Unit Ozkan -- Catalyst for Production of Hydrogen from
Ethanol

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

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**Umit OZKAN**

**Catalyst**

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[**http://www.chbmeng.ohio-state.edu/people/ozkan.html**](http://www.chbmeng.ohio-state.edu/people/ozkan.html)

**Umit OZKAN**

![](pic_ozkan.jpg)

Contact:  Umit Ozkan, (614) 292-6623; Ozkan.1@osu.edu

---

[**http://researchnews.osu.edu/archive/biohydro.htm**](http://researchnews.osu.edu/archive/biohydro.htm)

**A BETTER WAY TO MAKE HYDROGEN FROM BIOFUELS**

 by Pam Frost Gorder

COLUMBUS, Ohio -- Researchers here have found a way to convert
ethanol and other biofuels into hydrogen very efficiently.

A new catalyst makes hydrogen from ethanol with 90 percent
yield, at a workable temperature, and using inexpensive
ingredients.

Umit Ozkan, professor of chemical and biomolecular engineering
at Ohio State University, said that the new catalyst is much
less expensive than others being developed around the world,
because it does not contain precious metals, such as platinum or
rhodium.   
Umit Ozkan

"Rhodium is used most often for this kind of catalyst, and it
costs around $9,000 an ounce," Ozkan said. "Our catalyst costs
around $9 a kilogram."

She and her co-workers presented the research Wednesday, August
20 at the American Chemical Society meeting in Philadelphia.

The Ohio State catalyst could help make the use of
hydrogen-powered cars more practical in the future, she said.

"There are many practical issues that need to be resolved
before we can use hydrogen as fuel -- how to make it, how to
transport it, how to create the infrastructure for people to
fill their cars with it," Ozkan explained.

"Our research lends itself to what's called a 'distributed
production' strategy. Instead of making hydrogen from biofuel at
a centralized facility and transporting it to gas stations, we
could use our catalyst inside reactors that are actually located
at the gas stations. So we wouldn't have to transport or store
the hydrogen -- we could store the biofuel, and make hydrogen on
the spot."

The catalyst is inexpensive to make and to use compared to
others under investigation worldwide. Those others are often
made from precious metals, or only work at very high
temperatures.

"Precious metals have high catalytic activity and -- in most
cases -- high stability, but they're also very expensive. So our
goal from the outset was to come up with a precious-metal-free
catalyst, one that was based on metals that are readily
available and inexpensive, but still highly active and stable.
So that sets us apart from most of the other groups in the
world."

"Whenever a process works at a lower temperature, that brings
energy savings and cost savings," Ozkan said. Also, if the
catalyst is highly active and can achieve high hydrogen yields,
we dont need as much of it. That will bring down the size of
the reactor, and its cost.

The new dark gray powder is made from tiny granules of cerium
oxide -- a common ingredient in ceramics -- and calcium, covered
with even smaller particles of cobalt. It produces hydrogen with
90 percent efficiency at 660 degrees Fahrenheit (around 350
degrees Celsius) -- a low temperature by industrial standards.

"Whenever a process works at a lower temperature, that brings
energy savings and cost savings," Ozkan said. Also, if the
catalyst is highly active and can achieve high hydrogen yields,
we dont need as much of it. That will bring down the size of
the reactor, and its cost.

The process starts with a liquid biofuel such as ethanol, which
is heated and pumped into a reactor, where the catalyst spurs a
series of chemical reactions that ultimately convert the liquid
to a hydrogen-rich gas.

One of the biggest challenges the researchers faced was how to
prevent "coking" -- the formation of carbon fragments on the
surface of the catalyst. The combination of metals -- cerium
oxide and calcium -- solved that problem, because it promoted
the movement of oxygen ions inside the catalyst. When exposed to
enough oxygen, the carbon, like the biofuel, is converted into a
gas and gets oxidized; it becomes carbon dioxide.

At the end of the process, waste gases such as carbon monoxide,
carbon dioxide and methane are removed, and the hydrogen is
purified. To make the process more energy-efficient, heat
exchangers capture waste heat and put that energy back into the
reactor.  Methane recovered in the process can be used to
supply part of the energy.

Though this work was based on converting ethanol, Ozkan's team
is now studying how to use the same catalyst with other liquid
biofuels. Her coauthors on this presentation included Ohio State
doctoral students Hua Song and Lingzhi Zhang.

This research was funded by the Department of Energy.

---

[**http://www.technologynewsdaily.com/node/10180**](http://www.technologynewsdaily.com/node/10180)  
**Technology News ( 08/22/2008 )**

**Hydrogen From Biofuels**

Researchers at Ohio State University have found a way to
convert ethanol and other biofuels into hydrogen very
efficiently. A new catalyst makes hydrogen from ethanol with 90
percent yield, at a workable temperature, and using inexpensive
ingredients. Umit Ozkan, professor of chemical and biomolecular
engineering at Ohio State University, said that the new catalyst
is much less expensive...

Researchers at Ohio State University have found a way to
convert ethanol and other biofuels into hydrogen very
efficiently.

A new catalyst makes hydrogen from ethanol with 90 percent
yield, at a workable temperature, and using inexpensive
ingredients.

Umit Ozkan, professor of chemical and biomolecular engineering
at Ohio State University, said that the new catalyst is much
less expensive than others being developed around the world,
because it does not contain precious metals, such as platinum or
rhodium.

"Rhodium is used most often for this kind of catalyst, and it
costs around $9,000 an ounce," Ozkan said. "Our catalyst costs
around $9 a kilogram."

She and her co-workers presented the research Wednesday, August
20 at the American Chemical Society meeting in Philadelphia.

The Ohio State catalyst could help make the use of
hydrogen-powered cars more practical in the future, she said.

"There are many practical issues that need to be resolved
before we can use hydrogen as fuel -- how to make it, how to
transport it, how to create the infrastructure for people to
fill their cars with it," Ozkan explained.

"Our research lends itself to what's called a 'distributed
production' strategy. Instead of making hydrogen from biofuel at
a centralized facility and transporting it to gas stations, we
could use our catalyst inside reactors that are actually located
at the gas stations. So we wouldn't have to transport or store
the hydrogen -- we could store the biofuel, and make hydrogen on
the spot."

The catalyst is inexpensive to make and to use compared to
others under investigation worldwide. Those others are often
made from precious metals, or only work at very high
temperatures.

"Precious metals have high catalytic activity and -- in most
cases -- high stability, but they're also very expensive. So our
goal from the outset was to come up with a precious-metal-free
catalyst, one that was based on metals that are readily
available and inexpensive, but still highly active and stable.
So that sets us apart from most of the other groups in the
world."

The new dark gray powder is made from tiny granules of cerium
oxide -- a common ingredient in ceramics -- and calcium, covered
with even smaller particles of cobalt. It produces hydrogen with
90 percent efficiency at 660 degrees Fahrenheit (around 350
degrees Celsius) -- a low temperature by industrial standards.

"Whenever a process works at a lower temperature, that brings
energy savings and cost savings," Ozkan said. Also, if the
catalyst is highly active and can achieve high hydrogen yields,
we dont need as much of it. That will bring down the size of
the reactor, and its cost.

The process starts with a liquid biofuel such as ethanol, which
is heated and pumped into a reactor, where the catalyst spurs a
series of chemical reactions that ultimately convert the liquid
to a hydrogen-rich gas.

One of the biggest challenges the researchers faced was how to
prevent "coking" -- the formation of carbon fragments on the
surface of the catalyst. The combination of metals -- cerium
oxide and calcium -- solved that problem, because it promoted
the movement of oxygen ions inside the catalyst. When exposed to
enough oxygen, the carbon, like the biofuel, is converted into a
gas and gets oxidized; it becomes carbon dioxide.

At the end of the process, waste gases such as carbon monoxide,
carbon dioxide and methane are removed, and the hydrogen is
purified. To make the process more energy-efficient, heat
exchangers capture waste heat and put that energy back into the
reactor. Methane recovered in the process can be used to supply
part of the energy.

Though this work was based on converting ethanol, Ozkan's team
is now studying how to use the same catalyst with other liquid
biofuels. Her coauthors on this presentation included Ohio State
doctoral students Hua Song and Lingzhi Zhang.

---

[**http://www.guardian.co.uk/environment/2008/aug/21/biofuels.travelandtransport**](http://www.guardian.co.uk/environment/2008/aug/21/biofuels.travelandtransport) 
(
Thursday August 21 2008 09:57 )

**New Catalyst Boosts Hydrogen as Transport
Fuel**

---

[**http://domesticfuel.com/2008/08/24/turning-ethanol-into-hydrogen/**](http://domesticfuel.com/2008/08/24/turning-ethanol-into-hydrogen/)

**Turning Ethanol Into Hydrogen**

---

[**http://www.thaindian.com/newsportal/south-asia/new-method-enables-conversion-of-biofuels-into-hydrogen-more-efficiently\_10086918.html**](http://www.thaindian.com/newsportal/south-asia/new-method-enables-conversion-of-biofuels-into-hydrogen-more-efficiently_10086918.html)  
Thaindian News ( 08/21/2008 )

**New Method Enables Conversion of Biofuels into Hydrogen
more Efficiently**

---

  
[**http://www.greencarcongress.com/2008/08/new-low-cost-no.html**](http://www.greencarcongress.com/2008/08/new-low-cost-no.html)  
Green Car Congress ( 08/20/2008 )

**New Low-Cost Non-noble Metal Catalyst for Hydrogen
Production from Biofuels**

---

**<http://thomasfortenberry.net/?p=3552>** 
(
08/20/2008 )

**A Better Way to Make Biofuel Hydrogen**

---

[**http://www.thehindu.com/seta/2008/08/21/stories/2008082150971600.htm**](http://www.thehindu.com/seta/2008/08/21/stories/2008082150971600.htm)
( 08/21/2008 )

**Extracting More Hydrogen from Ethanol**

---

[**http://feeds.bignewsnetwork.com/index.php?sid=397111**](http://feeds.bignewsnetwork.com/index.php?sid=397111)  
Big News Network.com ( 08/21/2008 )

**New Method Enables Conversion of Biofuels
into Hydrogen More Efficiently**

---

[**http://www.theengineer.co.uk/Articles/Article.aspx?liArticleID=307647**](http://www.theengineer.co.uk/Articles/Article.aspx?liArticleID=307647)  
The engineer ( 08/21/2008 )

**Efficient Conversion**

---

[**http://www.enn.com/sci-tech/article/37976**](http://www.enn.com/sci-tech/article/37976)  
ENN  ( 08/20/2008 )

**A Better Way to Make Hydrogen from Biofuels**

---

[**http://www.physorg.com/news138450335.html**](http://www.physorg.com/news138450335.html)  
Physorg ( 08/20/2008 )

**A Better Way to Make Hydrogen from Biofuels**

---

[**http://www.newswise.com/articles/view/543567/?sc=rssn**](http://www.newswise.com/articles/view/543567/?sc=rssn)  
Newswise ( 08/20/2008 )

**A Better Way to Make Hydrogen from Biofuels**

---

[**http://www.sciencedaily.com/releases/2008/08/080820163111.htm**](http://www.sciencedaily.com/releases/2008/08/080820163111.htm)  
Science Daily ( 08/20/2008 )

**A Better Way To Make Hydrogen From Biofuels**

---



**US Patent Application   20070110651**   
**Ozkan; Umit S.,   et al.**   
**(  May 17, 2007 )**

**Multi-Stage Catalyst Systems and Uses Thereof**

**Abstract**

Catalyst systems and methods provide benefits in reducing the
content of nitrogen oxides in a gaseous stream containing nitric
oxide (NO), hydrocarbons, carbon monoxide (CO), and oxygen
(O.sub.2). The catalyst system comprises an oxidation catalyst
comprising a first metal supported on a first inorganic oxide
for catalyzing the oxidation of NO to nitrogen dioxide
(NO.sub.2), and a reduction catalyst comprising a second metal
supported on a second inorganic oxide for catalyzing the
reduction of NO.sub.2 to nitrogen (N.sub.2).

Inventors:  Ozkan; Umit S.; (Worthington, OH) ; Holmgreen;
Erik M.; (Columbus, OH) ; Yung; Matthew M.; (Columbus, OH)

**FIELD OF THE INVENTION**

[0002] The present invention is generally directed to systems
and methods of catalytic removal of pollutants in a gaseous
stream, and is specifically directed to systems and methods of
catalytic removal of pollutants via catalyst systems comprising
oxidation and reduction catalysts.

**BACKGROUND OF THE INVENTION**

[0003] Nitrogen oxides (NO, NO.sub.2, N.sub.2O) contribute to
several environmental hazards including global warming, smog,
ground level ozone formation, and acid rain. Emission reduction
is possible through modification of combustion parameters, but
reducing NO.sub.x emissions to acceptable levels requires
effective aftertreatment technologies. Current catalytic
NO.sub.x reduction control technologies include three-way
catalysts and ammonia-based selective catalytic reduction. While
these methods are highly effective for current combustion
technologies, they are unsuitable for the next generation of
high efficiency lean-burn natural gas engines. Three-way
catalysts are inactive in oxygen rich environments, while the
large size and expense of ammonia SCR installations make them an
impractical solution in a distributed energy context.

[0004] NO.sub.x, trap systems have received attention as a
possible solution for lean NO.sub.x removal. These traps rely on
bifunctional materials to store and reduce NO.sub.x under
different engine cycles. Under lean conditions NO.sub.x is
`trapped` on alkali metal oxides, and the engine is then
periodically run under rich conditions to accomplish reduction
over precious metals. These changes in engine operating
conditions would necessitate additional engine controls.
Additionally, current trap materials such as Ba and Pt are
susceptible to sintering and SO.sub.2 poisoning.

[0005] The use of hydrocarbons as reducing agents in NO removal
has attracted significant attention. The presence of
hydrocarbons in current engine exhaust streams would make them a
readily available and cost effective choice. However,
hydrocarbon combustion, particularly in oxygen rich
environments, may block NO reduction reactions.

[0006] As demands increase for methods of removing pollutants,
the need arises for improved systems and methods of pollutant
removal, especially systems operable to offset the hydrocarbon
combustion in oxygen rich environments.

**SUMMARY OF THE INVENTION**

[0007] According to a first embodiment of the present
invention, a catalyst system for reducing the content of
nitrogen oxides in a gaseous stream containing nitric oxide
(NO), hydrocarbons, carbon monoxide (CO), and oxygen (O.sub.2)
is provided. The catalyst system comprises an oxidation catalyst
comprising a first metal supported on a first inorganic oxide
for catalyzing the oxidation of NO to nitrogen dioxide
(NO.sub.2), and a reduction catalyst comprising a second metal
supported on a second inorganic oxide for catalyzing the
reduction of NO.sub.2 to nitrogen (N.sub.2).

[0008] According to a second embodiment of the present
invention, a catalyst system for reducing the content of
nitrogen oxides in a gaseous stream containing nitric oxide
(NO), hydrocarbons, carbon monoxide (CO), and oxygen is
provided. The catalyst system comprises an oxidation catalyst
comprising cobalt on a zirconia support for catalyzing the
oxidation of nitric oxide (NO) to nitrogen dioxide (NO.sub.2),
and a reduction catalyst comprising palladium on a sulfated
zirconia or tungstated zirconia support for catalyzing the
reduction of NO.sub.2 to nitrogen (N.sub.2).

[0009] According to a third embodiment of the present
invention, a method of reducing the level of pollutants in a
gaseous stream is provided. The method comprises providing a
catalyst system comprising an oxidation catalyst and a reduction
catalyst, and feeding a gaseous stream comprising nitric oxide
(NO), hydrocarbons, carbon monoxide (CO), and oxygen (O.sub.2)
to the catalyst system. Additionally, the method comprises
oxidizing the NO to nitrogen dioxide (NO.sub.2) in the presence
of the oxidation catalyst, and reducing the NO.sub.2 to nitrogen
(N.sub.2) by reacting with hydrocarbons in the presence of the
reduction catalyst to form a treated gaseous stream.

[0010] Additional features and advantages provided by
embodiments of the present invention will be more fully
understood in view of the following detailed description.

**DETAILED DESCRIPTION**

[0011] In accordance with one embodiment of the present
invention, a catalyst system for reducing the content of
nitrogen oxides in a gaseous stream containing nitric oxide
(NO), hydrocarbons, carbon monoxide (CO), and oxygen (O.sub.2)
is provided. The catalyst system comprises an oxidation catalyst
comprising a first metal supported on a first inorganic oxide
for catalyzing the oxidation of NO to nitrogen dioxide
(NO.sub.2). The oxidation catalyst may comprise any combination
of metals with inorganic oxides, which are suitable to
accelerate the reaction of NO with oxygen to produce NO.sub.2.
The first metal may include, but is not limited to, cobalt,
silver, or combinations thereof, and the first inorganic oxide
may include, but is not limited to, titania, zirconia, alumina,
or combinations thereof. In one exemplary embodiment, the
oxidation catalyst may comprise cobalt on a zirconia support,
wherein the oxidation catalyst comprises from about 1 to about
10% by weight of cobalt. The oxidation reaction may convert
about 50% to about 90% by weight of the NO to NO.sub.2, and, in
one embodiment, may produce a conversion of between about 70% to
about 90% by weight. The temperature of the oxidation may vary
based on the components of the gaseous stream and the catalysts.
The oxidation generally occurs at a temperature of about 200 to
about 500.degree. C. In a further embodiment, the above
conversions may be achieved at a temperature of about
300.degree. C.

[0012] Furthermore, the catalyst system also comprises a
reduction catalyst comprising a second metal supported on a
second inorganic oxide for catalyzing the reduction of NO.sub.2
to nitrogen (N.sub.2). The reduction catalyst may comprise any
combination of metals with inorganic oxides suitable to
accelerate the reaction of NO.sub.2 with hydrocarbons in the
gaseous stream to produce N.sub.2. In some embodiments, the
second metal may comprise palladium, and the second inorganic
oxide may comprise titania, zirconia, alumina, or combinations
thereof. The palladium may comprise about 0.1 to about 0.5% by
weight of cobalt; however, other amounts are contemplated
depending on the catalytic requirements of the reduction
reaction. In one exemplary embodiment, the reduction catalyst
comprises palladium on a sulfated zirconia support. The
reduction reaction may convert about 50% to about 80% by weight
of the NO.sub.2 to N.sub.2, and, in a further embodiment, may
produce a conversion of between about 60% to about 80% by
weight.

[0013] The high degree of conversion in the reduction step is
due, in large part, to the initial oxidation step. NO.sub.2 is
more easily reduced than NO in a gaseous stream that includes
both oxygen and hydrocarbons. For NO reduction, the combustion
reaction of hydrocarbon in the presence of oxygen dominates over
the reduction reaction of NO to N.sub.2. By oxidizing NO to
NO.sub.2 and then reducing the NO.sub.2, the conversion to
N.sub.2 is greatly enhanced, because the NO.sub.2 reduction
reaction is not substantially blocked by the hydrocarbon
combustion, which is the case for NO reduction.

[0014] In the gaseous stream, the hydrocarbons may comprise
various compounds known to one skilled in the art. These
hydrocarbon compounds may include, but are not limited to,
methane, ethane, propane, or combinations thereof. The oxygen in
the gaseous stream may be fed in excess to overcome any
thermodynamic limitations of the oxidation reaction. In one
embodiment, the gaseous stream may comprise about 2 to about 15%
O.sub.2.

[0015] The catalyst system may comprise various configurations
known to one skilled in the art. In one embodiment, the
oxidation catalyst and the reduction catalyst are disposed on a
catalyst bed. In a few exemplary embodiments, the catalyst bed
may define a mixed bed, a monolith bed structure having
oxidation and reduction catalysts embedded therein, or a bed
comprising alternating layers or sections of oxidation and
reduction catalysts. The catalysts can be combined in the system
in several ways: physically mixing of catalyst powders, layering
the catalyst powders, impregnating a single monolith support
with both catalysts, or alternating sections of impregnated
monolith support. The following catalyst production methods
provide exemplary procedures for producing the oxidation and
reduction catalysts of the present invention.

[0016] An oxidation catalyst comprised of cobalt supported on
either titania or zirconia may be produced through incipient
wetness or sol-gel techniques. The catalyst may contain between
1% and 10% cobalt by weight. The incipient wetness catalyst is
prepared by first calcining the support (titania or zirconia) at
500.degree. C. for 3 hours. Cobalt is then added to the support
by the addition of a cobalt nitrate in water or ethanol
solution, in amount equal to the pore volume of the support. The
sample is then dried at 100.degree. C. overnight. After drying
the catalyst sample is calcined in air at temperatures between
300-600.degree. C. for 3 hours. Based on final desired weight
loading of cobalt several additions of cobalt nitrate solution
may be used. The catalyst can be prepared either by drying, or
by calcining the catalysts between cobalt nitrate solution
additions. The sol-gel prepared catalysts are synthesized in a
single step. A solution of titanium isopropoxide or zirconia
propoxide (depending on the desired support material) in
isopropyl alcohol is hydrolyzed with a solution of cobalt
nitrate in water. The water is added under stirring, and once
complete the resulting gel is dried in air overnight and then
calcined at between 300-600.degree. C. for 3 hours in air.

[0017] In producing the reduction catalyst comprising palladium
supported on a sulfated zirconia support, the sulfated zirconia
support is first prepared by pore volume addition of ammonium
sulfate in water solution to a zirconia support. After the
addition step, the treated support is dried at 100.degree. C.
overnight, then calcined in air at 500.degree. C. for 3 hours.
Palladium is added through pore volume additions of a palladium
chloride and water solution. Small amounts of hydrochloric acid
may be used to dissolve the palladium chloride. After adding the
palladium chloride solution, the catalyst sample is dried at
100.degree. C. overnight and then calcined in oxygen at
500.degree. C. for 3 hours.

[0018] In addition to the removal of nitrogen oxides
(NO.sub.x), the catalyst system may also be operable to oxidize
carbon monoxide and/or hydrocarbons. In one embodiment, the CO
in the gaseous stream may be oxidized to carbon dioxide
(CO.sub.2) in the presence of the oxidation catalyst. In yet
another embodiment, the catalyst system may also be operable to
oxidize the hydrocarbons in the gaseous stream in the presence
of the oxidation catalyst. Oxidizing the hydrocarbons may reduce
the amount of unoxidized hydrocarbons, which may enhance the
reduction of NO.sub.2 to N.sub.2. Thus, in a further embodiment,
the catalyst system may comprise an additional oxidation
catalyst, e.g. oxidation catalyst bed, to oxidize unreacted
hydrocarbons after the reduction step. In an exemplary
embodiment, a hydrocarbon feed comprising 85% methane/10%
ethane/5% propane may be oxidized in the presence of an
oxidation catalyst, wherein the ethane and propane are
substantially oxidized at a temperature of about 275 to about
325.degree. C. and the methane is substantially oxidized at a
temperature of about 425 to about 450.degree. C.

[0019] The present invention has numerous applications for
pollutant removal from gaseous streams. In one embodiment, the
catalyst system may be incorporated in a lean exhaust pollutant
removal system. The lean exhaust removal system, which is
applicable for lean burn engines, e.g. natural gas fuel engines,
comprises an exhaust outlet in communication with the catalyst
system and configured to deliver the gaseous stream to the
catalyst system. To minimize costs, the lean exhaust removal
system eliminates the need for the injection of additional
hydrocarbon reducing agent in the reduction of NO.sub.2. The
system relies on the unburned hydrocarbon fuel remaining in
exhaust. The lean exhaust removal system, as described herein,
may also be applied to other devices, such as diesel engines and
advanced gas reciprocating engines.

[0020] It is noted that terms like "preferably," "generally",
"commonly," and "typically" are not utilized herein to limit the
scope of the claimed invention or to imply that certain features
are critical, essential, or even important to the structure or
function of the claimed invention. Rather, these terms are
merely intended to highlight alternative or additional features
that may or may not be utilized in a particular embodiment of
the present invention.

[0021] For the purposes of describing and defining the present
invention it is noted that the term "substantially" is utilized
herein to represent the inherent degree of uncertainty that may
be attributed to any quantitative comparison, value,
measurement, or other representation. The term "substantially"
is also utilized herein to represent the degree by which a
quantitative representation may vary from a stated reference
without resulting in a change in the basic function of the
subject matter at issue.

[0022] Having described the invention in detail and by
reference to specific embodiments thereof, it will be apparent
that modifications and variations are possible without departing
from the scope of the invention defined in the appended claims.
More specifically, although some aspects of the present
invention are identified herein as preferred or particularly
advantageous, it is contemplated that the present invention is
not necessarily limited to these preferred aspects of the
invention.

---



**Novel Catalyst Systems and Uses Thereof**

**Abstract**

A method of carbon monoxide (CO) removal comprises providing an
oxidation catalyst comprising cobalt supported on an inorganic
oxide. The method further comprises feeding a gaseous stream
comprising CO, and oxygen (O.sub.2) to the catalyst system, and
removing CO from the gaseous stream by oxidizing the CO to
carbon dioxide (CO.sub.2) in the presence of the oxidation
catalyst at a temperature between about 20 to about 200.degree.
C.

Inventors:  Ozkan; Umit S.; (Worthington, OH) ; Holmgreen;
Erik M.; (Columbus, OH) ; Yung; Matthew M.; (Columbus, OH)   
Correspondence Name and Address:

DINSMORE & SHOHL LLP   
ONE DAYTON CENTRE, ONE SOUTH MAIN STREET  SUITE
1300    DAYTON  OH  45402-2023  US

U.S. Current Class:  423/247   
U.S. Class at Publication:  423/247   
Intern'l Class:  B01D 53/62 20060101 B01D053/62

**Description**

**CROSS-REFERENCE TO RELATED APPLICATIONS**

[0001] This application claims the benefit of U.S. Provisional
Application Ser. No. 60/674,992 filed on Apr. 26, 2005, and
incorporates the application in its entirety.

**FIELD OF THE INVENTION**

[0002] The present invention is generally directed to systems
and methods of catalytic removal of pollutants in a gaseous
stream, and is specifically directed to systems and methods of
catalytic removal of pollutants at low temperatures.

**BACKGROUND OF THE INVENTION**

[0003] Air pollution continues to be a serious global problem.
The present industrial plants and automobiles burn fossil fuels
and emit a staggering amount of gaseous pollutants, principally
unburned or partially burned fossil fuels, carbon monoxide,
nitrogen oxides, and sulfur dioxide. Thus, there is a high
demand for air purification methods, which remove these
pollutants, such as carbon monoxide.

[0004] Numerous technologies have been developed; however, many
of these technologies are costly and/or inefficient. As a
result, there is a continuing desire to develop systems and
methods to effectively remove carbon monoxide from gaseous
streams at minimal cost.

**SUMMARY OF THE INVENTION**

[0005] In a first embodiment of the present invention, a method
of carbon monoxide (CO) removal is provided. The method
comprises providing an oxidation catalyst comprising cobalt
supported on an inorganic oxide. The method further comprises
feeding a gaseous stream comprising CO, and oxygen (O.sub.2) to
the catalyst system, and removing CO from the gaseous stream by
oxidizing the CO to carbon dioxide (CO.sub.2) in the presence of
the oxidation catalyst at a temperature between about 20 to
about 200.degree. C.

[0006] In a second embodiment of the present invention, another
method of CO removal is provided. The method comprises providing
an oxidation catalyst comprising cobalt on a titania or a
zirconia support, feeding a gaseous stream comprising carbon
monoxide (CO), and oxygen (O.sub.2) to the catalyst system, and
oxidizing the CO to carbon dioxide (CO.sub.2) in the presence of
the oxidation catalyst at a temperature between about 100 to
about 200.degree. C.

[0007] Additional features and advantages provided by
embodiments of the present invention will be more fully
understood in view of the following detailed description.

**DETAILED DESCRIPTION**

[0008] In accordance with one embodiment of the present
invention, a method of carbon monoxide (CO) removal is provided.
The method comprises providing an oxidation catalyst comprising
cobalt supported on an inorganic oxide. The inorganic oxide,
when used in combination with the cobalt, may comprise any
material effective at oxidizing CO to carbon dioxide (CO.sub.2).
The inorganic oxide may include, but is not limited to, titania,
zirconia, or combinations thereof. In one embodiment, the
catalyst comprises from about 1 to about 10% by weight of
cobalt.

[0009] The method further comprises feeding a gaseous stream
comprising CO, and oxygen (O.sub.2) to the catalyst system. The
gaseous stream may comprise up to about 3% CO, or in a further
embodiment, from about 600 ppm to about 3% CO. The gaseous
stream may comprise less than about 10% H.sub.2O, or in a
further embodiment, less than about 2% H.sub.2O. In one
embodiment, the gaseous stream may comprise up to about 15%
O.sub.2, or in a further embodiment, about 2% to about 10%
O.sub.2.

[0010] The method then includes removing CO from the gaseous
stream by oxidizing the CO to CO.sub.2 in the presence of the
oxidation catalyst at a temperature between about 20 to about
200.degree. C. In a further embodiment, the temperature ranges
from between about 100 to about 200.degree. C. It is further
contemplated to conduct the oxidation at higher temperatures,
for example, up to about 500.degree. C. At temperatures above
100.degree. C., there is less likelihood of catalyst
deactivation. In one embodiment, the oxidation of CO to CO.sub.2
defines a conversion of about 90% to substantially about 100%.
In a further embodiment, the conversion of CO to CO.sub.2 is
maximized at temperatures between about 100 to about 200.degree.
C.

[0011] Oxidizing the CO at low temperatures, for example, at
room temperature, benefits the system. For instance, minimizing
the temperature may minimize the heating and/or electric costs
required. Moreover, at temperatures below 200.degree. C., the
combustion of hydrocarbons present in the gaseous stream is
minimal, and thus does not affect the reaction kinetics of other
reactions, for example, the CO oxidation.

[0012] The catalyst system may comprise various configurations
known to one skilled in the art. In one embodiment, the
oxidation catalyst may be disposed on a catalyst bed. In some
exemplary embodiments, the catalyst bed may define a powder bed,
or a monolith bed structure having the cobalt embedded in the
inorganic oxide support. The catalyst can be combined in the
system in several ways: producing a bed of powdered catalyst, or
impregnating a single monolith support with the oxidation
catalyst. The following catalyst production methods provide
exemplary procedures for producing the oxidation catalyst of the
present invention.

[0013] An oxidation catalyst comprised of cobalt supported on
either titania or zirconia may be produced through incipient
wetness or sol-gel techniques. The catalyst can contain between
1% and 10% cobalt by weight. The incipient wetness catalyst is
prepared by first calcining the support (titania or zirconia) at
500.degree. C. for 3 hours. Cobalt is then added to the support
by the addition of a cobalt nitrate in water solution, in amount
equal to the pore volume of the support. The sample is then
dried at 100.degree. C. overnight. After drying, the catalyst
sample is calcined in air at temperatures between
300-600.degree. C. for 3 hours. Based on the final desired
weight of cobalt, several additions of cobalt nitrate solution
may be used. The catalyst can be prepared either by drying, or
by calcining the catalysts between cobalt nitrate solution
additions. The sol-gel prepared catalysts are synthesized in a
single step. A solution of titanium isopropoxide or zirconia
propoxide (depending on the desired support material) in
isopropyl alcohol is hydrolyzed with a solution of cobalt
nitrate in water or ethanol. The water is added under stirring,
and once complete the resulting gel is dried in air overnight
and then calcined at between 300-600.degree. C. for 3 hours in
air.

[0014] The method has numerous pollutant removal applications,
for example, in respiratory and environmental pollution control
processes. The method may be applicable for use in sealed
environments, for example, a submarine or a spacecraft. In
addition, these catalysts could be used for gas purification in
closed-cycle CO.sub.2 lasers, and CO gas sensors. Furthermore,
the method may be applicable for selectively oxidizing CO in
steam reforming reactions, and for fuel cell applications in
which CO must be removed from the gas feed to prevent poisoning
of the electrodes. This method can also be used to remove CO
from indoor air, which would help to prevent bodily harm/death
from carbon monoxide poisoning. Furthermore, it can be used to
purify exhaust gases from combustion processes.

[0015] It is noted that terms like "preferably," "generally,"
"commonly," and "typically" are not utilized herein to limit the
scope of the claimed invention or to imply that certain features
are critical, essential, or even important to the structure or
function of the claimed invention. Rather, these terms are
merely intended to highlight alternative or additional features
that may or may not be utilized in a particular embodiment of
the present invention.

[0016] For the purposes of describing and defining the present
invention it is noted that the term "substantially" is utilized
herein to represent the inherent degree of uncertainty that may
be attributed to any quantitative comparison, value,
measurement, or other representation. The term "substantially"
is also utilized herein to represent the degree by which a
quantitative representation may vary from a stated reference
without resulting in a change in the basic function of the
subject matter at issue.

[0017] Having described the invention in detail and by
reference to specific embodiments thereof, it will be apparent
that modifications and variations are possible without departing
from the scope of the invention defined in the appended claims.
More specifically, although some aspects of the present
invention are identified herein as preferred or particularly
advantageous, it is contemplated that the present invention is
not necessarily limited to these preferred aspects of the
invention.

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**CATALYST FOR HYDROGEN PRODUCTION FROM WATER GAS SHIFT
REACTION**   
**EP1901844**

2008-03-26   
Inventor: OZKAN UMIT S (US); WANG XUEQIN (US); ZHANG LINGZHI (US);
NATESAKHAWAT SITICHAI (US)   

Also published as: WO2006138485 (A1) // EP1901844 (A0) //
AU2006259326 (A1)

Abstract --- Fe-Al-Cu catalysts have numerous industrial
applications, for example, as catalysts in a water gas shift
reactor. A method of producing a Fe-Al-Cu catalyst comprises the
steps of providing an organic iron precursor, dissolving the
organic iron precursor in a solvent solution, adding an aqueous
solution comprising aluminum nitrate and copper nitrate to the
organic iron precursor-solvent solution, precipitating a gel
comprising Fe-Al-Cu by adding a base, and drying the gel to form
the Fe-Al-Cu catalyst.

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