Patent Owner’s Demonstratives
`
`IPR2015-01121, -23, -24, -25
`Umicore AG & CO. KG v. BASF Corporation
`(Oral Hearing – July 28, 2016)
`
`1
`
`
`
`IPR2015-01121, -23, -24, -25
`Umicore AG & CO. KG v. BASF Corporation
`(Oral Hearing – July 28, 2016)
`
`1
`
`
`
`Metal-Exchanged Zeolite Catalysts
`
`2
`
`
`
`Zeolite Overview
`
`• Crystalline framework materials that contain pores of a molecular size.
`• Framework types are cataloged by the IZA.
`
`Framework
`
`Materials
`chabazite (natural)
`SSZ‐13
`SSZ‐62
`
`Pore Size
`3.8 Angstroms
`
`Ring Structure
`8‐ring
`
`faujasite (natural)
`zeolite‐Y
`
`7.4 Angstroms
`
`12‐ring
`
`Ex. 2018, ¶¶56‐61
`
`3
`
`
`
`Zeolite SCR Catalysts: Pre-662 Patent
`
`“Indeed, several unresolved problems limit the outlook for
`successful use of zeolites in automotive converters: (i)
`hydrothermal stability, (ii) sensitivity to poisoning….A low
`hydrothermal stability, in particular, is the more critical
`weakness of copper‐containing zeolites.”
`
`Ex. 2012.005 (1995)
`
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`4
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`
`
`Zeolite SCR Catalysts: Pre-662 Patent
`
`“The catalyst was tested for durability in both wet and sulphur containing gases, but
`even water had a negative long‐term effect on the catalyst and its applicability must
`be regarded as rather low. One can be quite pessimistic about the use of zeolites
`for several reasons:
`(i) The catalyst types have been tested in the SCR reaction since the eighties
`without a commercial breakthrough.
`(ii) Zeolites have been extensively tested in the so‐called HC‐SCR reaction with
`insufficiently long‐term stability….
`
`Ex. 2026.006 (2004)
`
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`5
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`
`
`Zeolite SCR Catalysts: Pre-662 Patent
`
`“The aim of this study was to obtain knowledge
`about the activity of zeolite‐based catalysts in
`the NH3‐SCR reaction with excess of oxygen.
`The limited hydrothermal stability of zeolites
`may restrict their use.”
`
`Ex. 2021.002 (2004)
`
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`6
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`
`
`Zeolite SCR Catalysts: Pre-662 Patent
`
`“Consequently, achieving hydrothermal stability of the catalyst is a critical issue in
`the commercial application of urea SCR technology to the exhaust stream from diesel
`engines.”
`
`“CuZSM5 has been reported as one of the most promising catalysts for the SCR of
`NOx from light‐ and heavy‐ duty diesel engines with urea. However, the
`hydrothermal stability of the catalyst is another critical issue to be resolved for the
`commercial application of urea SCR technology to automotive engines. CuZSM5 after
`hydrothermal aging under simulated flue gas stream at temperature above 600° C
`with 10% water reveals significant catalyst deactivation.
`
`Ex.2024.001, .010 (2006)
`
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`7
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`
`
`Zeolite SCR Catalysts: Pre-662 Patent
`
`“Although metal‐exchanged zeolites have proven to be very active SCR catalysts, using these
`materials in exhaust after‐treatment systems on diesel vehicles is a difficult task. One of the
`challenges for the practical application of SCR catalysts is their durability under hydrothermal
`conditions. Fe‐ZSM‐5 catalysts, for instance, have been reported to be very stable even in the
`presence of H2O, but at temperatures above 500° C deactivation is always observed.”
`
`“One of the major requirements for the practical application of zeolites in the SCR process is
`their durability under hydrothermal conditions, which is not yet sufficient. There is no
`guarantee that a zeolite‐based catalyst will be found that meets all of the diverse requirements
`for future SCR systems on diesel vehicles. Research is now targeting catalysts that combine
`both high activity at low temperatures and hydrothermal stability at high temperatures.”
`
`Ex. 2022.016, .029 (2008)
`
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`
`
`Zeolite SCR Catalysts: Post-662 Patent
`
`“Improvements in the thermal durability of Cu/zeolite based SCR formulations has
`been highly desirable and pursued by many research institutes and catalyst
`suppliers.”
`
`“In this work, a laboratory flow reactor was utilized to hydrothermally age and
`evaluate the latest state‐of‐the‐art Cu/zeolite formulations. Results confirm
`remarkable high temperature stability up to 950 °C while maintaining stable low
`temperature NOx activity. A broad range of time‐at‐temperature hydrothermal aging
`was carried out to clearly define the full durability range. The aging time was varied
`from 1 hour to 256 hours while aging temperature was varied from 670 °C to 1100
`°C.”
`Ex. 2002.001‐.002 (2008)
`
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`9
`
`
`
`Zeolite SCR Catalysts: Post-662 Patent
`
`“In the very recent patent literature, Cu2+ ion‐exchanged SSZ‐13 (Cu‐SSZ‐13) has
`been reported to exhibit NOx conversions of 90‐100% over a wide temperature
`range in the NH3‐SCR process, and its activity exceeded 80% even after extensive
`high‐temperature hydrothermal aging [9]. The SSZ‐13 has chabazite (CHA)
`structure with a relatively small pore radius (~3.8 A) in an eight‐membered ring
`[10].”
`
`“Our results confirm that the activity and selectivity of the Cu‐SSZ‐13 catalyst for
`both NOx SCR with NH3 and NH3 oxidation are superior to those of both Cu‐beta
`and Cu‐ZSM‐5.”
`Ex. 2014.001 (2010)
`
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`10
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`
`
`Non-CHA Framework Types: Pre-662 Patent
`
`Ex. 2029.001
`MFI
`
`Ex. 2031.001
`MFI
`
`Ex. 2030
`FAU (zeolite‐Y)
`MFI (ZSM‐5)
`
`Ex. 2025.001
`MOR (mordenite)
`
`Ex. 2022.027
`MFI, MOR, BEA,
`FER
`
`Ex. 2032.001
`MFI
`
`Exs. 2023.001
`MFI
`
`Ex. 2021.002
`MFI, MOR, FAU
`FER (ferrierite)
`
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`11
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`
`
`CHA Framework Type: Pre-662 Patent
`
`MOR
`ERI
`NAT
`CHA
`FAU
`
`Ex. 1002 at 4:6‐12, 36‐38
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`12
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`
`
`CHA Framework Type: Pre-662 Patent
`
`“…it appears that SO2 poisoning has both short term and long term effects. For
`example, flowing a gas stream containing 2,000 parts per million by volume
`("Vppm") SO2 through catalysts comprising copper‐promoted small to medium
`pore zeolites such as…naturally occurring chabazite…resulted in 10 to 40 percent
`reduction in SCR process activity. Even at So2 levels as low as 130 Vppm SO2,
`significant activity reduction for the SCR process was noted for such catalysts.”
`
`“A 60 percent reduction in SCR process activity is typical for Fe2O3 containing
`natural chabazite.”
`
`“It has been found that zeolites which are highly resistant to sulfate poisoning
`and provide good activity….are zeolites which have pores which exhibit a pore
`diameter of at least about 7 Angstroms and are interconnected in three
`dimensions.”
`
`Ex. 1010 at 4:62‐68, 5:23‐25 6:12‐20
`
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`13
`
`
`
`CHA Framework Type: Pre-662 Patent
`
`“Also provided by the present invention is an improved process for the
`reduction of oxides of nitrogen contained in a gas stream in the
`presence of oxygen wherein said process comprises contacting the gas
`stream with a zeolite, the improvement comprising using as the zeolite
`a zeolite having the CHA crystal structure, a mole ratio greater than
`about 10 of silicon oxide to aluminum oxide and having a crystallite size
`of 0.5 micron or less. The zeolite may contain a metal or metal ions
`(such as cobalt, copper or mixtures thereof) capable of catalyzing the
`reduction of the oxides of nitrogen, and may be conducted in the
`presence of a stoichiometric excess of oxygen. In a preferred
`embodiment, the gas stream is the exhaust stream of an internal
`combustion engine.”
`
`Ex. 1004 at 1:54‐67
`
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`14
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`
`
`CHA Framework Type: Post-662 Patent
`
`Ex. 2002
`Cavataio, G., et al. “Enhanced Durability of a Cu/Zeolite
`Based SCR Catalyst,” SAR Int. J. Fuels. Lubr., Vol. 1, Issue 1.
`
`Ex. 2014
`Kwak, J., et al., “Excellent Activity and Selectivity of Cu‐SSZ‐13 in the
`Selective Catalytic Reduction of NOx with NH3,” Journal of Catalysis.
`
`Ex. 2020
`
`Gao F., et al., “Effects of Si/Al ratio on Cu/SSZ‐13 NH3‐SCR catalysts:
`Implications for the active species and the roles of Bronsted acidity,”
`Journal of Catalysis.
`
`2005
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`2010
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`2015
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`15
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`
`
`’662 and ’203 Patents
`
`16
`
`
`
`• Claim 1 (catalyst):
`– aluminosilicate CHA
`– SAR: 15-150
`– Cu/Al: 0.25-1
`– NH3-SCR of NOx
`• Dep. Claims 2-8:
`– SAR: 15-100, 25-40, 30
`– Cu/Al: 0.30-0.50, 0.40
`
`’662 Claims
`
`• Dep. Claims 12-14, 32, 39, 40
`– Catalyst deposited on substrate
`• Dep. Claims 15-20, 41-46
`– Substrate coated with CuCHA,
`or coated with Pt and CuCHA
`• Dep. Claims 21-24, 47-50
`– Catalyst disposed downstream
`of a diesel engine
`• Dep. Claims 33-38
`– Exhaust gas treatment system
`including catalyzed soot filter
`and diesel oxidation catalyst
`located upstream of the CuCHA
`catalyst
`
`17
`
`
`
`Properties of the Claimed CuCHA Catalyst
`
`Example 1 of ’662 Patent
`SAR = 30, Cu/Al = 0.30
`
`Example 2 of ’662 Patent
`SAR = 30, Cu/Al = 0.33
`
`18
`
`
`
`Criticality of Claimed Ranges: Cu/Al
`
`Ex. 2018 at ¶149
`
`19
`
`
`
`Criticality of Claimed Ranges: Cu/Al
`
`Ex. 2018 at ¶148
`
`20
`
`
`
`Criticality of Claimed Ranges: SAR
`
`Ex. 2018 at ¶150
`
`21
`
`
`
`Properties of Prior Art CuCHA
`
`Natural Chabazite
`SAR 6.3, Cu/Al 0.32
`
`Synthetic Chabazite
`SAR 4.5, Cu/Al 0.33
`
`Ex. 2011 at ¶¶11‐14
`
`22
`
`
`
`Properties of Prior Art Cu-Y, Cu-Beta, and Cu-ZSM
`
`“Our results confirm that the activity and selectivity
`of the Cu‐SSZ‐13 catalyst for both NOx SCR with NH3
`and NH3 oxidation are superior to those of both Cu‐
`beta and Cu‐ZSM‐5.”
`
`Ex. 2014.001 (2010)
`
`Cu‐Y
`Cu‐Beta
`
`23
`
`
`
`Zones in view of Maeshima
`(’662 Claims 1-8, 30)
`(’203 Claims 1, 14, 15, 17-22, 26, 27)
`
`24
`
`
`
`Zones ’644: Small Crystal Size CHA Zeolite
`
`Ex.1004 at 1:5‐15
`
`25
`
`
`
`Zones ’644: General Disclosure Regarding Processes
`
`“converting lower alcohols and other oxygenated hydrocarbons”
`Ex.1004 at 1:46‐53, 5:17‐35, 7:4‐23
`
`“catalyzing the reduction of oxides of nitrogen, and may be conducted in the
`presence of a stoichiometric excess of oxygen”
`Ex.1004 at 1:61‐65
`
`“as a catalyst to prepare dimethylamine”
`
`Ex.1004 at 5:36‐64
`
`“SSZ‐62 can also be used to separate gasses”
`
`Ex.1004 at 5:66‐6:2
`
`26
`
`
`
`Zones ’644: General Disclosure Regarding Processes
`
`“Also provided by the present invention is
`an improved process for the reduction of
`oxides of nitrogen contained in a gas
`stream in the presence of oxygen wherein
`said process comprises contacting the gas
`stream with a zeolite, the improvement
`comprising using as the zeolite a zeolite
`having the CHA crystal structure, a mole
`ratio greater than about 10 of silicon oxide
`to aluminum oxide and having a crystallite
`size of 0.5 micron or less. The zeolite may
`contain a metal or metal ions (such as
`cobalt, copper or mixtures thereof) capable
`of catalyzing the reduction of the oxides of
`nitrogen, and may be conducted in the
`presence of a stoichiometric excess of
`oxygen. In a preferred embodiment, the
`gas stream is the exhaust stream of an
`internal combustion engine.”
`
`Ex.1004 at 1:54‐67
`
`‐ Reduction of NO without reducing agents
`‐ Decomposition of NO in presence of oxygen
`‐ N2O decomposition
`‐ NH3‐SCR of NOx
`‐ HCR‐SCR of NOx
`
`Ex.2009 at ¶8
`Ex.2018 at ¶79
`Ex.2027 at 37:19‐38:22
`
`27
`
`
`
`Zones ’644: No Disclosure of Using SSZ-62 for NH3-SCR of NOx
`
`Ex. 2006.026-.027
`
`28
`
`
`
`Zones ’644: No Disclosure of the Properties of
`SSZ-62 for the SCR of NOx
`
`Reduction of NOx
`
`Converting Methanol
`“The catalyst gives greater than 90%
`selectivity for C2‐C4 olefins and does
`not show methanol breakthrough for
`greater than 15 hours. Prior art
`catalysts with larger crystallite sizes
`than SSZ‐62 (like SSZ‐13 with a
`crystallite size of about 1.2 microns
`and a silica/alumina mole ratio of
`about 9 or 18) show breakthrough at
`about 5 hours on stream under these
`conditions. The smaller crystallite SSZ‐
`62 gives superior performance in this
`application.”
`
`Ex.1004 at 7:16‐23
`
`Ex.1004
`
`29
`
`
`
`Zones ’644 Compared to Byrne
`
`Byrne
`“…copper‐promoted small to medium
`pore zeolites such…naturally occurring
`chabazite…resulted in 10 to 40
`percent reduction in SCR process
`activity. Even at SO2 levels as low as
`130 Vppm SO2, significant activity
`reduction for the SCR process was
`noted for such catalysts. On the other
`hand, larger pore zeolites such as Y, L
`and USY exhibited no short‐term SO2
`susceptibility….A 60 percent reduction
`in SCR process activity is typical for
`Fe2O3 containing natural chabazite.”
`
`Ex.1010 at 4:65‐5:26
`
`Zones ’644
`“…a zeolite having the CHA crystal
`structure, a mole ratio greater than
`about 10 of silicon oxide to aluminum
`oxide and having a crystallite size of 0.5
`micron or less. The zeolite may contain
`a metal or metal ions (such as cobalt,
`copper or mixtures thereof) capable of
`catalyzing the reduction of the oxides
`of nitrogen, and may be conducted in
`the presence of a stoichiometric excess
`of oxygen.”
`
`Ex.1004 at 1:61‐65
`
`30
`
`
`
`Maeshima: NH3-SCR of NOx in Stationary Source
`
`Ex.1002 at 2:9‐21
`
`31
`
`
`
`Maeshima: Temperature Limitations
`
`Ex.1002 at 3:23‐32
`
`32
`
`
`
`Maeshima: Zeolite Frameworks
`
`Ex.1002 at 4:6‐35
`
`33
`
`
`
`Maeshima: Use Low SAR, Large Pore Size Zeolite
`Frameworks
`
`Ex.1002 at 4:36‐43
`
`34
`
`
`
`Maeshima: Metal Ions
`
`Ex.1002 at 6:1‐7
`
`35
`
`
`
`Maeshima: Ion Exchange Ratio Not Critical
`
`Ex.1002 at 4:44‐50
`
`36
`
`
`
`Petitioner Assumes That CuCHA Is Used For
`NH3-SCR of NOx
`
`Ex. 1008, Lercher Decl. at ¶ 152
`
`37
`
`
`
`Petitioner Asserts That Increasing Cu/Al Ratio
`Predictably Enhances Zeolite Properties
`
`Ex. 1008, Lercher Decl. at ¶ 153
`
`38
`
`
`
`Petitioner’s Evidence of Predictability
`
`39
`
`
`
`Unpredictability of Increasing Amount of Copper
`
`40
`
`
`
`Unpredictability of Increasing Amount of Copper
`
`• Ex. 2012.005 (1995)
`– “A low hydrothermal stability, in particular, is the more critical
`weakness of copper-containing zeolites.”
`• Ex. 2002.001 (2008)
`– “Fe/zeolite formulations are known to exhibit superior hydrothermal
`stability over Cu/zeolite formulation”
`• Ex. 2022.026 (2008)
`– “Iron-exchange ZSM-5 has received much attention because of its
`promising activity and stability in the NH3-SCR process. The SCR
`activity of Fe-ZSM-5 has even shown to exceed that of the
`established commercial V2O5-WO3-TiO2 catalysts. Cu-containing
`zeolites are also very active, though they suffer from low
`hydrothermal stability and high NH3 oxidation activity.”
`
`41
`
`
`
`Petitioner Correlates The Metal Percentages in
`Zones and Maeshima
`
`Ex. 1008, Lercher Decl. at ¶ 157
`
`42
`
`
`
`Zones ’644: Metal Weight Unrelated to SCR of NOx
`
`Ex.1004 at 1:5‐15
`
`43
`
`
`
`Petitioner Asserts That Zones and Maeshima Are
`Directed To The Same Problem
`
`Ex. 1008, Lercher Decl. at ¶ 158
`
`44
`
`
`
`Petitioner Asserts That Improving Zeolite SCR
`Performance is Simple and Straightforward
`
`Ex. 1008, Lercher Decl. at ¶ 159
`
`45
`
`
`
`Zones ‘538: Metal-Exchanged High SAR, CHA Zeolite
`
`• Metal-exchanged high SAR synthetic CHA zeolite was
`known in the art two decades before Zones ’644
`
`“Usually, it is desirable to remove
`the alkali metal cation by ion
`exchange and replace it with
`hydrogen, ammonium, or any
`desired metal ion.”
`
`Ex.1016 at 5:41‐44
`
`“SSZ‐13 zeolites can have a
`YO2:W2O3 mole ratio greater
`than about 5:1. As prepared,
`the silica:alumina mole ratio
`is typically in the range of 8:1
`to about 50:1; higher mole
`ratios can be obtained by
`varying the relative ratios of
`reactants.”
`
`Ex.1016 at 2:53‐58
`
`46
`
`
`
`Timeline Does Not Support Petitioner’s Assertion
`
`“The elapsed time between the prior art and the ’013 patent’s filing date evinces that the
`’031 patent’s claimed invention was not obvious to try. Indeed this considerable time lapse
`suggests instead that the Board only traverses the obstacles to this inventive enterprise
`with resort to hindsight.”
`
`Leo Pharm. Prods. v. Rea, 726 F.3d 1346, 1356‐1357 (Fed. Cir. 2013)
`
`Maeshima
`
`Zones ’538
`
`Publications describing the
`problem limiting usefulness of
`metal exchanged zeolites
`
`’662 Patent
`
`1975
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`2015
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`47
`
`
`
`Zones + Maeshima + Patchett 843
`(’662 Claims 12-24, 32-50)
`(’203 Claims 2-13, 16, 23-25, 28-31)
`
`48
`
`
`
`Petitioner Acknowledges The Zeolite
`Requirements Specified in Patchett ’843
`
`Ex. 1008, Lercher Decl. at ¶ 246
`
`49
`
`
`
`Petitioner Asserts That Patchett ’843 Would
`Direct POSITA to CHA Zeolite
`
`Ex. 1008, Lercher Decl. at ¶¶ 249‐250
`
`50
`
`
`
`Patchett ’843 Teaches Away from CHA Zeolites
`
`Ex.1005 at [0066]
`
`51
`
`
`
`Patchett ’843 Teaches Away from CHA Zeolites
`
`Ex.1005 at [0065]
`
`52
`
`
`
`Patchett ’843 Teaches Away from CHA Zeolites
`
`• Speronello (Ex. 1011 at 6:43-59)
`– “Specifically, an average pore size of about 7 Angstroms or
`more, e.g., about 7 to about 8 Angstroms is preferred for
`enhanced resistance to sulfur poisoning…[A] particularly
`suitable class of such sulfur-resistant zeolite materials is
`comprised of Beta zeolites, ultrastable Y (“USY”) zeolites, and
`ZSM-20 zeolites.”
`
`53
`
`
`
`Patchett ’843 Teaches Away from CHA Zeolites
`
`• Byrne (Ex. 1010 at 4:57-5:26, 6:12-32)
`– “For example, flowing a gas stream containing 2,000 parts per million by
`volume ("Vppm") SO2 through catalysts comprising copper-promoted small to
`medium pore zeolites such as ZSM-5, naturally occurring chabazite and
`clinoptilolite, resulted in 10 to 40 percent reduction in SCR process activity.
`Even at SO2 levels as low as 130 Vppm SO2, significant activity reduction for
`the SCR process was noted for such catalysts.….In the case of the small to
`medium pore zeolites, this competition absorption with NH3 and NO probably
`results in a physical blockage and/or diffusional restriction….A 60 percent
`reduction in SCR process activity is typical for Fe2 O3 containing natural
`chabazite.”
`– “It has been found that zeolites which are highly resistant to sulfate poisoning
`and provide good activity for both the SCR process ….are zeolites which
`have pores which exhibit a pore diameter of at least about 7 Angstroms and
`are interconnected in three dimensions….[S]pecific zeolites which meet
`these criteria are USY, Beta, and ZSM-20.”
`
`54
`
`
`
`Petitioner Disregards Relevant Parts of Prior Art
`
`“This type of reasoning—where relevant parts of the
`reference are disregarded for the proposed
`combination without sufficient explanation of why a
`person of ordinary skill would do so—is precisely the
`type of hindsight reasoning that must be rejected.”
`Oracle Corp., et al., v. Crossroads Systems, Inc., IPR2014‐01207, Paper 78 at 37 (Jan. 29, 2016)
`
`55
`
`
`
`Patchett ’514: Wall Flow Filter
`
`•
`•
`
`’662 claims 13, 18-20, 23, 24, 39, 44-46, 49, 50
`’203 claims 5-7, 24, 30
`
`Ex.1006 at [0011]
`
`56
`
`
`
`Zones ’644 and Maeshima: No Disclosure of
`Stability at High Temperatures
`
`Maeshima
`“As the reaction conditions, there may be
`adopted a reaction temperature of about
`200° to about 500° C, preferably about
`250° to about 400° C, and a gas space
`velocity of about 2,000 to about 100,000
`V/H/V, preferably about 5,000 to about
`30,000 V/H/V. Since the activity of the
`ammonia reduction of nitrogen oxides is
`lowered at higher or lower temperatures,
`good results are obtained when a mixture
`of the exhaust gas and ammonia is
`contacted with the catalyst bed at a
`temperature within the above‐mentioned
`range.”
`Ex.1004 at 7:16‐23
`
`Zones ’644
`
`Ex.1004
`
`57
`
`
`
`Zones ’644 and Maeshima: No Disclosure of
`Stability at High Temperatures
`
`Maeshima
`As the reaction conditions, there may be
`adopted a reaction temperature of about
`200° to about 500° C., preferably about
`250° to about 400° C…Since the activity of
`the ammonia reduction of nitrogen oxides
`is lowered at higher or lower temperatures,
`good results are obtained when a mixture
`of the exhaust gas and ammonia is
`contacted with the catalyst bed at a
`temperature within the above‐mentioned
`range.
`
`Petitioner’s Expert on Zones
`Q: A slightly broader question: Does the
`Zones patent specifically recognize the
`problem of hydrothermal stability of a
`zeolite for the SCR of NOX?
`[Form Objection]
`A: I do understand your question, but you're
`asking whether Zones is referring to the
`problem of hydrothermal stability with
`respect to NOX removal.
`Q: Yes.
`A: I do not see this in this document.
`
`Ex. 1002 at 3:23‐32
`
`Ex. 2027 at 48:5‐17
`
`58
`
`
`
`Maeshima + Breck
`(’662 Claims 1, 2, 5, 6, 30)
`(’203 Claims 1, 14, 15, 19, 20, 26, 27)
`
`59
`
`
`
`Breck: Dealumination of Zeolites
`
`Ex. 2018 at ¶93
`
`60
`
`
`
`Breck: Dealuminating Zeolites
`
`Ex. 2018 at ¶96
`
`61
`
`
`
`Breck: Aluminum Removal Inefficient for Chabazite
`
`Ex.1003 at 38:44‐48
`
`62
`
`
`
`Maeshima: Zeolite Frameworks
`
`Ex.1002 at 4:6‐35
`
`63
`
`
`
`Maeshima: Use Low SAR, Large Pore Size
`Zeolite Frameworks
`
`Ex.1002 at 4:36‐43
`
`64
`
`
`
`Petitioner Asserts That Dealumination Will Not
`Detrimentally Impact Zeolite Activity
`
`Ex. 1108, Lercher Decl. at ¶¶ 166‐167
`
`65
`
`
`
`Dr. Lercher Cross-Examination
`
`Q: Does de-aluminating the zeolite impact the activity or stability of
`the zeolite?
`A: It impacts both. As we have said before, the concentration of
`aluminum in the lattice determines how many ion exchange positions
`you have, or in the case of an acid material, how many protons you
`have. Therefore, the rates that you have are in the first
`approximation directly proportional to that concentration. In opposite,
`for gas phase reactions, the concentration of aluminum has an
`adverse effect on the hydrothermal stability of that zeolite in two
`ways: One is you remove a particular aluminum out of that lattice.
`That means when you treat it by steam, you just have less elements.
`On the other side, if you have -- like, you should see that lattice like a
`building. If you remove too many bricks, your whole building
`collapses, so structures of that zeolite collapse.
`Q: So, in a sense, de-illuminating the zeolite can decrease the
`activity but may improve the stability?
`A: Yes.
`
`Ex. 2027 at 94:23‐95:25
`
`66
`
`
`
`Dr. Tsapatsis Declaration
`
`Ex. 2018 at ¶122
`
`67
`
`
`
`Dr. Tsapatsis Declaration
`
`Ex. 2018 at ¶123
`
`68
`
`
`
`Maeshima: Starting SAR
`
`Ex.1002 at 4:36‐43
`
`69
`
`
`
`Breck: Increasing SAR of Chabazite is Not Efficient
`
`Ex.1003 at 38:1‐10
`
`Ex.1003 at 38:44‐48
`
`70
`
`
`
`Petitioner Asserts That Breck and Maeshima Are
`Directed To The Same Problem
`
`Ex. 1108, Lercher Decl. at ¶ 169
`
`71
`
`
`
`Petitioner Asserts That Increasing SAR
`Predictability Increases SCR Activity
`
`Ex. 1108, Lercher Decl. at ¶¶ 411‐421
`
`72
`
`
`
`Prior Art: Increasing SAR Can Decrease Activity
`
`Ex.2025.001
`
`Ex.2025.012
`
`73
`
`
`
`Prior Art: Increasing SAR Can Decrease Activity
`
`Ex.2023.004
`
`74
`
`
`
`Petitioner Asserts That Improving Zeolite SCR
`Performance is Simple and Straightforward
`
`Ex. 1108, Lercher Decl. at ¶ 170
`
`75
`
`
`
`Timeline Does Not Support Petitioner’s Assertion
`
`“The elapsed time between the prior art and the ’013 patent’s filing date evinces that the
`’031 patent’s claimed invention was not obvious to try. Indeed this considerable time lapse
`suggests instead that the Board only traverses the obstacles to this inventive enterprise
`with resort to hindsight.”
`
`Leo Pharm. Prods. v. Rea, 726 F.3d 1346, 1356‐1357 (Fed. Cir. 2013)
`
`Maeshima
`
`Breck
`
`Publications describing the
`problem limiting usefulness of
`metal exchanged zeolites
`
`’662 Patent
`
`1975
`
`1980
`
`1985
`
`1990
`
`1995
`
`2000
`
`2005
`
`2010
`
`2015
`
`76
`
`
`
`Dedecek + Breck
`(’662 Claims 1, 2, 5, 6, 30)
`(’203 Claims 1, 14, 15, 19, 20, 26, 27)
`
`77
`
`
`
`Dedecek: Study About Cu+ Ion Siting
`
`• Title: Siting of the Cu+ ions in dehydrated ion
`exchanged and natural chabasites: a Cu+
`photoluminescence study
`
`Ex.1007.001
`
`78
`
`
`
`Dedecek: ZSM-5 for SCR of NOx
`
`“Zeolites containing Cu ions attract attention owing to their high catalytic
`activity in NO [1‐5] and N2O decomposition [6] and selective catalytic
`reduction (SCR) of NO with ammonia [7‐9] and hydrocarbons [10‐12].”
`
`Ex.1007.001
`
`MFI framework
`[ZSM‐5]
`
`79
`
`Ex.2028, 2029, 2030
`
`
`
`Petitioner’s Expert Testimony Regarding Dedecek
`
`Q: Do you agree that there is no discussion, teaching or data in
`Dedecek regarding the use of copper chabazite in any one of those
`reactions?
`[Form Objection]
`A: Dedecek describes materials; he does not address reactions.
`Q: Okay.
`A: He links to those reactions through his introduction.
`Q: That’s the only place --
`A: That’s the only place.
`Q: -- in the first sentence of page 1?
`A: Yes.
`
`Ex.2027 at 79:12‐25
`
`80
`
`
`
`Petitioner Asserts That Dealumination Will Not
`Detrimentally Impact Zeolite Activity
`
`Ex. 1108, Lercher Decl. at ¶ 345
`
`81
`
`
`
`Dedecek: Starting SAR
`
`Ex. 1108 at ¶276
`
`82
`
`
`
`Petitioner Asserts That Dedecek Contemplates
`Higher SAR
`
`Ex. 1108, Lercher Decl. at ¶ 339
`
`83
`
`
`
`Petitioner Asserts That Breck and Maeshima Are
`Directed To The Same Problem
`
`Ex. 1108, Lercher Decl. at ¶ 347
`
`84
`
`
`
`Maeshima/Dedecek + Breck +
`Patchett ’843
`(’662 Claims 12-24, 32-50)
`(’203 Claims 2-13, 16, 23-25, 28-31)
`
`85
`
`
`
`Secondary Considerations
`
`86
`
`
`
`Commercial Success: Product Specification
`
`• BASF’s CuCHA Product (Ex. 2019)
`– SAR: 28-34 (target 31)
`– Cu/Al: 0.38-0.42
`– NH3-SCR of NOx in diesel engine
`– Sold on flow-through substrate or wall-flow filter
`• Claims Practiced (Ex. 2018 at ¶ 175-177)
`– 662 Claims: 1-8, 12-15, 18, 21, 23, 39, 40, 41, 44, 47, 50
`– 203 Claims: 1-3, 5, 6, 14-24, 26-30
`• Market Size and Share
`– Ex. 2034 (Schmidt Declaration)
`
`87
`
`
`
`Commercial Success: Market Size and Share
`
`- Estimated Global Diesel SCR Market (Ex. 2034):
`
`Total Global SCR Market b Units Sold Qn million)
`
`- CuCHA Estimate Market Share (Ex. 2034)
`
`— 2 (combined BASF and 662 licensee)
`
`
`
`
`
`
`
`CERTIFICATE OF SERVICE
`
`The undersigned hereby certifies that on July 25, 2016 the foregoing
`
`PATENT OWNER’S DEMONSTRATIVES FOR THE 2015-01121, 2015-01123,
`
`2015-01124 AND 2015-01125 was served via electronic mail, upon the following:
`
`Elizabeth Gardner
`Richard L. DeLucia
`K. Patrick Herman
`A. Anthony Pfeffer
`Orrick, Herrington & Sutcliffe LLP
`51 West 52nd Street
`New York, NY 10019-6142
`egardner@orrick.com
`rdelucia@orrick.com
`pherman@orrick.com
`apfeffer@orrick.com
`
`/s/ Timothy J. Andersen i
`Timothy J. Andersen
`Case Manager
`Weil, Gotshal & Manges LLP
`1300 Eye Street NW, Suite 900
`Washington, DC 20005
`T: 202-682-7075
`timothy.andersen@weil.com
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