`
`BEFORE THE PATENT TRIAL AND APPEAL BOARD
`
`UMICORE AG & CO. KG,
`
`Petitioner
`
`Patent No. 8,404,203
`
`Issue Date: March 16, 2013
`Title: PROCESS FOR REDUCING NITROGEN OXIDES USING COPPER
`
`CHA ZEOLITE CATALYSTS
`
`DECLARATION OF Dr. FRANK-WALTER SCHUTZE
`
`Case No. IPR2015—01124
`
`Umicore AG & Co. KG
`Exhibit 1115
`Page 1 of 24
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`
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`I, Dr. Frank—Walter Schutze, declare as follows:
`
`BACKGROUND
`
`I am currently a Senior Manager R&D / Strategic Projects and I am
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`involved in SCR research and development as well as zeolite related topics in
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`connection with automotive catalysts at Umicore AG & Co. KG (“Umicore”), which
`
`is located in Hanau—Wolfgang, Germany.
`
`I studied chemistry at the University of Leipzig (Germany) and received
`
`my PhD. in Chemistry in 1997. From 1997 to 2001, I was a post doc researcher at
`
`the University of Oldenburg (Germany) and the Institute of Applied Catalysis Berlin
`
`I have held my current position at Umicore since the 1st of January
`
`2015. Prior to that, I was Senior Manager R&D / Research and Customer Projects
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`and was involved in SCR / ASC development. Since I joined Umicore in 2001, I was
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`involved in R&D for automotive catalysts on several topics, very often related to
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`application of zeolites in catalyst formulations.
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`ASSIGNMENT
`
`I was asked to make samples of copper—loaded chabazite zeolite (“Cu—
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`CI—IA”) catalysts with varying silica to alumina molar ratios (which I will refer to as the
`
`“SAR”) and copper to aluminum atomic ratios (which I will refer to as the “Cu/Al
`
`I was asked to test the catalyst samples I made in different ways. In
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`Umicore AG & Co. KG
`Exhibit 1115
`Page 2 of 24
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`particular, I was asked to assess each sample’s effectiveness at catalyzing the reduction
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`of nitrogen oxides in a gas stream both before and after hydrothermal aging.
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`III. MATERIALS TESTED
`
`I started my preparation of Cu—CHA catalyst samples by obtaining
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`various ammonium—type chabazite zeolite (NH4—CHA) materials with different
`
`framework SARs. I obtained chabazite materials with SARs of 13, 19, 21, 27, and 30.
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`Next, I copper-loaded these various NH4—CHA materials to produce Cu-
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`CHA zeolite samples with different Cu/Al ratios ranging from O to 1. Copper—
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`loading of the NH4—CHA materials was performed by aqueous ion—exchange. The
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`required amount of copper-acetate needed to produce a given Cu/Al ratio was mixed
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`with the NH4—CHA and the suspension was then heated for 2 hours at 65 OC.
`
`For the creation of recipes related to the targeted Cu/Al ratios for CHA
`
`materials with the different SAR, I have used molar relationships of the components
`
`based on their direct structural correlations. Based on the SAR of the CHA material,
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`I determined the molar composition of the so called “unit cell” (or “u.c.”) of the
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`material. The unit cell of a protonated CHA material has the formula ([Siwx A1,, 072]
`
`HX). Using this formula, the molar amount of aluminum or alumina in this structural
`
`building unit, and thus the ion—exchange capacity, can be calculated. I used the well
`
`accepted stoichiometric assumption that 1 Cu2+ ion balance the charge introduced by
`
`2 Al atoms in the structural building unit.
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`Umicore AG & Co. KG
`Exhibit 1115
`Page 3 of 24
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`the framework of the unit cell, introducing 3 moles of positive charge into 1 mole of
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`the appropriate unit cell. From this I calculated the target amount of Cu2+ for the
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`appropriate ion—exchange level (using the above explained assumption) based on the
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`molar mass of Cu (63.546 g/mole). The stoichiometric maximum amount of copper
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`that can be ion—exchanged into a zeolite with a SAR of 22 is 1.5 mole of Cu, or 95.319
`
`g Cu/mole CHA unit cell.
`
`The unit cell formula for a complete stoichiometric ion—exchange is
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`represented by ([Si33Al3O72] Cum). From this formula I have calculated (based on the
`
`molar masses of the elements in the unit cell) an amount of 4.226 wt 0/o of Cu in the
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`material. This is the stoichiometric maximum 100% ion—exchange corresponding to a
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`Cu/Al ratio of 0.5.
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`11. With these correlations, I created the preparation recipes for the
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`different CHA—catalyst samples with the different SAR values and Cu/Al ratios (or Cu
`
`and CuO concentrations, respectively). In these calculations, I determined the
`
`appropriate amount of Cu—precursor needed (Cu—acetate) to produce the desired
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`Cu/Al ratio via ion exchange given the SAR and amount of zeolite in the ion—
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`exchange slurry.
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`12. When calculating the Cu/Al ratios of the materials I prepared, I was
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`asked to include only the aluminum from the zeolite and ignore any other aluminum
`
`present in the resultant catalyst material, including any aluminum from the binder or
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`Umicore AG & Co. KG
`Exhibit 1115
`Page 4 of 24
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`I then coated these Cu—CHA zeolite materials onto ceramic cordierite
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`substrates with a cell density of 400 cpsi (cells per square inch) and a wall thickness of
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`6.5 mil. The substrates had either a 3.66 or 5.66 inch diameter, and a length of 3
`
`inches. To improve the adhesion properties of the Cu—CHA zeolite to the substrate, a
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`binder was used in an amount of 12 wt °/o, resulting in an overall washcoat loading
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`amount of 150 g/L coated catalyst volume. After coating, the substrates were dried
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`and calcined. The catalysts with a SAR of 13 were calcined for 2 hours at 500 °C in
`
`air, while the other catalysts were calcined for 4 hours at 640 °C in air.
`
`In addition to the Cu—CI—IA zeolite coated substrates, I was also asked to
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`make a number of copper loaded beta zeolite (BEA) coated substrates. To create
`
`these samples, I used a BEA zeolite with a SAR of 30, which I copper loaded using
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`the same procedure described above to produce Cu/Al ratios in the range of
`
`approximately 0.15 to 0.55. I then coated substrates with the copper loaded BEA
`
`zeolite material in the same manner I describe above for the Cu—CI—IA materials.
`
`Then multiple 1 inch diameter x 3 inch length core samples were drilled
`
`out of each Cu—CHA coated substrate to allow for testing. A fresh core sample was
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`retained from each Cu—CHA coated substrate. And, a core sample from each Cu—
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`CHA coated substrate was aged for 50 hours at 800 °C using a forced flow—through of
`
`hydrothermal atmosphere containing 10 vol. 0/0 of oxygen and 10 vol. 0/o of water
`
`vapor balanced by nitrogen. This treatment is assigned as 50 B 800 in the attached
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`Umicore AG & Co. KG
`Exhibit 1115
`Page 5 of 24
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`IV. TESTING PERFORMED
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`Each of the samples was tested for performance and its activity in the
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`selective catalytic reduction (or “SCR”) of nitrogen oxides.
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`SCR activity testing of the samples was carried out using a feed gas
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`mixture containing 500 ppm nitrogen monoxide (N O), 500 ppm ammonia (NH3), 5
`
`vol.°/o water vapor (H20), 10 vol.°/o oxygen (02), 10 vol.°/o carbon dioxide (C02), and
`
`the balance nitrogen. The space velocity for the feed gas was 80.000 h‘]. NOx
`
`concentration and N20 concentrations were measured after observation of stable
`
`product composition downstream the catalyst samples. The product gas stream
`
`components were evaluated by a FTIR—spectrometer. For each tested core sample,
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`the percentage of NOx from the feed gas that had been reduced by the sample was
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`DATA COLLECTED
`
`Performance and SCR Activity of Cu-CHA Core Samples
`
`The performance and SCR activity data I collected for the fresh Cu—
`
`CHA coated core samples is attached to this declaration as Exhibit A.
`
`The performance and SCR activity data I collected for the aged Cu—CHA
`
`coated core samples is attached to this declaration as Exhibit B.
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`To help analyze the trends and patterns I observed in the collected data,
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`I have prepared a few summary graphs.
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`The following graph compares the NOx conversion performance of the
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`Umicore AG & Co. KG
`Exhibit 1115
`Page 6 of 24
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`fresh Cu—CHA coated core sample with a SARs of 30, 27, 21, 19, and 13 and various
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`Cu/Al ratios at a reaction temperature of 200 0C:
`
`.
`
`NOX Conversion % of Fresh Cu—CHA
`
`Samples at 200 °C
`
` s"
`
`6z
`
`----- SAR 19
`
`......... SAR 13
`
`0.00
`
`0.20
`
`0.40
`
`0.60
`
`0.80
`
`1.00
`
`1.20
`
`Cu/Al Ratio
`
`Figure 1
`
`As can be seen, at a SAR of 30, increasing the Cu/Al ratio results in a
`
`steady increase in NOX conversion performance until a Cu/Al ratio of approximately
`
`0.5 was reached. A Cu/Al ratio of 0.5 is close to the maximum theoretical copper ion
`
`exchange ratio for a CHA zeolite. It appears that adding additional copper beyond
`
`the maximum theoretical copper ion exchangeable amount does not further improve
`
`NOX conversion performance. I observed similar trends in the data I collected for
`
`the other fresh Cu—CHA coated core samples with SARs of 27, 21, 19, and 13. While
`
`the relative change in performance was not very large, increasing the Cu/Al ratio from
`
`around 0.25 to around 0.5 once again resulted in a steady, linear increase in NOX
`
`conversion performance.
`
`SAR 30
`
`- - - SAR 27
`
`— —SAR 21
`
`.5
`
`e g
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`C 8
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`Umicore AG & Co. KG
`Exhibit 1115
`Page 7 of 24
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`Another graph showing the NOX conversion performance of the Cu—
`
`CHA coated samples with a SAR of 30 and Cu/Al ratios ranging from about 0.15 to
`
`0.55 in fresh state at a reaction temperature of 200 0C is plotted below:
`
`NOx Conversion % of Fresh Cu-CHA Samples
`
`with a SAR of 30 at 200°C
`
`
`
`N0xconversion,%
`
`01mCO
`
`1.2
`
`20
`
`O
`
`
`
`0.0
`
`0.1
`
`0.2
`
`0.3
`
`0.4
`
`0.5
`
`0.6
`
`Cu / Al ratio
`
`Figure 2
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`The following graph compares the NOX conversion performance of the
`
`aged Cu—CHA coated core sample with a SAR of 30 and various Cu/Al ratios at a
`
`reaction temperature of 200 0C:
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`Umicore AG & Co. KG
`Exhibit 1115
`Page 8 of 24
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`NOX Conversion % of Aged Cu—CHA
`
`Samples with a SAR of 30 at 200 °C
`
`o
`,A:
`
`NOXconversion
`
`100
`
`80
`
`60
`
`4’0
`
`20
`
`O
`
`
`
`0.00
`
`0.20
`
`0.40
`
`0.130
`
`0.80
`
`1.00
`
`1.20
`
`—SAR 30
`
`Cu / AI Ratio
`
`Figure 3
`
`As can be seen, the aging conditions I used resulted in a large reduction
`
`in the samples’ NOX conversion performance. Regardless, the same trend 1 observed
`
`in connection with the fresh samples was present. Increasing the Cu/Al ratio up to
`
`about 0.5 results in a steady increase in NOX conversion performance. After a Cu/Al
`
`ratio of 0.5 was reached, I observed that incorporation of additional copper caused
`
`the performance of the sample to decrease.
`
`The following graph compares the NOX conversion performance of the
`
`aged Cu—CHA coated core sample with SARs of 27, 21, 19, and 13 and various Cu/Al
`
`ratios at a reaction temperature of 200 °C:
`
`Umicore AG & Co. KG
`Exhibit 1115
`Page 9 of 24
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`NOx Conversion % of Aged Cu-CHA
`
`Samples with SARs of 27, 217, 19, and 13 at 200 °C
`100
`
`- - - SAR 27
`
`— —SAR 21
`----- SAR 19
`
`......... SAR 13
`
`~
`'h‘fi-hg
`
`
`0,00
`
`0.20
`
`0.40
`
`0.00
`
`0.00
`
`1.00
`
`1.20
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`Cu / AI Ratio
`
`Figure 4
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`8'0
`
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`'00
`
`40
`
`38
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`
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`
`5
`z 20
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`27. With respect to the aged Cu—CHA coated core samples with SARs of 27,
`
`21, 19, and 13, I observed that the NOx conversion performance actually declined as
`
`the Cu/Al ratio was increased from about 0.25 to 0.5 at a reaction temperature of
`
`I also observed that the samples with higher SAR values exhibited higher
`
`NOx conversion percentages after aging. This is shown, for instance, in the following
`
`graph which shows the data collected for the aged Cu—CHA coated core samples with
`
`a Cu/Al ratio of approximately 0.45 at a temperature of 250 °C. As the SAR value
`
`increased, the NOx conversion performance after aging increased steadily and in a
`
`linear fashion. As shown in Exhibit B, the same basic trend was exhibited by the
`
`samples with different Cu/Al ratios, including, for instance a Cu/Al ratios of 0.25 and
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`Umicore AG & Co. KG
`Exhibit 1115
`Page 10 of 24
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`NOx Conversion % of Samples with a Cu/AI Ratio of
`
`About 0.45 at 250 0C After Aging
`
`NOconversion%
`
`20
`
`O
`
`10
`
`15
`
`20
`
`25
`
`3O
`
`35
`
`40
`
`SAR of zeolite
`
`Figure 5
`
`Performance / SCR Activity of BEA Zeolite Core Samples
`
`The performance and SCR activity data I collected for the Cu—BEA
`
`zeolite coated core samples is attached to this declaration as Exhibit C.
`
`A graph showing the NOX conversion performance of the fresh Cu—
`
`BEA zeolite coated samples with Cu/Al ratios ranging from about 0.15 to 0.55 in
`
`fresh state at a reaction temperature of 200 °C is plotted below:
`
`Umicore AG & Co. KG
`Exhibit 1115
`Page 11 of 24
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`NOX Conversion % for Fresh Cu—BEA
`
`Samples with a SAR of 30 at 200°C
`
`NOXconversion,%
`
`0.0
`
`0.1
`
`0.2
`
`0.3
`
`0.4
`
`0.5
`
`0.5
`
`
`
`Cu /Al ratio
`
`Figure 6
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`I declare that all statements made herein of my own knowledge are true and
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`that all statements made on information and belief are believed to be true, and further
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`that these statements were made with the knowledge that willful false statements and
`
`the like so made are punishable by fine or imprisonment, or both, under Section 1001
`
`of Title 18 of the United States Code.
`
` Date:M)? (S\
`
`Dr. Frank—Walter Schutze
`
`Umicore AG & Co. KG
`Exhibit 1115
`Page 12 of 24
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`EXHIBIT A
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`Umicore AG & Co. KG
`Exhibit 1115
`Page 13 of 24
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`Umicore AG & Co. KG
`Exhibit 1115
`Page 14 of 24
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`Exhibit 1115
`Page 16 of 24
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`Umicore AG & Co. KG
`Exhibit 1115
`Page 17 of 24
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`Umicore AG & Co. KG
`Exhibit 1115
`Page 18 of 24
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`Page 19 of 24
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`Exhibit 1115
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`Umicore AG & Co. KG
`Exhibit 1115
`Page 21 of 24
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`Umicore AG & Co. KG
`Exhibit 1115
`Page 22 of 24
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`Umicore AG & Co. KG
`Exhibit 1115
`Page 23 of 24
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`Umicore AG & Co. KG
`Exhibit 1115
`Page 24 of 24
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