UNITED STATES PATENT AND TRADEMARI<:. OFFICE
`
`BEFORE THE PATENT TRIAL AND APPEAL BOARD
`
`UMICORE AG & CO. KG,
`
`Petitioner
`
`Patent No. 7,601,662
`Issue Date: October 13, 2009
`Title: COPPER CHA ZEOLITE CATALYSTS
`
`DECLARATION OF Dr. FRANK-WALTER SCHUTZE
`
`Case No. IPR2015-01121
`
`Umicore AG & Co. KG
`Exhibit 1015
`Page 1 of 24
`
`

`
`I, Dr. Frank-Walter Schi.itze, declare as follows:
`
`I.
`
`BACKGROUND
`
`1.
`
`I am currently a Senior Manager R&D I Strategic Projects and I am
`
`involved in SCR research and development as well as zeolite related topics in
`
`connection with automotive catalysts at Umicore AG & Co. KG ("Umicore"), which
`
`is located in Hanau-Wolfgang, Germany.
`
`2.
`
`I studied chemistry at the University of Leipzig (Germany) and received
`
`my Ph.D. in Chemisuy 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
`
`(Germany).
`
`3.
`
`I have held my current position at Umicore since the 1st of Januaty
`
`2015. Prior to that, I was Senior Manager R&D I Research and Customer Projects
`
`and was involved in SCR I ASC development. Since I joined Umicore in 2001, I was
`
`involved in R&D for automotive catalysts on several topics, vety often related to
`
`application of zeolites in catalyst formulations.
`
`II. ASSIGNMENT
`
`4.
`
`I was asked to make samples of copper-loaded chabazite zeolite ("Cu-
`
`CHA") catalysts with vatying 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 "Cui Al
`
`ratio").
`
`5.
`
`I was asked to test the catalyst samples I made in different ways. In
`
`-1-
`
`Umicore AG & Co. KG
`Exhibit 1015
`Page 2 of 24
`
`

`
`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 hydrothetmal aging.
`
`III. MATERIALS TESTED
`
`6.
`
`I started my preparation of Cu-CHA catalyst samples by obtaining
`
`various ammonium-type chabazite zeolite (NH4-CHA) matetials with different
`
`framework SARs. I obtained chabazite materials with SARs of 13, 19, 21, 27, and 30.
`
`7.
`
`Next, I copper-loaded these various NH4-CHA materials to produce Cu-
`
`CHA zeolite samples with different Cu/ Al ratios ranging from 0 to 1. Copper(cid:173)
`
`loading of the NH4-CHA materials was performed by aqueous ion-exchange. The
`
`required amount of copper-acetate needed to produce a given Cu/ Al ratio was mixed
`
`with the NH4-CHA and the suspension was then heated for 2 hours at 65 °C.
`
`8.
`
`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,
`
`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 ([Si36_x ~ 0 72]
`
`HJ. Using this formula, the molar amount of aluminum or alumina in this sttuctural
`
`building unit, and thus the ion-exchange capacity, can be calculated. I used the well
`
`accepted stoichiomett1c assumption that 1 Cu2+ ion balance the charge introduced by
`
`2 Al atoms in the sttuctural building unit.
`
`9.
`
`For example: a CHA zeolite with an SAR of 22 contains 3 moles of Al in
`
`-2-
`
`Umicore AG & Co. KG
`Exhibit 1015
`Page 3 of 24
`
`

`
`the framework of the unit cell, introducing 3 moles of positive charge into 1 mole of
`
`the appropriate unit cell. From this I calculated the target amount of Cu2
`
`+ for the
`
`appropriate ion-exchange level (using the above explained assumption) based on the
`
`molar mass of Cu (63.546 g/mole). The stoichiometric maximum amount of copper
`
`that can be ion-exchanged into a zeolite with a SAR of22 is 1.5 mole ofCu, or 95.319
`
`g Cu/mole CHA unit cell.
`
`10.
`
`The unit cell formula for a complete stoichiometric ion-exchange is
`
`represented by ([Si33Al30 72] Cu1.5). From this formula I have calculated (based on the
`
`molar masses of the elements in the unit cell) an amount of 4.226 wt % of Cu in the
`
`material. This is the stoichiometric maximum 100% ion-exchange corresponding to a
`
`Cu/ Al ratio of 0.5.
`
`11 . With these correlations, I created the preparation recipes for the
`
`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
`
`Cu/ Al ratio via ion exchange given the SAR and amount of zeolite in the ion(cid:173)
`
`exchange slurry.
`
`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
`
`other sources.
`
`-3-
`
`Umicore AG & Co. KG
`Exhibit 1015
`Page 4 of 24
`
`

`
`13.
`
`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 amount of 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 were calcined for 2 hours at 500 °C in
`
`air, while the other catalysts were calcined for 4 hours at 640 °C in air.
`
`14.
`
`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 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-CHA materials.
`
`15.
`
`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(cid:173)
`
`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 treatment is assigned as 50 B 800 in the attached
`
`exhibits.
`
`-4-
`
`Umicore AG & Co. KG
`Exhibit 1015
`Page 5 of 24
`
`

`
`IV. TESTING PERFORMED
`
`16.
`
`Each of the samples was tested for performance and its activity in the
`
`selective catalytic reduction (or "SCR") of nitrogen oxides.
`
`17.
`
`SCR activity testing of the samples was carried out using a feed gas
`
`mixture containing 500 ppm nitrogen monoxide (NO), 500 ppm ammonia (NH3), 5
`
`vol.% water vapor (H20), 10 vol.% oxygen (0;), 10 vol.% carbon dioxide (CO;), and
`
`the balance nitrogen. The space velocity for the feed gas was 80.000 h-1
`
`. NOx
`
`concentration and N 20 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,
`
`the percentage of NOx from the feed gas that had been reduced by the sample was
`
`calculated.
`
`V.
`
`DATA COLLECTED
`
`A.
`
`Performance and SCR Activity of Cu-CHA Core Samples
`
`18.
`
`The performance and SCR activity data I collected for the fresh Cu-
`
`CHA coated core samples is attached to this declaration as Exhibit A.
`
`19.
`
`The performance and SCR activity data I collected for the aged Cu-CHA
`
`coated core samples is attached to this declaration as Exhibit B.
`
`20. To help analyze the trends and patterns I observed in the collected data,
`
`I have prepared a few summary graphs.
`
`21.
`
`The following graph compares the NOx conversion performance of the
`
`-5-
`
`Umicore AG & Co. KG
`Exhibit 1015
`Page 6 of 24
`
`

`
`fresh Cu-CHA coated core sample with a SARs of 30, 27, 21, 19, and 13 and various
`
`Cu/ Al ratios at a reaction temperature of 200 oe:
`
`NOx Conversion %of Fresh Cu-CHA
`Samples at 200 °(
`
`100
`
`*-
`c::
`0
`- ~ 60
`Q) > c::
`
`80
`
`40
`
`0
`u
`X
`0
`z
`
`20
`
`0
`0.00
`
`0.20
`
`0.40
`
`0.60
`
`0.80
`
`1.00
`
`1.20
`
`Cu/AI Ratio
`
`Figure 1
`
`-
`
`SAR30
`
`- - - SAR 27
`
`-
`
`- SAR21
`
`----- SAR 19
`
`...... ... SAR 13
`
`22. 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 of27, 21, 19, and 13. While
`
`the relative change in performance was not vety 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 perfotmance.
`
`-6-
`
`Umicore AG & Co. KG
`Exhibit 1015
`Page 7 of 24
`
`

`
`23. 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 oc is plotted below:
`
`NOx Conversion %of Fresh Cu-CHA Samples
`with a SAR of 30 at 200°(
`
`100
`
`• • •
`
`*' 80
`c.'
`0
`-~ 60
`a! > c.
`
`40
`
`0
`u
`X
`
`0 z
`
`20
`
`0
`
`0.0
`
`0.1
`
`0.2
`
`0.3
`CuI AI ratio
`
`0.4
`
`0.5
`
`0.6
`
`Figure 2
`
`24.
`
`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 oC:
`
`-7-
`
`Umicore AG & Co. KG
`Exhibit 1015
`Page 8 of 24
`
`

`
`'
`c:
`0
`·~
`Q) > c:
`
`0
`u
`X
`
`0 z
`
`NOx Conversion %of Aged Cu-CHA
`Samples with a SAR of 30 at 200 °C
`
`100
`
`*' 80
`
`60
`
`40
`
`20
`
`0
`0.00
`
`-
`
`SAR30
`
`0 .20
`
`040
`
`0.60
`
`0.80
`
`1.00
`
`1.20
`
`Cu /AI Ratio
`
`Figure 3
`
`25. 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/ 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.
`
`26.
`
`The following graph compares the NOx convenion performance of the
`
`aged Cu-CHA coated core sample with SARs of27, 21, 19, and 13 and various Cu/Al
`
`ratios at a reaction temperature of 200 oC:
`
`-8-
`
`Umicore AG & Co. KG
`Exhibit 1015
`Page 9 of 24
`
`

`
`*-'
`c:
`0
`'!:2
`<J) > c:
`
`0
`u
`X
`
`0 z
`
`NOx Conversion % of Aged Cu-CHA
`Samples with SARs of 27, 21, 19, and 13 at 200 °C
`
`100
`
`80
`
`60
`
`40
`
`20
`
`0
`0.00
`
`- - - SAR 27
`
`-
`
`-SAR21
`
`-----SAR 19
`
`········· SAR 13
`
`0.20
`
`0.40
`
`0.60
`Cu /AI Ratio
`
`0 .80
`
`1.00
`
`1.20
`
`Figure 4
`
`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 rea.ction temperature of
`200 oc.
`
`28.
`
`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 oc. As the SAR value
`
`increased, the N Ox 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
`
`0.5.
`
`-9-
`
`Umicore AG & Co. KG
`Exhibit 1015
`Page 10 of 24
`
`

`
`NOx Conversion% of Samples with a Cu/AI Ratio of
`About 0.45 at 250 °C After Aging
`
`•
`
`100
`
`80
`
`60
`
`40
`
`20
`
`0
`
`*-s:::
`
`0
`·~
`Q) > s:::
`
`0
`u
`
`0 z
`
`10
`
`15
`
`20
`
`25
`SAR of zeolite
`
`30
`
`35
`
`40
`
`Figure 5
`
`B.
`
`Performance I SCR Activity of BEA Zeolite Core Samples
`
`29.
`
`The performance and SCR activity data I collected for the Cu-BEA
`
`zeolite coated core samples is attached to this declaration as Exhibit C.
`
`30. 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 oc is plotted below:
`
`-10-
`
`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
`
`<[?..
`c.'
`0
`·~ 60
`Q) > c.
`
`80
`
`40
`
`0
`u
`X
`
`0 z
`
`20
`
`0
`
`0.0
`
`0.1
`
`0. 2
`
`0.3
`CuI AI ratio
`
`0 .4
`
`0.5
`
`0.6
`
`I declare that all statements made herein of my own knowledge are true and
`
`that all statements made on information and belief are believed to be t1ue, and further
`
`that these statements were made with the knowledge that willful false statements and
`
`the like so made are punishable by flne or imprisonment, or both, under Section 1001
`
`of Title 18 of the United States Code.
`
`-11-
`
`Umicore AG & Co. KG
`Exhibit 1015
`Page 12 of 24
`
`

`
`EXHIBIT A
`
`Umicore AG & Co. KG
`Exhibit 1015
`Page 13 of 24
`
`

`
`Conv. NOx
`
`90.15
`79.71
`65.05
`48.75
`[%]
`
`Conv. NOx
`
`92.34
`84.12
`72.47
`59.42
`[%]
`
`Conv. NOx
`
`91.59
`90.73
`86.74
`80.52
`[%]
`
`4.755
`0.559
`CHA27
`210879
`fresh
`
`I
`
`3.918
`0.457
`CHA27
`210878
`fresh
`
`I
`
`2.207
`0.254
`CHA27
`210877
`fresh
`
`I
`
`Temperature
`
`400.11
`448.79
`497.11
`544.66
`[DegC]
`
`CuO wt%
`Cu/AI ratio
`
`zeolite
`catalyst
`stage
`
`--
`
`1-
`
`(2) Fresh Cu-CHA coated core samples (SAR 27):
`
`'
`
`12.73
`27.70
`51.03
`81.77
`79.97
`79.22
`89.43
`91.79
`90.49
`85.14
`
`NOx [%]
`Conv.
`alumina
`CuO on
`
`CHA30
`210885
`fresh
`
`15.96
`43.58
`73.79
`94.75
`96.99
`95.21
`86.96
`70.69
`50.32
`30.25
`
`NOx [%]
`Conv.
`7.880
`
`0.987
`CHA30
`210884
`fresh
`
`15.15
`41.95
`73.15
`95.36
`97.57
`96.28
`89.71
`76.28
`59.22
`41.87
`
`NOx [%]
`Conv.
`5.127
`
`0.655
`CHA30
`210883
`fresh
`
`19.09
`49.58
`79.89
`94.60
`96.23
`94.94
`89.45
`76.92
`60.17
`43.01
`
`17.94
`48.12
`79.63
`95.24
`96.48
`95.23
`89.99
`78.40
`62.72
`47.08
`
`18.32
`47.64
`80.11
`95.11
`96.55
`95.40
`91.26
`81.35
`65.95
`49.21
`
`16.30
`42.40
`74.91
`94.80
`96.46
`95.11
`92.96
`89.30
`82.68
`73.76
`
`11.88
`28.42
`57.30
`93.36
`94.21
`92.02
`91.80
`92.25
`90.20
`85.97
`
`7.91
`15.50
`28.34
`68.37
`64.76
`59.00
`87.08
`91.38
`92.11
`92.11
`
`0.00
`0.00
`0.00
`0.00
`0.61
`1.43
`1.19
`1.71
`3.23
`6.00
`
`N.Ox [%]
`Conv.
`4.325
`
`NOx [%]
`Conv.
`3.944
`
`NOx [%]
`Conv.
`3.561
`
`NOx [%]
`Conv.
`2.787
`
`NOx [%]
`Conv.
`2.004
`
`NOx [%]
`Conv.
`1.210
`
`NOx[%]
`Conv.
`0.000
`
`0.559
`CHA30
`210853
`fresh
`
`0.508
`CHA30
`210852
`fresh
`
`0.457
`CHA30
`210851
`fresh
`
`0.355
`CHA30
`210854
`fresh
`
`0.245
`CHA30
`210849
`fresh
`
`0.150
`CHA30
`210848
`fresh
`
`0.000
`CHA30
`210847
`fresh
`
`Temperature
`
`149.99
`174.82
`199.97
`249.79
`299.77
`349.63
`400.05
`448.75
`497.08
`544.71
`[DegC]
`
`CuO wt%
`
`Cu/AI ratio
`
`zeolite
`catalyst
`stage
`
`(1) Fresh Cu-CHA coated core samples (SAR 30):
`
`Umicore AG & Co. KG
`Exhibit 1015
`Page 14 of 24
`
`

`
`14.47
`40.13
`72.18
`94.78
`96.27
`94.21
`86.24
`69.61
`47.70
`25.27
`[%]
`
`16.01
`43.85
`75.42
`95.05
`96.24
`93.84
`86.27
`71.84
`53.81
`36.08
`[%]
`
`12.64
`33.71
`65.19
`93.60
`95.62
`94.31
`89.94
`80.99
`67.90
`53.00
`[%]
`
`Conv. NOx
`
`Conv. NOx
`
`Conv. NOx
`
`6.037
`0.550
`CHA21
`210991
`fresh
`
`5.10
`0.440
`CHA21
`210887
`fresh
`
`2.818
`0.249
`CHA21
`210890
`fresh
`
`150.09
`174.97
`200.16
`249.95
`299.92
`349.72
`400.20
`448.84
`497.00
`544.44
`[DegC]
`
`Temperature
`
`CuO wt%
`Cu/AI ratio
`
`zeolite
`catalyst
`stage
`
`(3) Fresh Cu-CHA coated core samples (SAR 21):
`
`17.01
`47.33
`79.04
`94.99
`96.34
`94.98
`
`15.93
`43.85
`76.99
`95.39
`96.66
`95.57
`
`11.72
`28.34
`59.37
`91.23
`92.75
`91.72
`
`150.07
`174.97
`200.14
`250.00
`299.93
`349.74
`
`Umicore AG & Co. KG
`Exhibit 1015
`Page 15 of 24
`
`

`
`Conv. NOx
`
`95.02
`88.16
`72.36
`50.47
`27.25
`[%]
`
`8.386
`0.505
`CHA 13
`210882
`fresh
`
`Conv. NOx
`
`95.76
`90.97
`79.09
`61.80
`42.55
`[%]
`
`7.490
`0.450
`CHA13
`210881
`fresh
`
`Conv. NOx
`
`95.86
`92.83
`86.01
`74.38
`60.06
`[%]
`
`4.360
`0.255
`CHA13
`210880
`fresh
`
`Temperature
`
`349.68
`400.13
`448.81
`497.16
`544.67
`[DegC]
`
`CuO wt%
`Cu/AI ratio
`
`zeolite
`catalyst
`stage
`
`(5) Fresh Cu-CHA coated core samples (SAR 13):
`
`Conv. NOx
`
`19.69
`52.70
`82.54
`95.31
`95.92
`93.53
`84.70
`65.78
`43.68
`24.32
`[%]
`
`Conv. NOx
`
`19.11
`50.47
`82.38
`95.88
`97.12
`95.55
`90.39
`79.22
`64.76
`50.31
`[%]
`
`Conv. NOx
`
`13.88
`39.23
`74.72
`95.05
`96.36
`94.86
`91.10
`84.56
`75.37
`65.96
`[%]
`
`Temperature
`
`149.97
`174.86
`200.02
`249.85
`299.76
`349.60
`399.98
`448.80
`497.26
`544.92
`[DegC]
`
`5.913
`0.500
`CHA19
`210874
`fresh
`
`4.198
`0.350
`CHA19
`210873
`fresh
`
`2.434
`0.200
`CHA19
`210872
`fresh
`
`CuO wt%
`Cu/AI ratio
`
`zeolite
`catalyst
`stage
`
`(4) Fresh Cu-CHA coated core samples (SAR 19):
`
`Umicore AG & Co. KG
`Exhibit 1015
`Page 16 of 24
`
`

`
`27.28
`66.65
`86.03
`95.35
`96.41
`
`27.70
`66.70
`86.25
`95.50
`96.79
`
`27.01
`65.98
`86.67
`95.45
`96.75
`
`149.97
`174.84
`200.07
`249.88
`299.88
`
`Umicore AG & Co. KG
`Exhibit 1015
`Page 17 of 24
`
`

`
`EXHIBITB
`
`Umicore AG & Co. KG
`Exhibit 1015
`Page 18 of 24
`
`

`
`2.75
`7.66
`15.34
`42.52
`57.00
`55.03
`53.70
`56.97
`58.71
`55.25
`
`NOx [%]
`Conv.
`alumina
`CuO on
`
`CHA30
`210885
`508800
`
`0.01
`0.38
`0.89
`4.76
`11.46
`16.23
`18.69
`21.46
`20.90
`14.04
`
`1.31
`4.68
`11.01
`35.31
`54.14
`56.64
`54.89
`54.24
`47.55
`33.80
`
`NOx [%]
`Conv.
`7.880
`
`NOx [%]
`Conv.
`5.127
`
`0.987
`CHA30
`210884
`508800
`
`0.655
`CHA30
`210883
`508800
`
`3.58
`9.59
`20.14
`53.75
`71.00
`71.53
`69.31
`67.93
`59.80
`44.25
`NOx [%]
`Conv.
`4.325
`
`0.559
`CHA30
`210853
`508800
`
`3.67
`9.56
`21.13
`55.63
`72.26
`72.20
`70.25
`68.94
`60.51
`43.97
`
`NOx [%]
`Conv.
`3.944
`
`0.508
`CHA30
`210852
`508800
`
`I
`
`4.69
`11.85
`24.64
`63.46
`79.11
`78.33
`76.03
`74.38
`65.62
`49.11
`
`NOx [%]
`Conv.
`3.561
`
`0.457
`CHA30
`210851
`508800
`
`49.19
`49.30
`44.57
`31.71
`[%]
`
`64.45
`62.66
`55.05
`40.66
`[%]
`
`63.63
`65.24
`61.02
`48.13
`[%]
`
`Conv. NOx
`
`Conv. NOx
`
`Conv. NOx
`
`4.755
`0.559
`CHA27
`210879
`I 50 8 800 -lso8 800 1 50 8 800
`
`3.918
`0.457
`CHA27
`210878
`
`2.207
`0.254
`CHA27
`210877
`
`400.11
`448.79
`497.11
`544.66
`[DegC]
`
`Temperature
`
`CuO wt%
`Cu/AI ratio
`
`zeolite
`catalyst
`stage
`
`-
`
`I
`
`(2) Aged Cu-CHA coated core samples (SAR 27):
`
`3.89
`10.55
`22.86
`60.52
`76.68
`75.02
`73.05
`72.39
`63.12
`45.30
`
`NOx [%]
`Conv.
`2.787
`
`0.355
`CHA30
`210854
`508800
`
`3.10
`7.30
`14.69
`43.96
`63.02
`61.05
`60.45
`65.43
`66.40
`59.50
`
`NOx [%]
`Conv.
`2.004
`
`0.245
`CHA30
`210849
`508800
`
`2.05
`3.69
`6.29
`18.94
`31.90
`33.69
`37.27
`44.53
`49.94
`51.13
`
`NOx [%]
`Conv.
`1.210
`
`0.150
`CHA30
`210848
`508800
`
`0.00
`-0.04
`-0.03
`-0.14
`0.29
`0.24
`0.49
`1.02
`1.98
`3.72
`
`NOx [%]
`Conv.
`0.000
`
`0.000
`CHA30
`210847
`508800
`
`150.25
`175.14
`200.40
`250.23
`300.39
`350.50
`401.21
`450.12
`498.85
`547.18
`[DegC]
`
`Temperature
`
`CuO wt%
`
`Cu/AI ratio
`
`zeolite
`catalyst
`stage
`
`(1) Aged Cu-CHA coated core samples (SAR 30):
`
`Umicore AG & Co. KG
`Exhibit 1015
`Page 19 of 24
`
`

`
`Conv. NOx
`
`1.12
`2.91
`6.52
`21.28
`35.03
`36.25
`36.55
`39.17
`36.10
`20.93
`[%]
`
`I
`
`Conv. NOx
`
`1.45
`3.42
`7.72
`24.15
`38.68
`39.53
`39.86
`42.39
`40.29
`29.16
`[%]
`
`6.037
`0.55Q
`CHA21
`210991
`508800
`
`5.10
`0.440
`CHA21
`210887
`508800
`
`I
`
`2.12
`5.16
`11.39
`35.87
`54.83
`54.33
`53.32
`56.85
`56.10
`47.51
`[%]
`
`I
`
`Conv. NOx
`
`2.818
`0.249
`CHA21
`210890
`508800
`
`Temperature
`
`150.09
`174.97
`200.16
`249.95
`299.92
`349.72
`400.20
`448.84
`497.00
`544.44
`[DegC)
`
`CuO wt%
`Cu/AI ratio
`
`zeolite
`catalyst
`stage
`
`I
`
`(3) Aged Cu-CHA coated core samples (SAR 21):
`
`1.16
`2.95
`6.99
`25.10
`45.01
`50.15
`
`2.35
`6.24
`13.88
`42.49
`62.87
`66.14
`
`2.92
`7.38
`16.38
`48.32
`67.87
`66.66
`
`150.07
`174.97
`200.14
`250.00
`299.93
`349.74
`
`Umicore AG & Co. KG
`Exhibit 1015
`Page 20 of 24
`
`

`
`9.90
`16.13
`21.29
`21.06
`10.95
`[%]
`
`8.74
`14.33
`19.34
`20.93
`14.94
`[%]
`
`19.32
`19.83
`22.41
`24.57
`23.97
`[%]
`
`Conv. NOx
`
`Conv. NOx
`
`Conv. NOx
`
`8.386
`0.505
`CHA13
`210882
`508800
`
`I
`
`7.490
`0.450
`CHA13
`210881
`508800
`
`I
`
`4.360
`0.255
`CHA 13
`210880
`508800
`
`I
`
`350.33
`400.99
`450.06
`498.93
`547.40
`[DegC]
`
`Temperature
`
`GuO wt%
`Gu/AI ratio
`
`zeolite
`cata!vst
`stage
`
`I
`
`(5) Aged Cu-CHA coated core samples (SAR 13):
`
`Conv. NOx
`
`1.24
`3.12
`6.99
`23.38
`39.64
`42.47
`43.24
`46.49
`44.27
`31.40
`[%]
`
`Conv. NOx
`
`1.98
`4.73
`10.57
`32.41
`51.03
`52.39
`51.96
`55.11
`53.01
`41.04
`[%]
`
`5.913
`0.500
`CHA19
`210874
`508800
`
`4.198
`0.350
`CHA19
`210873
`508800
`
`1.61
`4.55
`10.89
`36.23
`55.41
`55.58
`55.10
`59.28
`59.99
`53.20
`[%]
`
`Conv. NOx
`
`2.434
`0.200
`CHA19
`210872
`508800
`
`149.97
`174.86
`200.02
`249.85
`299.76
`349.60
`399.98
`448.80
`497.26
`544.92
`[DegC]
`
`Temperature
`
`GuO wt%
`Gu/AI ratio
`
`zeolite
`catalyst
`stage
`
`( 4) Aged Cu-CHA coated core samples (SAR 19):
`
`Umicore AG & Co. KG
`Exhibit 1015
`Page 21 of 24
`
`

`
`0.60
`0.76
`1.07
`2.34
`5.19
`
`-0.06
`0.20
`0.57
`1.98
`4.43
`
`0.13
`0.65
`1.90
`7.57
`15.93
`
`150.12
`174.98
`200.19
`250.14
`300.27
`
`Umicore AG & Co. KG
`Exhibit 1015
`Page 22 of 24
`
`

`
`EXHIBIT C
`
`Umicore AG & Co. KG
`Exhibit 1015
`Page 23 of 24
`
`

`
`18.86
`52.28
`82.75
`94.88
`95.69
`93.83
`90.27
`88.34
`87.68
`85.34
`f%1
`
`14.70
`42.77
`74.67
`91.77
`93.17
`91.74
`88.91
`87.40
`88.19
`88.46
`f%1
`
`NOxconv.
`
`NOx conv.
`
`NOx conv.
`
`6.46
`18.09
`35.52
`58.74
`64.69
`72.03
`76.22
`79.52
`83.36
`85.91
`[%]
`
`NOxconv.
`
`3.50
`8.37
`12.95
`23.89
`37.11
`49.77
`59.01
`67.11
`73.40
`78.02
`[%]
`
`Temperature
`
`150.15
`175.04
`200.19
`250.05
`300.08
`349.98
`400.44
`449.36
`498.04
`546.18
`[DegC]
`
`3.994
`0.559
`BEA30
`
`3.561
`0.457
`BEA30
`
`2.004
`0.245
`BEA30
`
`1.210
`0.148
`BEA30
`
`RAC210858
`
`RAC210857
`
`RAC210856
`
`RAC210855
`
`fresh
`
`fresh
`
`fresh
`
`fresh
`
`CuOwt.%
`
`Cu/ AI
`zeolite
`
`Fresh Cu-BEA coated core samples (SAR 30):
`
`Umicore AG & Co. KG
`Exhibit 1015
`Page 24 of 24