Mitsubishi Heavy Industries Technical Review Vol. 49 No. 1 (March 2012)
88Technologies for Multifunctional De-NOx Catalyst
and Recycling of Spent catalyst intended
for Eco-Friendly Thermal Power Plants
MASASHI KIYOSAWA*1 MASANORI DEMOTO*2

HIROSHI KAKO*2

TOMOTSUGU MASUDA*3MASANAO YONEMURA*3 KATSUMI NOCHI*3Emission control regulations have been tightened year after year throughout the world inresponse to increased desire for environmental conservation. To meet the new demands, moresophisticated flue gas cleaning technologies are needed that reduce nitrogen oxide (NOx)emissions, which cause acid rain and photochemical smog. Meanwhile, there is also increased
interest in improved use of scarce resources through reduction of waste products and better
recycling of rare metals. Mitsubishi Heavy Industries, Ltd. (MHI) has developed two unique
catalysts for De-NOx used in thermal power plants and aims to respond quickly to the wide rangeof customer needs in the global market. The two types of catalyst are: (1) a catalyst intended forgas turbine power plants with high NO2/NOx ratios and (2) a regenerated catalyst intended forcoal-fired power plants.

|1. Introduction
Operation of the first dry De-NOx system for boilers started in 1977, and it is estimated that
more than 1,000 units are currently being used in commercial and industrial boilers as well as ingas turbines.1
MHI began development of De-NOx systems intended for boilers in 1974, and we have since
been developing catalysts in response to the needs of customers and making efforts to improvereliability of the equipment. In the course of our development, we have delivered more than 500
De-NOx systems in Japan, mainly for use in commercial and industrial power plants. In addition,
we have licensed our expertise to manufacturers in the United States and the European Union.2
In this paper, we present an overview of our recent De-NOx catalyst improvements anddevelopments from the perspective of advanced technology for flue gas cleaning and rare metalrecycling.

|2. Improvement of Catalysts Intended for Gas Turbine Plants
The principal component of NOx (NO and NO2) in combustion exhaust gas is NO.
Therefore, the De-NOx reactions, in which NOx is reducted into nitrogen by NH3, generally
progress according to reaction (1) below. In cases where NO2 coexists with NO, reactions (2) and(3) occur. If the percentage of NO2 in NOx is less than 50%, NO2 and NO are removed by reaction(2), and the NO that remains is removed by reaction (1). If the percentage of NO2 in NOx is higher
than 50%, however, NO2 in the remaining NOx component system becomes rich in line as reaction(2) progresses. Under this circumstance, the De-NOx ratio drops because reaction (3) is slow, asshown in Figure 1.
4NO + 4NH3 + O2 => 4N2 + 6H2O･･･ (1)NO + NO2 + 2NH3 => 2N2 + 3H2O･･･ (2)
6NO2 + 8NH3=> 7N2 + 12H2O･･･ (3)*1Manager, Boiler Engineering Department, Power Systems*3Hiroshima Research and Development Center, Technology & Innovation Headquarters*2

Boiler Engineering Department, Power Systems

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In exhaust gas from gas turbines, the NO2/NOx ratio tends to increase during startup and lowload operation. The high NO2/NOx ratio poses a potential risk of reducing the De-NOxperformance. Therefore, De-NOx catalysts that are not affected by the NO2/NOx ratio are needed.
In response to this need, MHI developed a multifunctional De-NOx catalyst featuring both
NH3-NO2 reaction and NH3-NO reaction properties to reducing NOx with a high ratio of NO2content.
When the NO2/NOx ratio is larger than 0.5, the steady De-NOx performance of the improved
catalyst described above is equivalent to that of a conventional catalyst at high temperatures. At
low temperatures, however, the De-NOx performance of a conventional catalyst drops
substantially, while the performance of the improved catalyst is maintained at an acceptable level.
As shown in Figure 2, the improved catalyst provides high, steady De-NOx performance, even if
the NO2/NOx ratio is 0.9. Furthermore, we have confirmed that the De-NOx performance of theimproved catalyst is equivalent to that of a conventional catalyst under normal conditions where theNO2/NOx ratio is low.

Figure 1
Correlation between NO2/NOx
ratio and De-NOx efficiency
De-NOx efficiency in response to changes in NO2 ratio.

Figure 2
De-NOx performance of theimproved catalyst intended for gas
turbines, for NOx with a high ratio ofNO2 content
A conventional catalyst is compared with the improved
catalyst.

The NO2/NOx ratio in the exhaust gas from gas turbines increases during load drop, thereby
posing the risk that NOx emissions will temporarily exceed the regulation value at the plant outlet.
To eliminate this possibility, response control under high NH3/NOx molar ratios is very important.
The De-NOx speed of a conventional catalyst is slow when the NO2/NOx ratio is high, and theNOx concentration at the catalyst outlet drops gradually in response to changes in the NH3/NOx
molar ratio, as shown in Figure 3. However, the De-NOx speed of the improved catalyst is
extremely high when the NO2/NOx ratio is high, and the NOx concentration at the catalyst outlet
drops rapidly immediately after changes are detected in the NH3/NOx molar ratio. The behavior isclearly different between a conventional catalyst and the improved catalyst.
In the final stage of development, the durability of the improved catalyst was evaluated byexhaust gas exposure tests in actual gas turbines in Japan and abroad. Securing of durability inactual exhaust gas environments is essential for commercialization of the catalyst. It was verified
that MHI improved catalyst has good durability enough to commercialize after exposure tests ofabout 14,000 hours in total (Figure 4). The exposure tests proved that there is little decline in theDe-NOx performance of the improved catalyst as is the case with a conventional catalyst intended
for gas turbine power plants, and that the improved catalyst is remarkably stable and without any
significant changes in properties.

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Figure 3
Results of tests for De-NOx
reaction/response with changes inNH3/NOx molar ratio

Responsiveness is compared between the conventional
catalyst and the improved catalyst.

Figure 4 Results of actual gas exposure tests
using the improved catalyst
The figure indicates that the De-NOx performanceremains the same before and after exposure to actualgas.

|3. Improvement and Development of Catalysts Intended for
Coal-Fired Boiler Plant
If the fly ash generated by coal combustion passes through a honeycomb catalyst together
with the exhaust gas, components in the fly ash, such as calcium, gradually adhere to the innersurface of the catalyst and block further De-NOx reaction on the catalyst surface. Furthermore, thefly ash will form partial sediments along the gas path in the catalyst and gradually prevent smoothpassage of the exhaust gas. Eventually, complete blockage of the gas path occurs, causing
deterioration of the De-NOx performance. Thus, De-NOx catalysts are periodically replaced inorder to maintain De-NOx performance. However, fresh De-NOx catalysts are expensive because
they contain rare metals such as titanium, tungsten, and molybdenum. This leads to the strong needfor cost reductions in both the renewal of De-NOx catalysts and in the disposal of spent catalysts.
Effective recycling of spent catalysts that were usually disposed would address this need. At thesame time, catalyst recycling would lead to a reduction in the disposal of rare metals and contributeto global environmental conservation.
According to some information some spent De-NOx catalysts for coal-fired boiler plants arefinely ground, formed into honeycombs, and calcined. That makes fly ash and its components, suchas calcium, mixed in the honeycomb catalysts. Portions of the catalyst that have not deteriorated
during the operation are distributed on the surface of catalyst to recycle spent catalysts.3 Other
recycling method was also proposed in which spent catalysts are crushed into fine powders, mixed
with fresh materials, formed, and calcined, in an effort to reduce fly ash and components such ascalcium mixed in the honeycomb catalysts.4 In these methods, however, the regenerated De-NOx
catalysts contain fly ash and other components, thereby reducing the catalyst component per gas
contact area and showing lower the De-NOx performance than the fresh De-NOx catalyst. To
improve performance, MHI developed regenerated catalysts that feature the De-NOx performanceequivalent to that of fresh catalysts.5 In the MHI method, the NOx performance was recovered byan activation treatment, in which fresh catalyst components were coated after removal ofsubstances that caused deterioration. The renewed catalysts are classified into two types: type I,
which employs spent catalysts removed from De-NOx reactors as the honeycomb substrates, andtype II, which uses honeycombs made by forming ground product of spent catalysts as thesubstrates. In Type I, spent catalysts are employed as substrates without processing. Therefore,
spent catalysts with severe cracks and damage cannot be recycled unless amount of the damaged
catalyst are replaced with brand-new catalyst. In contrast, in type II, spent catalysts are crushed toproduce raw materials, which are then formed into the honeycomb shape to create substrates.
Therefore, damaged catalysts can be used effectively in type II structures. Catalysts manufactured
by MHI do not contain inactive materials in the substrates, and the substrates consist almost totallyof materials that exhibit catalytic activity. To maximize the advantage of recycling the entire
honeycomb catalyst, spent catalysts are crushed into powders, which are then formed into thehoneycomb shape with the cell width and length that meet the needs of customers. Through thesemethods, we succeeded in remarkably expanding the application range of replacement catalysts.

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When spent catalysts are recycled, catalytic components are coated for activation, asdescribed above. The coated layer on the honeycomb catalyst exhibits superior durability in theexhaust gas from coal-fired boilers, which contains a large amount of fly ash, because of the uniquebimodal technology shown in Figure 5. Furthermore, the De-NOx performance of spent catalysts
deteriorated is recovered nearly to the initial value by MHI’s original regeneration technology, as
shown in Figure 6, making it possible to recycle rare metals. With respect to the durability of theregenerated catalysts in long-term use, deterioration has been demonstrated to be not much fasterthan in conventional catalysts, and the products are in practical use today.

Figure 5 Pattern diagram of the regenerated
catalyst
The honeycomb catalyst is covered with a coatedlayer. The sizes of the circles indicate the sizes ofparticles used for coating. The coated layer isstabilized by a unique bimodal technology.

Figure 6 Comparison of De-NOx efficiency
in a brand-new catalyst, a spent catalyst,
and a regenerated catalyst

The figure indicates that De-NOx efficiency of thespent catalyst is inferior to that of the brand-new
catalyst, while De-NOx efficiency of the regenerated
catalyst is equivalent to that of the brand-new catalyst.

|4. Conclusion
Emission control regulations have been tightened year after year throughout the world inconsideration of environmental conservation. Under these circumstances, more sophisticated fluegas cleaning catalyst technologies are needed, and there is increased need for reduction of waste
products and improved recycling of rare metals. To address these needs and to respond quickly to
the wide range of customer needs in the global marketplace, MHI developed two unique types ofcatalysts for De-NOx: (1) a catalyst intended for gas turbine power plants with high NO2/NOx
ratios and (2) a regenerated catalyst intended for coal-fired power plants. Both types of catalyst
have been commercialized. In the future, properties of exhaust gases treated by De-NOx systems
will continue to change in response to diversification of fuels and improvements in the main units(boilers, gas turbines). MHI will continue to promote further developments, aiming to deliver
De-NOx equipment with high reliability and economic potential.

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