`
`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. IPR2015-01123
`
`Umicore AG & Co. KG
`Exhibit 1015
`Page 1 of 24
`
`
`
`I, Dr. Frank-Walter Schutze, declare as follows:
`
`BACKGROUND
`
`Tam currently a Senior Manager R&D / Strategic Projects and I am
`
`involved in SCR research and developmentas well as zeolite related topics in
`
`connection with automotivecatalysts 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 Ph.D. in Chemistry in 1997. From 1997 to 2001, I was a post doc researcherat
`
`the University of Oldenburg (Germany) and the Institute of Applied Catalysis Berlin
`
`I have held my current position at Umicoresince the 1st of January
`
`2015. Prior to that, I was Senior Manager R&D / Research and Customer Projects
`
`and was involved in SCR / ASC development. Since I joined Umicote in 2001, I was
`
`involved in R&D for automotive catalysts on several topics, very often related to
`
`application of zeolites in catalyst formulations.
`
`ASSIGNMENT
`
`I was asked to make samples of copper-loaded chabazite zeolite (“Cu-
`
`CHA”) catalysts with varyingsilica 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 totest the catalyst samples I made in different ways. In
`
`Umicore AG & Co. KG
`Exhibit 1015
`Page 2 of 24
`
`
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`particular, I was asked to assess each sample’s effectiveness at catalyzing the reduction
`
`of nitrogen oxides in a gas stream both before and after hydrothermalaging.
`
`Ill. MATERIALS TESTED
`
`I started my preparation of Cu-CHA catalyst samples by obtaining
`
`vatious ammonium-type chabazite zeolite (NH,-CHA)materials with different
`
`framework SARs. I obtained chabazite materials with SARs of 13, 19, 21, 27, and 30.
`
`Next, I coppet-loaded these various NH,-CHA materials to produce Cu-
`
`CHA zeolite samples with different Cu/Alratios ranging from 0 to 1. Copper-
`
`loading of the NH,-CHA materials was performed by aqueous ion-exchange. The
`
`tequited amount of copper-acetate needed to produce a given Cu/Al ratio was mixed
`
`with the NH,-CHA and the suspension was then heated for 2 hours at 65 °C.
`
`Forthe 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,
`
`I determined the molar composition of the so called “unit cell” (or “u.c.”) of the
`
`material. The unit cell of a protonated CHA material has the formula ((Si,,, Al, O75]
`
`H,). Using this formula, the: molar amount of aluminum or aluminain this structural
`
`building unit, and thus the ion-exchange capacity, can be calculated. I used the well
`
`accepted stoichiometric assumption that 1 Cu** ion balance the chatge introduced by
`
`2 Al atomsin the structural building unit.
`
`Umicore AG & Co. KG
`Exhibit 1015
`Page 3 of 24
`
`
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`the framework of the unitcell, introducing 3 moles of positive charge into 1 mole of
`
`the appropriate unit cell. From this I calculated the target amount of Cufor the
`
`appropriate ion-exchangelevel (using the above explained assumption) based on the
`
`molat mass of Cu (63.546 g/mole). The stoichiomettic maximum amount of copper
`
`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 unitcell.
`
`The unit cell formula for a complete stoichiometric ion-exchange1s
`
`represented by ({S1,,;A1,0,,] Cu,,;). From this formula I have calculated (based on the
`
`molar masses of the elements in the unit cell) an amountof 4.226 wt % of Cu in the
`
`material. This is the stoichiometric maximum 100% ion-exchange corresponding to a
`
`Cu/AI ratio of0.5.
`
`11. With these correlations, I created the preparation recipes for the
`
`different CHA-catalyst samples with the different SAR values and Cu/AlI ratios (or Cu
`
`and CuO concentrations, respectively). In these calculations, I determined the
`
`approptiate amount of Cu-precursor needed (Cu-acetate) to produce the desired
`
`Cu/Alratio via ion exchange given the SAR and amountofzeolite in the ion-
`
`exchangeslurry.
`
`12. When calculating the Cu/Al ratios of the materials I prepared, I was
`
`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
`
`Umicore AG & Co. KG
`Exhibit 1015
`Page 4 of 24
`
`
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`I then coated these Cu-CHA zeolite materials onto ceramic cordierite
`
`substrates with a cell density of 400 cpsi (cells per square inch) and a wall thickness of
`
`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
`
`binder was used in an amountof 12 wt %, resulting in an overall washcoat loading
`
`amount of 150 g/L coated catalyst volume. After coating, the substrates were dried
`
`and calcined.
`
`‘The catalysts with a SAR of 13 wetecalcined for 2 hours at 500 °C in
`
`ait, while the other catalysts were calcined for 4 hours at 640 °C in air.
`
`In addition to the Cu-CHA zeolite coated substrates, I was also asked to
`
`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
`
`the same ptocedute 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-CHA 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
`
`retained from each Cu-CHA coated substrate. And, a core sample from each Cu-
`
`CHA coated substrate was aged for 50 hours at 800 °C using a forced flow-through of
`
`hydrothermal atmosphere containing 10 vol. % of oxygen and 10 vol. %of water
`
`vapor balanced by nitrogen. This treatmentis assigned as 50 B 800 in the attached
`
`Umicore AG & Co. KG
`Exhibit 1015
`Page 5 of 24
`
`
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`IV. TESTING PERFORMED
`
`Each of the samples was tested for performance andits activity in the
`
`selective catalytic reduction (or “SCR”) of nitrogen oxides.
`
`SCR activity testing of the samples was carried out using a feed gas
`
`mixture containing 500 ppm nitrogen monoxide (NO), 500 ppm ammonia (NH;,), 5
`
`vol.% water vapor (H,O), 10 vol.% oxygen (O,), 10 vol.% carbon dioxide (CO,), and
`
`the balance nitrogen. The space velocity for the feed gas was 80.000 h'. NOx
`
`concentration and N,O concentrations wete measuted after observation of stable
`
`product composition downstream the catalyst samples. The product gas stream
`
`components were evaluated by a FTTR-spectrometer. For each tested core sample,
`
`the percentage of NOx from the feed gas that had been reduced by the sample was
`
`DATA COLLECTED
`
`Performance and SCR Activity of Cu-CHA Core Samples
`
`The performance and SCRactivity data I collected for the fresh Cu-
`
`CHA coated core samplesis attached to this declaration as Exhibit A.
`
`‘The performance and SCRactivity data I collected for the aged Cu-CHA
`
`coated core samples is attached to this declaration as Exhibit B.
`
`To help analyze the trends and patterns I observed in the collected data,
`
`I have prepared a few summaty graphs.
`
`The following graph compares the NOx conversion performance of the
`
`Umicore AG & Co. KG
`Exhibit 1015
`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
`
`Cu/AI ratios at a reaction temperatute of 200 °C:
`
`NOx Conversion % of Fresh Cu-CHA
`Samples at 200 °C
`
`——= SAR 30
`
`— — -SAR 27
`— —SAR21
`
`seeeeouns SAR 13
`
`xe
`
`5
`
`v v
`
`< 8
`
`5S
`
`
`
`20|foa SAR 19
`
`0.00
`
`° 020
`
`0.40
`
`0.60
`
`0.80
`
`1.00
`
`1.20
`
`Cu/Al Ratio
`
`Figure 1
`
`As can be seen, at a SAR of30, increasing the Cu/Alratio 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 coppet ion exchangeable amount does not further improve
`
`NOxconversion 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 wasnotvety 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.
`
`Umicore AG & Co. KG
`Exhibit 1015
`Page 7 of 24
`
`
`
`Another graph showing the NOx conversion performance of the Cu-
`
`CHA coated samples with a SAR of 30 and Cu/Al ratios ranging from about0.15 to
`
`0.55 in fresh state at a reaction temperature of 200 °C 1s plotted below:
`
`NOx Conversion % of Fresh Cu-CHA Samples
`with a SAR of 30 at 200°C
`
`100
`
`80
`
`
`
`NOxconversion,%
`
`
`
`0.0
`
`0.1
`
`0.2
`
`0.3
`
`0.4
`
`0.5
`
`0.6
`
`Cu / Al ratio
`
`Figure 2
`
`Thefollowing graph compares the NOx conversion performance of the
`
`aged Cu-CHA coated core sample with a SAR of 30 and various Cu/Alratios at a
`
`reaction temperature of 200 °C:
`
`Umicore AG & Co. KG
`Exhibit 1015
`Page 8 of 24
`
`
`
`NOx Conversion % of Aged Cu-CHA
`Samples with a SAR of 30 at 200 °C
`
`
`
`NOxconversion,%
`
`
`
`0
`
`0.00
`
`0.20
`
`0.40
`
`0.60
`
`0.80
`
`1.00
`
`1.20
`
`—— SAR 30
`
`Cu / Al 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 I observed
`
`in connection with the fresh samples was present. Increasing the Cu/Alratio 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 1015
`Page 9 of 24
`
`
`
`NOx Conversion % of Aged Cu-CHA
`Samples with SARsof 27, 21, 19, and 13 at 200 °C
`100
`
`% 80
`
`_
`60
`
`.Q
`
`Po
`
`o
`BG
`oY
`é
`40
`9
`a SAR 19
`Zz
`20
`
`=- — — SAR 27
`— —SAR 21
`
`_w
`
`e SAR 13
`
`ee
`0.40
`
`0.00
`
`0.20
`
`0.60
`
`0.80
`
`1.00
`
`1.20
`
`Cu / Al Ratio
`
`Figure 4
`
`27. With respect to the aged Cu-CHA coated core samples with SARsof27,
`
`21, 19, and 13, I observed that the NOx conversion performanceactually declined as
`
`the Cu/AIratio was increased from about0.25 to 0.5 at a reaction temperature of
`
`also observed that the samples with higher SAR values exhibited higher
`
`NOxconversion petcentages after aging.
`
`‘This is shown, for instance, in the following
`
`graph which showsthe 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 performanceafter 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
`
`Umicore AG & Co. KG
`Exhibit 1015
`Page 10 of 24
`
`
`
`NOx Conversion % of Samples with a Cu/Al Ratio of
`About 0.45 at 250°C After Aging
`
`NOconversion%
`
`0
`
`10
`
`15
`
`20
`
`25
`
`30
`
`35
`
`40
`
`SAR ofzeolite
`
`Figure 5
`
`Performance / SCR Activity of BEA Zeolite Core Samples
`
`The performance and SCRactivity data I collected for the Cu-BEA
`
`zeolite coated core samplesis attached to this declaration as Exhibit C.
`
`A graph showing the NOx conversion performance ofthe 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 1015
`Page 11 of 24
`
`
`
`NOx Conversion % for Fresh Cu-BEA
`Samples with a SAR of 30 at 200°C
`
`100
`
`oo oO
`
`60
`
`40
`
`
`
`NOxconversion,%
`
`0.0
`
`0.1
`
`0.2
`
`0.3
`
`0.4
`
`0.5
`
`0.6
`
`Cu / Al ratio
`
`Figure 6
`
`I declare thatall statements made herein of my own knowledge ate true and
`
`that all statements made on information and belief are believed to be true, and further
`
`that these statements wete 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: ODBOEOne
`
`
`
`
`DIT iG < A Cc tow >
`
`Dr. Frank-Walter Schiitze
`
`Umicore AG & Co. KG
`Exhibit 1015
`Page 12 of 24
`
`
`
`EXHIBIT A
`
`Umicore AG & Co. KG
`Exhibit 1015
`Page 13 of 24
`
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`Page 17 of 24
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`Umicore AG & Co. KG
`Exhibit 1015
`Page 18 of 24
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`Exhibit 1015
`Page 19 of 24
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`Umicore AG & Co. KG
`Exhibit 1015
`Page 20 of 24
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`Umicore AG & Co. KG
`Exhibit 1015
`Page 21 of 24
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`Umicore AG & Co. KG
`Exhibit 1015
`Page 22 of 24
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`EXHIBIT C
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`Umicore AG & Co. KG
`Exhibit 1015
`Page 23 of 24
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`
`essolzovy|Zs80Lzove|9ssolzove|ssgorzowa|sida:(0€UVS)
`
`
`[see|orm[ereesse[|sezr_|[seve|arte|wres|eeez|sv'0se——[_srze__|_isvz__|eroozdCitCSC
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`"AUODXON"AUODXON"AUODXON*AUODXON
`vest|tere|vooz|oir|%¥moND
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`%%%%,
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`
`
`
`ZSv7'0Ssvc'08vL°0
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`80°00¢
`
`Umicore AG & Co. KG
`Exhibit 1015
`Page 24 of 24
`
`
`