stream 3 which is at an
elevated temperature; means for contacting the resultant HNCO
with the input stream, which here simply comprises the adjoining
conduits whereby the input stream heats the cyanuric acid and
the resultant HNCO is instantaneously mixed with the input
stream; and means for conducting the reaction, here illustrated
by furnace 4. Many other equivalents will be very clear to
skilled workers. For example, one or both of the storage chamber
and the furnace can be inductively, conductively, radiatively,
etc., heated using external sources other than the input stream
itself. One or both of storage chamber and furnace region can be
located anywhere along the path of the effluent stream, e.g.,
they can be located right at the head of an engine or the
exhaust outlet of a furnace or plant. As discussed above, it is
even possible for the storage means to be located upstream of
the chamber which produces the effluent stream where this is
practical. Conventional heat exchange means can also be
incorporated into the system wherever desirable. In FIG. 1, the
heat exchange means is the input gas itself.

Without wishging to be bound by theory, the following is a
proposed mechanism for the NO reduction system: ##STR4##

As can be seen, free radicals are generated which cause chain
reactions to ensue. This explains both the speed and high
efficiency of the system in removing NO from the gas stream. The
reaction mechanism is highly surprising since the weakest bond
in the HNCO molecule has a strength of about 60 kcal whereupon
it would have been expected that a much higher temperature than
those in the range of 400.degree.-800.degree. C. would be
necessary for a significant effect based on decomposition of
HNCO.

This mode of action also serves to further clarify the
distinction between this invention and the more conventional
chemistry known for HNCO, e.g., that is described in Back et
al., supra. In the latter, no elevated temperatures were used;
only a purely photolytic decomposition of HNCO was effected. In
addition, the lowering of NO content mentioned in this reference
related only to relatively high pressures of NO in the several
torr range.

This reaction mechanism also explains an observed interfering
effect of oxygen on the system of this invention. The hydrogen
atoms produced during the course of this invention will react
with oxygen to produce OH and O. In turn, these species will
result in production of NO and H:

H+O.sub.2 .fwdarw.OH+O

O+HNCO.fwdarw.HNO+CO

HNO.fwdarw.NO+H

This reaction mechanism will be significant at temperatures on
the order of 450.degree. C. or higher.

Fortunately, any of the known scavengers of O can be included
in the reaction system when oxygen is present in order to
eliminate or very significantly ameliorate the oxygen effect.
The preferred scavenger is water which exerts its effect in
accordance with the following equations:

O+H.sub.2 O.revreaction.2OH

OH+CO.fwdarw.CO.sub.2 +H

As a result, H atoms are regenerated without coproduction of
NO. This permits the reaction:

H+HNCO.fwdarw.NH.sub.2 +CO

to dominate with overall loss of NO.

Generally the molar ratio of H.sub.2 O ot O.sub.2 can be in the
range of 2-5 to 1.

Under typical operating conditions of vehicular engines now in
use, the above potential interfering effect of O.sub.2 will
inherently be avoided because of the inherent presence of
H.sub.2 O in the effluent gas streams emanating from such
engines. However, where oxygen is present and the necessary O
scavenger is not inherently provided, any conventional means for
introducing a scavenger such as water can be utilized. Many
other scavengers can also be employed, e.g., typical components
of fuels utilized in engines, furnaces, plants, etc., including
alkenes, other unsaturated hydrocarbons, and many other well
known organic compounds. As an alternative to use of suitable
scavengers, increased concentrations of HNCO can be used to
reduce nitric oxide that is produced by the presence of oxygen.

Under operating conditions usually encountered, there should be
not other significant interferants for the system of this
invention, i.e, no other species which will react fast with H
alone. In general, conditions under which high concentrations of
such species are generated will be conditions wherein not much
NO is generated anyway. Where NO is a problem, it is unlikely
that species other than O.sub.2 will be interferring. Where
species which are slow reacting with H atoms are present in high
concentration, they will pose much more significant pollution
problems than NO itself.

Without further elaboration, it is believed that one skilled in
the art can, using the preceding description, utilize the
present invention to its fullest extent. The following preferred
specific embodiments are, therefore, to be construed as merely
illustrative, and not limitative of the remainder of the
disclosure in any way whatsoever.

In the preceding text and the following examples, all
temperatures are set forth uncorrected in degrees Celsius and
all parts and percentages are by weight; unless otherwise
indicated.

**EXAMPLE 1**

A 7.2 horsepower Onan diesel engine was utilized for the
experiment. Its exhaust had a flow-rate of 100 l/m. A 2 l/m
sample was introduced into a cyanuric acid sublimation chamber.
The latter contained 50 g of cyanuric acid and the sublimation
occurred at 350.degree. C. Thereafter, the mixture of HNCO and
exhaust gas was passed through a furnace region packed with a
bed of steel ball bearings. The temperature in the furnace
region was maintained at a temperature equal to or greater than
450.degree. C. utilizing a conventional heater. The effluent
from the furnace region was passed into a NO.sub.x analyzer. The
residence time in the furnace was about 1 second.

The exhaust gas from the diesel engine included the usual soot,
water, oxygen and CO.sub.2. Its 500 ppm NO content was reduced
to less than 1 ppm (i.e., to the sensitivity level of the
NO.sub.x analyzer). The load on the engine varied from 0.23 to
0.8 with no effect observed on the process.

**EXAMPLE 2**

Under the conditions of Example 1, 5 pounds of cyanuric acid
(2.27 kg) is loaded into the holding chamber. This provides
enough active ingredient (53 moles of HNCO) to remove
approximately 50 moles of NO. At a typical NO concentration in a
vehicle exhaust of 500 ppm, 2.5.times.10.sup.7 liters of gas can
be scrubbed. This is sufficient to remove NO from the exhaust
gas of automobiles for a driving range of approximately 1,500
miles.

The preceding examples can be repeated with similar success by
substituting the generically or specifically described reactants
and/or operating conditions of this invention for those used in
the preceding examples.

From the foregoing description, one skilled in the art can
easily ascertain the essential characteristics of this
invention, and without departing from the spirit and scope
thereof, can make various changes and modifications of the
invention to adapt it to various usages and conditions.

---



**US Patent # 4,886,650**

**NOx reduction using sublimation of
cyanuric acid**

**Robert Perry**

**Abstract ~** An arrangement for reducing the NO
content of a gas stream comprises contacting the gas stream with
HNCO at a temperature effective for heat induced decomposition
of HNCO and for resultant lowering of the NO content of the gas
stream. Preferably, the HNCO is generated by sublimation of
cyanuric acid and CO or other H-atom generating species is also
present or added to the gas stream.

***Description ~*** BACKGROUND OF THE INVENTION

This invention relates to a new method and device for removing
NO.sub.x from gaseous material, e.g., from exhaust gas streams.

The recent emphasis on ecological and environmental concerns,
especially air pollution, acid rain, photochemical smog, etc.,
has engendered a wide variety of proposed methods for removing
NO.sub.x, especially NO, from gas streams.

Certain proposed techniques involve a great deal of capital
outlay and require major consumption of additives, scrubbers,
etc. For example, U.S. Pat. No. 3,894,141 proposes a reaction
with a liquid hydrocarbon; U.S. Pat. No. 4,405,587 proposes very
high temperature burning with a hydrocarbon; U.S.P. 4,448,899
proposes reaction with an iron chelate; and U.S. Pat. No.
3,262,751 reacts NO with a conjugated diolefin. Other methods
utilize reactions with nitriles (U.S. Pat. No. 4,080,425),
organic N-compounds (e.g., amines or amides) (DE No. 33 24 668)
or pyridine (No. J57190638). Application of these reactions
imposes organic pollutant disposal problems along with the
attendant problems of toxicity and malodorous environments. In
addition, they require the presence of oxygen and are relatively
expensive.

Other systems are based on urea reactions. For example, U.S.
Pat. No. 4,119,702 uses a combination of urea and an oxidizing
agent which decomposes it, e.g., ozone, nitric acid, inter alia;
U.S. Pat. No. 4,325,924 utilizes urea in a high temperature
reducing atmosphere; and U.S. Pat. No. 3,900,554 (the
thermodenox system) utilizes a combination of ammonia and oxygen
to react with nitric oxide. All of these methods must deal with
the problem of the odor of ammonia and its disposal. All require
oxygen or other oxidizing agents. These methods also suffer from
the drawback of requiring controlled environments which make
them difficult to use in mobile vehicles or smaller stationary
devices.

Japanese Publication No. J55051-420 does not relate to the
removal of nitric oxide from gaseous systems, at least as
reported in Derwent Abstract 38871C/22. It utilizes halocyanuric
acid to remove malodorous fumes, e.g., mercaptans, sulfides,
disulfides, ammonia or amines from gases by contact therewith
followed by contact with activated carbon. Temperatures are
reported as less than 80.degree. C.; classical acid/base
interactions appear to be involved (not pyrolysis decomposition
products of the halocyanuric acid).

Back et al, Can. J. Chem. 46, 531 (1968), discusses the effect
of NO on the photolysis of HNCO, the decomposition product of
cyanuric acid. An increase of nitrogen concentration in the
presence of large amounts of nitric oxide (torr levels) was
observed utilizing a medium pressure mercury lamp for photolysis
of HNCO. High temperature reactions were neither addressed nor
involved; similarly, the effect, if any, of HNCO under any
conditions on low amounts of NO (e.g., in the <torr to ppm
range) was also not addressed. In fact, the increased
concentration of nitrogen was associated by the authors with
high NO levels. Their theorized reactions explaining the results
would be important only at high NO levels.

Furthermore, use of cyanuric acid as a source of isocyanic acid
(HNCO) for purposes of studying various properties of the latter
or its subsequent degradation products is also known. See, e.g.,
Okabe, J. Chem. Phys., 53, 3507 (1970) and Perry, J. Chem.
Phys., 82, 5485 (1985).

J.P. No. 54-28771 discloses the addition of relatively large
particles (0.1-10 mm, preferably 0.5-5.0 mm) of cyanuric acid at
temperatures generically disclosed as 600.degree.-1500.degree.
C., but preferably at high temperatures of
1200.degree.-1300.degree. C., for removal of NO.sub.x from
exhaust gas. The theory of operation disclosed in this
publication appears to involve a reaction occurring on the
surface of the particle which leads to the requirements of the
high particle size and high temperature. It is explicitly stated
in the publication that, "If the diameter of the granule is too
small, the efficiency goes down." There is no suggestion in this
publication that the active species effecting the treatment of
the exhaust gas is itself gaseous and certainly no suggestion
that the gaseous species is HNCO. As a result, the conditions
disclosed in this reference lead away from those which are most
applicable to a reaction of NO.sub.x with gaseous HNCO.
Consequently, the process of this reference is believed not to
have been used on a technical scale.

As a result, there continues to be a need for a simple,
relatively inexpensive, non-polluting, non-toxic, non-malodorous
and regenerable system, method and device for removing nitric
oxide from gas streams.

**SUMMARY OF THE INVENTION**

Accordingly, it is an object of this invention to provide such
a system, method and device.

It is another object of this invention to provide such a
method, system and device which is applicable to small
stationary devices, mobile vehicles, as well as to larger
applications, including smokestacks from plants, furnaces,
manufacturing factories, kilns, vehicles, and essentially any
other source of exhaust gas containing NO, particularly
industrial gases.

Upon further study of the specification and appended claims,
further objects and advantages of this invention will become
apparent to those skilled in the art.

These objects have been attained by this invention by providing
a method of reducing the NO content of a gas stream comprising
contacting the gas stream with HNCO at a temperature effective
for heat induced decomposition of HNCO and for resultant
lowering of the NO content of the gas stream. It is preferred
that the HNCO be generated by sublimation of cyanuric acid.

In another aspect, these objects have been achieved by
providing a device useful for reducing the NO content of a gas
stream comprising:

means for storing a compound which upon sublimation generates
HNCO;

means for subliming said compound in operation;

means for contacting said NO-containing gas stream with said
generated HNCO; and

means for raising the temperature of said gas contacted with
HNCO to a level effective for heat induced decomposition of HNCO
and resultant lowering of the NO content of the gas stream.

In yet another aspect, these objects have been achieved by
providing in a conduit means for an effluent gas stream
containing NO, the improvement wherein the conduit means further
comprises device means for lowering the NO content of said gas,
said device means comprising:

compartment means for storing a compound which upon sublimation
generates HNCO;

means for heating said compound to a temperature at which it
sublimes;

means for contacting said NO-containing gas stream with said
generated HNCO; and

means for raising the temperature of said HNCO-contacted gas
stream to a level effective for heat induced decomposition of
HNCO and resultant lowering of the NO content of the gas stream.

**BRIEF DESCRIPTION OF THE DRAWINGS**

Various other objects, features and attendant advantages of the
present invention will be more fully appreciated as the same
becomes better understood when considered in connection with the
accompanying drawings, in which like reference characters
designate the same or similar parts throughout the several
views, and wherein:

FIG. 1 schematically illustrates one possible configuration for
carrying out the method of this invention and for configuring
the device and/or improved conduit of this invention.

**DETAILED DISCUSSION**

This invention provides many significant advantages over other
theoretical and/or commercially available NO reducers. It is
generically applicable to all industrial gas effluent streams,
e.g., those mentioned in the references discussed above. It is
very simple, inexpensive and portable. It does not require the
use of catalysts and/or co-agents. In addition, when the
preferred source of HNCO (cyanuric acid) is spent during
operation, it can be simply and inexpensively replaced. It
provides heretofore unachievable convenience and efficiency in
reducing NO. Its non-toxicity is another major advantage as is
its ready availability and cost.

As opposed to many of the other systems now available, that of
this invention imposes minimal changes in otherwise preferred
operating conditions for the engine, plant, factory, etc., which
generates the effluent gas stream being purified. For example,
as opposed to presently utilized catalytic converters, this
invention does not impose a requirement that a vehicular engine
be run rich with resultant undesirable lower compression ratios.
In addition, the requirement for use of unleaded gas in order to
avoid catalyst poisoning also does not apply. Overall, the
efficacy of the system of this invention in lowering NO contents
is extremely high.

Within the broadest scope of this invention, any source and/or
means of generating HNCO and admixing it with the effluent
stream can be used. For a variety of reasons including those
discussed above, in the preferred embodiment, sublimation of
cyanuric acid will be utilized: ##STR1##

Isocyanuric acid is a tautomer of cyanuric acid. For purposes
of this invention, the two are equivalent. The sublimation of
cyanuric acid in accordance with the following equation,
##STR2## can be conducted at any temperature effective to cause
a volatilization of sufficient HNCO for the desired purpose. In
general, temperatures greater than 300.degree. C. will be
utilized since sublimation rates at lower temperatures are
generally too low. Preferably, temperatures greater than
320.degree. C. will be used, especially greater than 350.degree.
C. There is no preferred upper limit on temperature; but
generally a temperature less than about 800.degree. C. will be
employed. The precise temperature for a given application can be
routinely selected, perhaps with a few orientation experiments,
in conjunction with considerations of the volume to be filled,
the flow rate of the gas, the resultant residence time of the
admixture of HNCO and NO in the effluent gas stream, the surface
area of the HNCO source which is being sublimed the sublimation
rate which ensues in a given system upon selection of the given
temperature. For example, for 50 g of a cyanuric acid sample
having a surface area of about 20 cm.sup.2, the sublimation rate
achieved at a temperature of 450.degree. C. is sufficient to
reduce the NO level from a 50 l/m gas stream from 1000 ppm to
essentially 0 ppm.

While cyanuric acid itself is the preferred source of HNCO,
other sublimable solids can also be used for its generation.
These include other compounds which are typical impurities in
samples of cyanuric acid, including ammelide and ammeline
##STR3## In general, cyanuric acid wherein the OH groups are
replaced by 1-3 NH.sub.2, alkyl, NH-alkyl or N-alkyl.sub.2
groups, are utilizable. Such alkyl groups typically will have
1-4 carbon atoms.

Also utilizable are oligomers of HNCO which are linear rather
than cyclic as in cyanuric acid. For example, cyamelide is
particularly noteworthy. Also utilizable are the known
halocyanuric acids such as the mono-, di- or tri-chloro, bromo,
fluoro or iodo acids or other various mixed-halo substituted
acids.

Any means or technique which results in admixture of HNCO with
the NO-containing gas is included within the scope of this
invention. For example, if the effluent gas stream itself is at
a sufficiently elevated temperature, it can be directly passed
over a solid sample of the HNCO source to effect sublimation and
instantaneous admixture. It is also possible to incorporate the
solid HNCO source into a solvent therefor, most preferably hot
water, and conventionally spray or inject the solution into the
effluent gas stream. Of course, it is also possible to use
conventional heating means (e.g., conductive, inductive, etc.)
to heat the sublimable source of HNCO and then to conventionally
conduct the resultant HNCO gas into admixture with the effluent
stream. Steam injection preceded by passage of the steam over,
through, etc., the HNCO source such as cyanuric acid can, of
course, also be utilized.

It is also possible to indirectly admix the HNCO with the
effluent gas stream. For example, if the HNCO is injected into
the combustion chamber which produces the effluent gas stream or
if the sublimable source such as cyanuric acid is so injected,
the HNCO will be incorporated into the effluent gas stream at
its point of generation. As long as the necessary reaction
conditions are maintained for subsequent interaction of the HNCO
with the NO in the gas stream, the NO reduction method of this
invention will be accomplished. The latter option pertains to
any system which generates an NO-containing stream, including
vehicular engines (wherein the injection of cyanuric acid or
HNCO can be accomplished via the conventional valves), furnaces,
plants, etc. Alternatively, the admixture can be effected
directly either downstream from the point of generation of the
effluent gas or directly near or at this point, e.g., right at
the head of the vehicular engine where the heat generated by the
latter can be utilized, not only for sublimation of the solid
source of HNCO, but also for effecting the NO reducing reactions
based on the presence of HNCO.

The NO content of the effluent streams into which the HNCO has
been admixed will be lowered as long as the temperature of the
effluent stream is raised to a level at which HNCO thermally
decomposes into products which result in lowering of the NO
content. The precise elevated temperature reached is not
critical and will be routinely selected, perhaps in conjunction
with preliminary orientation experiments, in dependence on the
relative amounts of NO and HNCO and especially the residence
time produced by the volumes and flow rates involved. Generally,
temperatures on the order of about 400.degree. C. will suffice
where residence times are greater than or equal to about one
second. Higher temperatures can also be utilized, e.g., about
400.degree. to 800.degree. C.; however, there will be an upper
limit where the nature of the dominant reactions will change. In
the regime of 450.degree.-700.degree. C. free radical reactions
can theoretically produce NO in the presence of oxygen. This
effect can be controlled if it were necessary by the addition of
oxygen scavengers or increased concentrations of HNCO to consume
the nitric oxide produced. At elevated temperatures, i.e.,
greater than 1200.degree. C., the presence of oxygen will make
the production of nitric oxide unacceptable.

Pressure is typically not a critical variable under all
realistic applications. Thus, pressures in the range from about
0.1-10 atmospheres as well as lower or higher values are
employable.

The relative amounts of NO and HNCO are not critical.
Typically, the system will be designed so that stoichiometric
amounts are employed. Of course, excesses of either ingredient
can be designed where desirable. In many applications, it will
be desired to utilize very slight, environmentally acceptable
excesses of NO in order to avoid excesses of HNCO. The latter is
an acid which might recyclize to cyanuric acid at the low
temperatures ensuing after the reaction has run its course.
Thus, since the excess of NO can be chosen to be benignly low in
view of the great efficacy of this invention in reducing NO
contents, and since the products of the overall NO-reduction
reactions are nitrogen, carbon dioxide, water and carbon
monoxide (with a minor component of CO), the resultant system
containing benign amounts of NO will cause no environmental
concerns. Of course, where otherwise desirable, the system can
also be run with slight excesses of HNCO. Where excesses are
employed of either ingredient, these can, e.g., be in the range
of about 1.01 to about 1.1 or more on a stoichiometric basis.

In a preferred mode of operation of this invention, the NO
reduction reactions will be conducted in the presence of
surfaces which act as a catalyst for the free radical reactions
which effect the NO reduction. The nature of the surface is not
critical as long as it is catalytically effective, metallic or
otherwise. All those surfaces well known to catalyze related
free radical reactions will be employable, e.g., metallic
surfaces, oxides, etc. For metallic systems, preferably, the
metal component will be iron which will typically be provided by
the steel, stainless steel, or other iron-based surfaces
utilized in plants, vehicles, factories, etc., and especially
utilized in the conduits containing effluent gas streams, e.g.,
mufflers, smokestacks, etc. Other typical metals include the
usual transition metals, e.g., the noble metals, including
platinum, palladium, rhodium, silver, gold, etc. as well as
nickel, cobalt, chromium, manganese, vanadium, titanium, etc. In
a further preferred embodiment, the reaction will be conducted
in a chamber containing particles of such catalytic surfaces,
e.g., pellets, beads, granules, etc. The particle sizes and
distributions are not critical. As usual, the greater the
surface area, the more efficient this effect will be. Where
catalytic surfaces are utilized, residence times can be shorter
and temperatures can be lower under otherwise identical
conditions. Without wishing to be bound by theory, it is felt
that the catalytic effect is primarily exerted in initiating the
generation of free radicals triggering chain reactions necessary
for the NO reduction.

Other components may also be present in the NO-containing
stream without adversely impacting this invention. For example,
where NO.sub.2 is involved, it also will be removed by this
invention. However, under the normal conditions where NO is a
problem, NO.sub.2 often is not a problem. The amount of NO in
the effluent gas stream also is not critical. Typically, the
amounts will be 1 ppm or more, e.g., 1-10,000 ppm or 10-5,000
ppm, typically 100-1,000 ppm, etc. By routine, judicious
selection of reaction conditions as described above, the amount
of NO after admixture with HNCO can be reduced to any desired
low level, including 0 ppm within limits of detection. Greater
reductions in NO contents in a given system can be achieved by
utilizing longer residence times and higher temperatures.

FIG. 1 illustrates one embodiment of a system of this
invention. The overall "device" 1 simply comprises means such as
chamber 2 for holding the sublimable compound; means for heating
the latter to its sublimation temperature, e.g., in FIG. 1 the
means simply being the input gas stream 3 which is at an
elevated temperature; means for contacting the resultant HNCO
with the input stream, which here simply comprises the adjoining
conduits whereby the input stream heats the cyanuric acid and
the resultant HNCO is instantaneously mixed with the input
stream; and means for conducting the reaction, here illustrated
by furnace 4. Many other equivalents will be very clear to
skilled workers. For example, one or both of the storage chamber
and the furnace can be inductively, conductively, radiatively,
etc., heated using external sources other than the input stream
itself. One or both of storage chamber and furnace region can be
located anywhere along the path of the effluent stream, e.g.,
they can be located right at the head of an engine or the
exhaust outlet of a furnace or plant. As discussed above, it is
even possible for the storage means to be located upstream of
the chamber which produces the effluent stream where this is
practical. Conventional heat exchange means can also be
incorporated into the system wherever desirable. In FIG. 1, the
heat exchange means is the input gas itself.

Without wishing to be bound by theory, the following is a
proposed mechanism for the NO reduction system: ##STR4##

As can be seen, free radicals are generated which cause chain
reactions to ensue. This explains both the speed and high
efficiency of the system in removing NO from the gas stream. The
reaction mechanism is highly surprising since the weakest bond
in the HNCO molecule has a strength of about 60 kcal whereupon
it would have been expected that a much higher temperature than
those in the range of 400.degree.-800.degree. C. would be
necessary for a significant effect based on decomposition of
HNCO.

This mode of action also serves to further clarify the
distinction between this invention and the more conventional
chemistry known for HNCO, e.g., that is described in Back et
al., supra. In the latter, no elevated temperatures were used;
only a purely photolytic decomposition of HNCO was effected In
addition, the lowering of NO content mentioned in this reference
related only to relatively high pressures of NO in the several
torr range.

This reaction mechanism also involves a possible interfering
effect of oxygen on the system of this invention. The hydrogen
atoms produced during the course of this invention will react
with oxygen to produce OH and O. In turn, these species will
result in production of NO and H: ##STR5## This mechanism of
producing NO, however, is generally not important at
temperatures of about 1100.degree.-1200.degree. C. or lower.
Another NO-producing, H-atom mechanism is ##STR6## This is
significant at low temperatures; its adverse influence can be
significantly ameliorated by the H atom producing or
regenerating species (e g., CO, etc.) mentioned herein.

Any of the known scavengers of O can be included in the
reaction system when oxygen is present in order to eliminate or
very significantly ameliorate the oxygen effect were it a
problem. The preferred scavenger is water which exerts its
effect in accordance with the following equation: ##STR7## As a
result, H atoms are regenerated without coproduction of NO. This
permits the reaction: ##STR8## to dominate with overall loss of
NO.

Generally the molar ratio of H.sub.2 O to O.sub.2 can be in the
range of 2-5 to 1.

Under typical operating conditions of vehicular engines now in
use, the above potential interfering effect of O.sub.2 will
inherently be avoided also because of the inherent presence of
H.sub.2 O in the effluent gas streams emanating from such
engines. However, where oxygen is present and were it a problem
and the necessary O scavenger is not inherently provided, any
conventional means for introducing a scavenger such as water can
be utilized. Many other scavengers can also be employed, e.g.,
typical components of fuels utilized in engines, furnaces,
plants, etc., including alkenes, other unsaturated hydrocarbons,
and many other well known organic compounds. As an alternative
to use of suitable scavengers, increased concentrations of HNCO
can be used to reduce nitric oxide that is produced by the
presence of oxygen were it a problem.

Under operating conditions usually encountered, there should be
no other significant interferants for the system of this
invention, i.e., no other species which will react fast with H
alone. In general, conditions under which high concentrations of
such species are generated will be conditions wherein not much
NO is generated anyway. Where NO is a problem, it is unlikely
that species other than O.sub.2 will be interfering. Where
species which are slow reacting with H atoms are present in high
concentration, they will pose much more significant pollution
problems than NO itself.

As is clear from the foregoing, the method of this invention
will be enhanced by addition to the gas stream of species which
enhance the production and/or regeneration of H. In addition to
the mentioned unsaturated hydrocarbons, a most preferred
embodiment of this aspect of the invention is that shown above
in the equation ##STR9## which as is self-evident, generates H
free radicals.

The carbon monoxide utilized in this reaction can have
exogenous or endogenous origin. In the former case, a source of
carbon monoxide can be added to the exhaust stream before,
during at or after the time and/or physical location of HNCO
addition. Any source of CO which is available will be
applicable, especially those which are most convenient, e.g., CO
contents of the same gas stream being treated or other gas
streams. Of course, a commercially available CO can also be
added where cost effective.

It is also possible to modify the apparatus which is the source
of the exhaust gas stream to operate in a manner which
inherently provides the desirable increased amounts of CO where
applicable. For example, an engine can be re- or de-tuned on one
or more cylinders in such a manner that the desired level of
increased CO production ensues. Alternatively, a secondary small
flame or other combustion can be effected, e.g., by flaming of a
small side stream under rich conditions, thereby producing an
exhaust gas having increased amounts of CO which can be mixed
with the primary effluent. The latter is especially applicable
to systems combusting diesel and other oil-based energy sources.
Such a secondary flame based on methane, for example, would also
have the advantage of producing not only CO but also H.sub.2
which further produces H atoms in the system of this invention.
Typically, such a secondary flame running 20% rich will produce
an exhaust stream containing on the order of 5% CO. Heat
generated in such a secondary combustion can, of course, be
conventionally recycled.

In yet another technique, a catalyst can be placed upstream of
the location of this invention under conditions which produce a
reaction generating CO from the exhaust stream components. It is
even possible to run a side stream of HNCO itself through an
appropriate catalyst to cause generation of CO. Suitable
catalysts, of course, are very well known and include those
widely used in automobile anti-pollution devices.

As can be seen, essentially any method of admixing CO into the
reaction regime where the reactions of this invention are
ongoing will be satisfactory and is included within the scope of
this invention. Generally, it will be preferred to employ in the
gas being treated in accordance with this invention an amount of
CO on the order of 1500-4500 ppm, typically 2000-4000 ppm.
However, much higher and much lower amounts of carbon monoxide
can be utilized as well. A primary advantage of carbon monoxide
addition is a lowering of the temperature needed for generation
of sufficient H atoms to result in the desired NO reduction.
Typically, for an addition of 2000-4000 ppm, there will be a
lowering of this minimum temperature by about 250.degree. C. Of
course, the precise correlation between the temperature lowering
and the amount of CO added will be a function of the particular
conditions and system involved. Where amounts of CO greater than
4000 ppm are utilized, the temperature will be lowered to a
greater degree; where amounts less than the preferred minimum of
2000 ppm are utilized, the temperature lowering will be lower
than mentioned. This temperature lowering effect of carbon
monoxide or other hydrogen generating species (as discussed
above and below) is a major advantage since it significantly
lowers the minimum temperature requirements. In many systems it
would otherwise be necessary to heat up the entire exhaust gas
for the most efficient operation of this invention. Typically,
by incorporating CO in accordance with this invention, the
method can operate very well in most systems at temperatures in
the range of 700.degree.-800.degree. C. In this sense, CO
addition causes an effect similar to that caused by the
catalytic surfaces mentioned above.

Other hydrogen atom generating species can also be employed
analogously to the details given above for CO. Examples include
those mentioned above, e.g., unsaturated hydrocarbons such as
the olefins (ethylene, propylene,. butylene, etc.) and the
alkenes (e.g., acetylene, propyne, butyne, etc.). Saturated
hydrocarbons are much less preferred because H atom generation
is much less efficient and significant side product production
ensues. Generally, where hydrocarbons are involved, the weaker
the CH bond provided by the species the better. Weaker bonds
provide more significant temperature lowering, i.e., require
lower temperatures for H atom extraction by a species such as
OH, O, etc. Thus, branched, unsaturated hydrocarbons are also
preferred.

Thus, as can be seen, the amount of CO or other H-atom
generating means desired in a given application will
straightforwardly vary with the desired operating temperatures.
Where it is desired to lower the operating temperature to a
greater degree, larger amounts of CO or other H atom generating
species will be added and vice-versa. The same relationship also
exists versus other reaction parameters such as residence time;
in essence, the less necessary it is to minimize the energy
needed for efficient NO reduction, the less necessary it will be
to add larger amounts of CO.

In essence, the amount of CO or other H-atom generating species
can be chosen at will within the above guidelines as long as the
amount added is not present in such large excess that it creates
an environmental concern itself or causes such a rapid
generation of free radicals and rapid temperature increase that
the overall reaction becomes out of control. Of course, these
effects can be readily avoided by routine considerations by
skilled workers, perhaps with a few routine optimization tests
where desired.

Without further elaboration, it is believed that one skilled in
the art can, using the preceding description; utilize the
present invention to its fullest extent. The following preferred
specific embodiments are, therefore, to be construed as merely
illustrative, and not limitative of the remainder of the
disclosure in any way whatsoever.

In the foregoing and in the following examples, all
temperatures are set forth uncorrected in degrees Celsius and
unless otherwise indicated, all parts and percentages are by
weight.

The entire text of all applications, patents and publications,
if any, cited above and below are hereby incorporated by
reference.

**EXAMPLE 1**

A 7.2 horsepower Onan diesel engine was utilized for the
experiment. Its exhaust had a flow-rate of 100 l/m. A 2 l/m
sample was introduced into a cyanuric acid sublimation chamber.
The latter contained 50 g of cyanuric acid and the sublimation
occurred at 350.degree. C. Thereafter, the mixture of HNCO and
exhaust gas was passed through a furnace region packed with a
bed of steel ball bearings. The temperature in the furnace
region was maintained at a temperature equal to or greater than
450.degree. C. utilizing a conventional heater. The effluent
from the furnace region was passed into a NO.sub.x analyzer. The
residence time in the furnace was about 1 second.

The exhaust gas from the diesel engine included the usual soot,
water, oxygen and CO.sub.2. Its 500 ppm NO content was reduced
to less than 1 ppm (i.e., to the sensitivity level of the
NO.sub.x analyzer). The load on the engine varied from 0.23 to
0.8 with no effect observed on the process.

**EXAMPLE 2**

Under the conditions of Example 1, 5 pounds of cyanuric acid
(2.27 kg) is loaded into the holding chamber. This provides
enough active ingredient (53 moles of HNCO) to remove
approximately 50 moles of NO. At a typical NO concentration in a
vehicle exhaust of 500 ppm, 2.5.times.10.sup.7 liters of gas can
be scrubbed. This is sufficient to remove NO from the exhaust
gas of automobiles for a driving range of approximately 1,500
miles.

The preceding examples can be repeated with similar success by
substituting the generically or specifically described reactants
and/or operating conditions of this invention for those used in
the preceding examples.

From the foregoing description, one skilled in the art can
easily ascertain the essential characteristics of this
invention, and without departing from the spirit and scope
thereof, can make various changes and modifications of the
invention to adapt it to various usages and conditions.

---



**US Patent # 4,908,893**

**No Reduction using Sublimation of Cyanuric
Acid**

**Robert Perry**

**Abstract ~** An arrangement for reducing the NO content
of a gas stream comprises contacting the gas stream with NHCO
into a temperature effective for heat induced decomposition of
HNCO and for resultant lowering of the NO content of the gas
stream. Preferably, the HNCO is generated by sublimation of
cyanuric acid.

**Description ~  BACKGROUND OF THE INVENTION**

This invention relates to a new method and device for removing
NO.sub.x from gaseous material, e.g., from exhaust gas streams.

The recent emphasis on ecological and environmental concerns,
especially air pollution, acid rain, photochemical smog, etc.,
has engendered a wide variety of proposed methods for removing
NO.sub.x, especially NO from gas streams.

Certain proposed techniques involve a great deal of capital
outlay and require major consumption of additives, scrubbers,
etc. For example, U.S. Pat. No. 3,894,141 proposes a reaction
with a liquid hydrocarbon; U.S. Pat. No. 4,405,587 proposes very
high temperature burning with a hydrocarbon; U.S. Pat. No.
4,448,899 proposes reaction with an iron chelate; and U.S. Pat.
No. 3,262,751 reacts NO with a conjugated diolefin. Other
methods utilize reactions with nitriles (U.S. Pat. No.
4,080,425), organic N-compounds (e.g., amines or amides) (DE 33
24 668) or pyridine (J57190638). Application of these reactions
imposes organic pollutant disposal problems along with the
attendant problems of toxicity and malodorous environments. In
addition, they require the presence of oxygen and are relatively
expensive.

Other systems are based on urea reactions. For example, U.S.
Pat. No. 4,119,702 uses a combination of urea and an oxidizing
agent which decomposes it, e.g., ozone, nitric acid, inter alia;
U.S. Pat. No. 4,325,924 utilizes urea in a high temperature
reducing atmosphere; and U.S. Pat. No. 3,900,554 (the
thermodenox system) utilizes a combination of ammonia and oxygen
to react with nitric oxide. All of these methods must deal with
the problem of the odor of ammonia and its disposal. All require
oxygen or other oxidizing agents. These methods also suffer from
the drawback of requiring controlled environments which make
them difficult to use in mobile vehicles or smaller stationary
devices.

Japanese Publication J55051-420 does not relate to the removal
of nitric oxide from gaseous systems, at least as reported in
Derwent Abstract 38871C/22. It utilizes halocyanuric acid to
remove malodorous fumes, e.g., mercaptans, sulfides, disulfides,
ammonia or amines from gases by contact therewith followed by
contact with activated carbon. Temperatures are reported as less
than 80.degree. C.; classical acid/base interactions appear to
be involved (not pyrolysis decomposition products of the
halocyanuric acid).

Back et al. Can. J. Chem. 46, 531 (1968), discusses the effect
of NO on the photolysis of HNCO, the decomposition product of
cyanuric acid. An increase of nitrogen concentration in the
presence of large amounts of nitric oxide (torr levels) was
observed utilizing a medium pressure mercury lamp for photolysis
of HNCO. High temperature reactions were neither addressed nor
involved; similarly, the effect, if any, of HNCO under any
conditions on low amounts of NO (e.g., in the <torr to ppm
range) was also not addressed. In fact, the increased
concentration of nitrogen was associated by the authors with
high NO levels. Their theorized reactions explaining the results
would be important only at high NO levels.

Furthermore, use of cyanuric acid as a source of isocyanic acid
(HNCO) for purposes of studying various properties of the latter
or its subsequent degradation products is also known. See, e.g.,
Okabe, J. Chem. Phys., 53, 3507 (1970) and Perry, J. Chem.
Phys., 82, 5485 (1985). J.P. 53-28771 discloses the addition of
relatively large particles (0.1-10 mm, preferably 0.5-5.0 mm) of
cyanuric acid at temperatures generically disclosed as
600.degree.-1500.degree. C., but preferably at high temperatures
of 1200.degree.-1300.degree. C., for removal of NO.sub.x from
exhaust gas. The theory of operation disclosed in this
publication appears to involve a reaction occurring on the
surface of the particle which leads to the requirements of the
high particle size and high temperature. It is explicitly stated
in the publication that, "If the diameter of the granule is too
small, the efficiency goes down." There is no suggestion in this
publication that the active species effecting the treatment of
the exhaust gas is itself gaseous and certainly no suggestion
that the gaseous species is HNCO. As a result, the conditions
disclosed in this reference lead away from those which are most
applicable to a reaction of NO.sub.x with gaseous HNCO.
Consequentially, the process of this reference is believed not
to have been used on a technical scale.

As a result, there continues to be a need for a simple,
relatively inexpensive, non-polluting, non-toxic non-malodorous
and regenerable system, method and device for removing nitric
oxide from gas streams.

**SUMMARY OF THE INVENTION**

Accordingly, it is an object of this invention to provide such
a system, method and device.

It is another object of this invention to provide such a
method, system and device which is applicable to small
stationary devices, mobile vehicles, as well as to larger
applications, including smokestacks from plants, furnaces,
manufacturing factories, kilns, vehicles, and essentially any
other source of exhaust gas containing NO, particularly
industrial gases.

Upon further study of the specification and appended claims,
further objects and advantages of this invention will become
apparent to those skilled in the art.

These objects have been attained by this invention by providing
a method of reducing the NO content of a gas stream comprising
contacting the gas stream with HNCO at a temperature effective
for heat induced decomposition of HNCO and for resultant
lowering of the NO content of the gas stream. It is preferred
that the HNCO be generated by sublimation of cyanuric acid.

In another aspect, these objects have been achieved by
providing a device useful for reducing the NO content of a gas
stream comprising:

means for storing a compound which upon sublimation generates
HNCO;

means for subliming said compound in operation;

means for contacting said NO-containing gas stream with said
generated HNCO; and

means for raising the temperature of said gas contacted with
HNCO to a level effective for heat induced decomposition of HNCO
and resultant lowering of the NO content of the gas stream.

In yet another aspect, these objects have been achieved by
providing in a conduit means for an effluent gas stream
containing NO, the improvement wherein the conduit means further
comprises device means for lowering the NO content of said gas,
said device means comprising:

compartment means for storing a compound which upon sublimation
generates HNCO;

means for heating said compound to a temperature at which it
sublimes;

means for contacting said NO-containing gas stream with said
generated HNCO; and

means for raising the temperature of said HNCO-contacted gas
stream to a level effective for heat induced decomposition of
HNCO and resultant lowering of the NO content of the gas stream.

**BRIEF DESCRIPTION OF THE DRAWINGS**

Various other objects, features and attendant advantages of the
present invention will be more fully appreciated as the same
comes better understood when considered in connection with the
accompanying drawings, in which like reference characters
designate the same or similar parts throughout the several
views, and wherein:

FIG. 1 schematically illustrates one possible configuration for
carrying out the method of this invention and for configuring
the device and/or improved conduit of this invention.

**DETAILED DISCUSSION**

This invention provides many significant advantages over other
theoretical and/or commercially available NO reducers. It is
generically applicable to all industrial gas effluent streams,
e.g., those mentioned in the references discussed above. It is
very simple, inexpensive and portable. It does not require the
use of catalysts and/or co-agents. In addition, when the
preferred source of HNCO (cyanuric acid) is spent during
operation, it can be simply and inexpensively replaced. It
provides heretofore unachievable convenience and efficiency in
reducing NO. Its non-toxicity is another major advantage as its
ready availability and low cost.

As opposed to many of the other systems now available, that of
this invention imposes minimal changes in otherwise preferred
operating conditions for the engine, plant, factory, etc., which
generates the effluent gas stream being purified. For example,
as opposed to presently utilized catalytic converters, this
invention does not impose a requirement that a vehicular engine
be run rich with resultant undesirable lower compression ratios.
In addition, the requirement for use of unleaded gas in order to
avoid catalyst poisoning also does not apply. Overall, the
efficacy of the system of this invention in lowering NO contents
is extremely high.

Within the broadest scope of this invention, any source and/or
means of generating HNCO and admixing it with the effluent
stream can be used. For a variety of reasons including those
discussed above, in the preferred embodiment, sublimation of
cyanuric acid will be utilized: ##STR1##

Isocyanuric acid is a tautomer of cyanuric acid. For purposes
of this invention, the two are equivalent. The sublimation of
cyanuric acid in accordance with the following equation,
##STR2## can be conducted at any temperature effective to cause
a volatilization of sufficient HNCO for the desired purpose. In
general, temperatures greater than 300.degree. C. will be
utilized since sublimation rates at lower temperatures are
generally too low. Preferably, temperatures greater than
320.degree. C. will be used, especially greater than 350.degree.
C. There is no preferred upper limit on temperature; but
generally a temperature less than about 1200 C. will be
employed. The precise temperature for a given application can be
routinely selected, perhaps with a few orientation experiments,
in conjunction with considerations of the volume to be filled,
the flow rate of the gas, the resultant residence time of the
admixture of HNCO and NO is the effluent gas stream, the surface
area of the HNCO source which is being sublimed and the
sublimation rate which ensues in a given system upon selection
of the given temperature. For example, for 50 g of a cyanuric
acid sample having a surface area of about 20 cm.sup.2, the
sublimation rate achieved at a temperature of 450.degree. C. is
sufficient to reduce the NO level from a 50 l/m gas stream from
1000 ppm to essentially 0 ppm.

While cyanuric acid itself is the preferred source of HNCO,
other sublimable solids can also be used for its generation.
These include other compounds which are typical impurities in
samples of cyanuric acid, including ammelide and ammeline
##STR3## In general, cyanuric acid wherein the OH groups are
replaced by 1-3 NH.sub.2, alkyl, NH-alkyl or N-alkyl.sub.2
groups, are utilizable. Such alkyl groups typically will have
1-4 carbon atoms.

Also utilizable are oligomers of HNCO which are linear rather
than cyclic as in cyanuric acid. For example, cyamelide is
particularly noteworthy. Also utilizable are the known
halocyanuric acids such as the mono-, di- or tri-chloro, bromo,
fluoro or iodo acids or other various mixed-halo substituted
acids.

Any means or technique which results in admixture of HNCO with
the NO-containing gas is included within the scope of this
invention. For example, if the effluent gas stream itself is at
a sufficiently elevated temperature, it can be directly passed
over a solid sample of the HNCO source to effect sublimation and
instantaneous admixture. It is also possible to incorporate the
solid HNCO source into a solvent therefor, most preferably hot
water, and conventionally spray or inject the solution into the
effluent gas stream. Of course, it is also possible to use
conventional heating means (e.g., conductive, inductive, etc.)
to heat the sublimable source of HNCO and then to conventionally
conduct the resultant HNCO gas into admixture with the effluent
stream. Steam injection preceded by passage of the steam over,
through, etc., the HNCO source such as cyanuric acid can, of
course, also be utilized.

It is also possible to indirectly admix the HNCO with the
effluent gas stream. For example, if the HNCO is injected into
the combustion chamber which produces the effluent gas stream or
if the sublimable source such as cyanuric acid is so injected,
the HNCO will be incorporated into the effluent gas stream at
its point of generation. As long as the necessary reaction
conditions are maintained for subsequent interaction of the HNCO
with the NO in the gas stream, the NO reduction method of this
invention will be accomplished. The latter option pertains to
any system which generates an NO-containing stream, including
vehicular engines (wherein the injection of cyanuric acid or
HNCO can be accomplished via the conventional valves), furnaces,
plants, etc. Alternatively, the admixture can be effected
directly either downstream from the point of generation of the
effluent gas or directly near or at this point, e.g., right at
the head of the vehicular engine where the heat generated by the
latter can be utilized, not only for sublimation of the solid
source of HNCO, but also for effecting the NO reducing reactions
based on the presence of HNCO.

The NO content of the effluent streams into which the HNCO has
been admixed will be lowered as long as the temperature of the
effluent stream is raised to a level at which HNCO thermally
decomposes into products which result in lowering of the NO
content. However, there will be an upper limit beyond which the
nature of the predominant reactions ensuing from the
decomposition of HNCO will change in such a fashion that the
desired reduction in NO.sub.x will not occur. At elevated
temperatures, greater than 1200.degree. C., the presence of
oxygen will make the production of nitric oxide un-acceptable.
Thus, the temperature at which the decrease in the effectiveness
of this invention will occur is on the order of 1200.degree. C.
and higher.

More generally, the preferred upper limit on the temperature
will be less than 1200.degree. C. (e.g., less than 1190) in
dependence on the usual factors, including diameter of the
effluent stream, its velocity, the particle size of the added
HNCO-generating agent where applicable, the gas or particle
injection technique and configuration, the residence time of the
reaction, e.g., the length available for the reaction, the
involved concentrations and amounts of NO.sub.x and agent of
this invention, etc. Thus, in dependence on such factors, the
upper limit can encompass a wide variety of values on the order
of the mentioned "less than 1200.degree. C.", e.g., less than
values such as 1195, 1190, 1175, 1150, 1125, 1100, 1075, 1050,
1025, 1000, 975, 950, etc. Typically, the upper limit will fall
in the range of 1100.degree.-1200.degree. C. or higher. This
relatively lower temperature regime is one aspect of the present
invention which clearly distinguishes it from the treatment of
JP 54-28771.

The preferred temperature of operation for a given system will
again vary with the usual considerations such as those mentioned
above. Typically, the higher available temperatures will be
preferred because of the more favorable reaction kinetics
associated therewith. Thus, reactions will often preferably be
conducted in the range of 700.degree.-1100.degree. C., more
preferably 900.degree.-1050.degree. C., especially
850.degree.-1000.degree. C. One of the major advantages of this
invention is that the reaction, once initiated, will continue to
occur to a substantial degree at significantly lower
temperatures, i.e., from the sublimation point of the solid
agent such as cyanuric acid up to these preferred temperatures.
Thus, the reaction will ensue substantively at temperatures such
as about 350.degree.-700.degree. C. or even lower, e.g., at
temperatures of 400.degree.-700.degree. C. or
450.degree.-600.degree. C. or temperatures less than 600.degree.
C. For example, temperatures on the order of about 400.degree.
C. will often suffice where residence times are greater than or
equal to about one second. For prior art systems, including the
prior art system of JP 54-28771, by implication, substantial
reduction of NO.sub.x at temperatures lower than the high
temperatures typically required (e.g., less than about
900.degree. C. for ammonia injection) does not occur.

On the other hand, for this invention, even when an exhaust gas
stream reaches a low temperature, e.g., less than 600.degree.
C., substantial reduction of NO.sub.x in accordance with this
invention will continue to occur. This represents a major
advantage since exhaust gas streams inevitably cool during their
passage from the point of generation. Thus, in those common
situations where not all of the NO.sub.x is removed during the
time that the exhaust gas stream is at the requisite high
temperature of the prior art, this invention will continue to
provide NO.sub.x reduction. This invention represents a very
efficient technique both at temperatures greater than
600.degree. C., e.g., 601.degree. C. to the upper limit
discussed above and also at temperatures less than 600.degree.
C., e.g., at temperatures from the lower limit discussed above
up to 599.degree. C.

Thus, in one unique aspect of this invention, there is provided
a method for at least partially decreasing the concentration of
NO.sub.x in an exhaust gas stream at a temperature less than
600.degree. C., e.g., at a temperature less than or equal to
590.degree. C., 570.degree. C., 550.degree. C., 500.degree. C.,
450.degree. C., 400.degree. C., etc.

The amount of NO.sub.x reduction which might occur at such
heretofore inoperable, low temperatures will be a function of
the usual parameters (see above) including the highest available
temperature upstream, the residence time upstream, the NO.sub.x
initial concentration, etc.

The temperature at which the HNCO or HNCO-generating solid is
added to the exhaust gas stream will also be a function of the
usual parameters including those mentioned above. Typically, it
will be desired to achieve the HNCO presence at as high a
temperature as possible within the constraints mentioned above
and the availability of suitable energy. Since a free radical
mechanism is involved, a suitably high initiation temperature
will more quickly achieve a sufficiently high concentration of
radicals to cause rapid achievement of an adequately high
concentration of the active species to correspondingly quickly
commence NO.sub.x reduction. Once free radical initiation
ensues, the preference for high reaction tempertures will be
lowered in accordance with the foregoing.

Another consequence of the discovery of this invention that
HNCO is the active species, i.e., that the active species is
itself gaseous in nature under the relevant conditions, is that
certain particle size ranges will be preferred when the HNCO is
not added directly to the gas stream as a gas, i.e., is added in
the form of a solid which produces HNCO, e.g., a sublimable
solid such as cyanuric acid. The basic principle is to produce
the active gaseous species as quickly and efficiently as
possible. Typically, the smaller the particle size the better,
taking into account the usual engineering considerations.
Preferably, the average particle size will be less than 100
microns, e.g., less than or equal to about 95, or 90, or 80, or
70, or 60, or 50, or 40, or 30, or 20, or 10, etc. Typically,
the preferred particle sizes will be in the range of 1 to less
than 100 microns, most preferably in the range of from 10 to
less than 100 microns. The precise particle size range preferred
for a given application will be a function of the usual
considerations including system temperature, exhaust stream
diameter, available residence times, the efficiency and
configuration of the injection system, etc.

As is well known, for smaller diameter streams, e.g., those
typically encountered in vehicular systems, direct admixture of
gaseous HNCO to the exhaust gas stream is typically preferred;
for larger cross-section systems such as those encountered in
typical smokestack exhausts, it is difficult to achieve adequate
gas-gas mixing in the available times whereupon injection or
other addition of particles is the preferred mode. It is also
possible to inject a combination of particles and gaseous HNCO,
e.g., by employing an injection configuration which provides the
possibility for preheating the particles to be injected in a
chamber whereupon both gaseous HNCO and solid material are
introduced directly into the exhaust gas system. This also
enhances the initiation of the reaction for the reasons
discussed above. In a related embodiment, it is also preferred
to include in the injection material (particles, gas or a
mixture thereof), HNCO generating substances which have a
particularly favorable decomposition profile such as ammeline.

Except as indicated otherwise herein, details of the mixing of
the exhaust gas stream with solid particles or directly with
gaseous HNCO will be in accordance with the usual conventional
considerations as discussed thoroughly in the literature, e.g,
in Combustion and Mass Transfer, D. Bryan Spalding, Pergammon
Press 1979.

As discussed above, the preferred technique is addition of
gaseous HNCO directly to the exhaust gas stream or addition of
particles having diameters as discussed above. In other
preferred aspects, the solid material can be added in the form
of a solution in a solvent preferably hot water or as a slurry
in an appropriate liquid, also preferably water, i.e., at a
temperature where the solid agent is not fully dissolved. Other
suitable solvents or dispersing fluids, e.g., liquid CO.sub.2,
N.sub.2, etc., of course can also be used. These aspects provide
ease of handling via conventional pumps.

Thus, for example, cyanuric acid can be dissolved in high
temperature, high pressure water, especially in power plant
environments where saturated water/steam is readily available,
e.g., typically at 180.degree. C. (150 psi). Solid or slurry
injection can, for example, be accomplished by the use of a lead
screw connecting the exhaust stream with the powder or slurry
reservoir of the solid agent such as cyanuric acid. Steam
injection is also preferred. Particle size considerations in
such slurries will be in accordance with the foregoing. Where
direct injection of gaseous HNCO is employed, it will be
preferred to use a heated pre-chamber to avoid occasional
plugging of metering devices where this may be a problem, e.g.,
due to polymerization of HNCO on cold surfaces.

As can be seen from the foregoing, this invention involves the
discovery that HNCO can be used to very efficiently remove
NO.sub.x from exhaust gas streams under conditions where the
reaction with NO.sub.x occurs substantially solely in the gas
phase with HNCO and not on the surfaces of particles of
substances which can optionally be used to generate the HNCO.
Accordingly, contrary to the disclosure of JP 54-28771, the
conditions are to be chosen in order to facilitate the
sublimation or other conversion of substantially all of such
solid particles into gaseous HNCO before and/or during the
reaction(s) which is effective to lower the NO.sub.x
concentration.

In a further feature of this invention, it has been discovered
that the underlying process is relatively insensitive to prior
art interferants including particulates such as fly ash and
oxygen. Because of its unique features, it is especially
advantageously applicable to systems which heretofore have
presented a relatively severe NO.sub.x problem such as systems
based on diesel or coal combustion, e.g., boilers, smokestack
exhausts, etc.

Pressure is typically not a critical variable under all
realistic applications. Thus, pressures in the range from about
0.1-10 atmospheres as well as lower or higher values are
employable.

The relative amounts of NO or HNCO are not critical. Typically,
the system will be designed so that approximately stoichiometric
amounts are employed. Of course, excesses of either ingredient
can be designed where desirable. In many applications, it will
be desired to utilize very slight, environmentally acceptable
excesses of NO in order to avoid excesses of HNCO. The latter is
an acid which might recyclize to cyanuric acid at the low
temperatures ensuing after the reaction has run its course.
Thus, since the excess of NO can be chosen to be benignly low in
view of the great efficacy of this invention in reducing NO
contents, and since the products of the overall NO-reduction
reactions are nitrogen, carbon dioxide, water and carbon
monoxide (with a minor component of CO), the resultant system
containing benign amounts of NO will cause no environmental
concerns. Of course, where otherwise desirable, the system can
also be run with slight excesses of HNCO. Where excesses are
employed of either ingredient, these can, e.g., be in the range
of about 1.01 to about 1.1 or more on a stoichiometric basis.
However, it also will often be desirable to use larger excesses
of HNCO to ensure the optimum NO.sub.x removed, e.g., molar
equivalent excesses in the range of 1.1-10/1, typically less
than 5/1, 4/1, 3/1, 2/1, etc., or generally in the range of 1/1
to 5/1, etc.

In a preferred mode of operation of this invention, the NO
reduction reactions will be conducted in the presence of
surfaces which act as a catalyst for the free radical reactions
which effect the NO reduction. The nature of the surface is not
critical as long as it is catalytically effective, metallic or
otherwise. All those surfaces well known to catalyze related
free radical reactions will be employable, e.g., metallic
surfaces, oxides, etc. For metallic systems, preferably, the
metal component will be iron which will typically be provided by
the steel, stainless steel, or other iron-based surfaces
utilized in plants, vehicles, factories, etc., and especially
utilized in the conduits containing effluent gas streams, e.g.,
mufflers, smokestacks, etc. Other typical metals include the
usual transition metals, e.g., the noble metals, including
platinum, palladium, rhodium, silver, gold, etc. as well as
nickel, cobalt, chromium, manganese, vanadium, titanium, etc. In
a further preferred embodiment, the reaction will be conducted
in a chamber containing particles of such catalytic surfaces,
e.g., pellets, beads, granules, etc. The particle sizes and
distributions are not critical. As usual, the greater the
surface area, the more efficient this effect will be. Where
catalytic surfaces are utilized, residence times can be shorter
and temperatures can be lower under otherwise identical
conditions. Without wishing to be bound by theory, it is felt
that the catalytic effect is primarily exerted in initiating the
generation of free radicals triggering chain reactions necessary
for the NO reduction.

Other components may also be present in the NO-containing
stream without adversely impacting this invention. For example,
where NO.sub.2 is involved, it also will be removed by this
invention. However, under the normal conditions where NO is a
problem, NO.sub.2 often is not a problem. The amount of NO in
the effluent gas stream also is not critical. Typically, the
amounts will be 1 ppm or more, e.g., 1-10,000 ppm or 10-5,000
ppm, typically 100-1,000 ppm, etc. By routine, judicious
selection of reaction conditions as described above, the amount
of NO after admixture with HNCO can be reduced to any desired
low level, including 0 ppm within limits of detection. Greater
reductions in NO contents in a given system can be achieved by
utilizing longer residence times and higher temperatures.

FIG. 1 illustrates one embodiment of a system of this
invention. The overall "device" 1 simply comprises means such as
chamber 2 for holding the sublimable compound; means for heating
the latter to its sublimation temperature, e.g., in FIG. 1 the
means simply being the input gas stream 3 which is at an
elevated temperature; means for contacting the resultant HNCO
with the input stream, which here simply comprises the adjoining
conduits whereby the input stream heats the cyanuric acid and
the resultant HNCO is instantaneously mixed with the input
stream; and means for conducting the reaction, here illustrated
by furnace 4. Many other equivalents will be very clear to
skilled workers. For example, one or both of the storage chamber
and the furnace can be inductively, conductively, radiatively,
etc., heated using external sources other than the input stream
itself. One or both of storage chamber and furnace region can be
located anywhere along the path of the effluent stream, e.g.,
they can be located right at the head of an engine or the
exhaust outlet of a furnace or plant. As discussed above, it is
even possible for the storage means to be located upstream of
the chamber which produces the effluent stream where this is
practical. Conventional heat exchange means can also be
incorporated into the system wherever desirable. In FIG. 1, the
heat exchange means is the input gas itself.

Without wishing to be bound by theory, the following is a
proposed mechanism for the NO reduction system: ##STR4##

As can be seen, free radicals are generated which cause chain
reactions to ensue. This explains both the speed and high
efficiency of the system in removing NO from the gas stream. The
reaction mechanism is highly surprising since the weakest bond
in the HNCO molecule has a strength of about 85 kcal whereupon
it would have been expected that a much higher temperature than
those in the range of 400.degree.-800.degree. C. would be
necessary for a significant effect based on decomposition of
HNCO.

This mode of action also serves to further clarify the
distinction between this invention and the more conventional
chemistry known for HNCO, e.g., that is described in Back et
al., supra. In the latter, no elevated temperatures were used;
only a purely photolytic decomposition of HNCO was effected. In
addition, the lowering of NO content mentioned in this reference
related only to relatively high pressures of NO in the several
torr range.

Without further elaboration, it is believed that one skilled in
the art can, using the preceding description; utilize the
present invention to its fullest extent. The following preferred
specific embodiments are, therefore, to be construed as merely
illustrative, and not limitative of the remainder of the
disclosure in any way whatsoever.

In the foregoing and in the following example, all temperatures
are set forth uncorrected in degrees Celsius and unless
otherwise indicated, all parts and percentages are by volume.

The entire text of all applications, patents and publications,
if any, cited above and below are hereby incorporated by
reference.

**EXAMPLE 1**

A 7.2 horsepower Onan diesel engine was utilized for the
experiment. Its exhaust had a flow-rate of 100 l/m. A 2 l/m
sample was introduced into a cyanuric acid sublimation chamber.
The latter contained 50 g of cyanuric acid and the sublimation
occurred at 350.degree. C. Thereafter, the mixture of HNCO and
exhaust gas was passed through a furnace region packed with a
bed of steel ball bearings. The temperature in the furnace
region was maintained at a temperature equal to or greater than
450.degree. C. utilizing a conventional heater. The effluent
from the furnace region was passed into a NO.sub.x analyzer. The
residence time in the furnace was about 1 second.

The exhaust gas from the diesel engine included the usual soot,
water, oxygen and CO.sub.2. Its 500 ppm NO content was reduced
to less than 1 ppm (i.e., to the sensitivity level of the
NO.sub.x analyzer). The load on the engine varied from 0.23 to
0.8 with no effect observed on the process.

**EXAMPLE 2**

Under the conditions of Example 1, 5 pounds of cyanuric acid
(2.27 kg) is loaded into the holding chamber. This provides
enough active ingredient (53 moles of HNCO) to remove
approximately 50 moles of NO. At a typical NO concentration in a
vehicle exhaust of 500 ppm, 2.5.times.10.sup.7 liters of gas can
be scrubbed. This is sufficient to remove NO from the exhaust
gas of automobiles for a driving range of approximately 1,500
miles.

The preceding examples can be repeated with similar success by
substituting the generically or specifically described reactants
and/or operating conditions of this invention for those used in
the preceding examples.

From the foregoing description, one skilled in the art can
easily ascertain the essential characteristics of this
invention, and without departing from the spirit and scope
thereof, can make various changes and modifications of the
invention to adapt it to various usages and conditions.

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**[http://reaflow.iwr.uni-heidelberg.de/~icders99/program/papers/201-300/254.pdf](http://reaflow.iwr.uni-heidelberg.de/%7Eicders99/program/papers/201-300/254.pdf)**

**"Non Catalytic NO Removal from Gas Turbine Exhaust with
Cyanuric Acid ..."**   
by   
**R. Perry, et al.**

California at Berkeley Berkeley, California 94720, USA   
Robert A. Perry ~ Technor, Inc .

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