UNITED STATES PATENT AND TRADEMARK OFFICE
`__________________
`
`BEFORE THE PATENT TRIAL AND APPEAL BOARD
`__________________________________________________________________
`
`UMICORE AG & CO. KG
`Petitioner
`
`v.
`
`BASF CORPORATION
`
`Patent Owner
`
`Cases IPR2015-01121, -1125
`U.S. Patent 7,601,662
`
`Cases IPR2015-01123, -1124
`U.S. Patent 8,404,203
`
`__________________________________________________________________
`
`PETITIONER’S ORAL ARGUMENT DEMONSTRATIVE EXHIBITS
`
`__________________________________________________________________
`
`1
`
`
`__________________
`
`BEFORE THE PATENT TRIAL AND APPEAL BOARD
`__________________________________________________________________
`
`UMICORE AG & CO. KG
`Petitioner
`
`v.
`
`BASF CORPORATION
`
`Patent Owner
`
`Cases IPR2015-01121, -1125
`U.S. Patent 7,601,662
`
`Cases IPR2015-01123, -1124
`U.S. Patent 8,404,203
`
`__________________________________________________________________
`
`PETITIONER’S ORAL ARGUMENT DEMONSTRATIVE EXHIBITS
`
`__________________________________________________________________
`
`1
`
`
`
`Grounds at Issue
`
`IPR2015-01121 (’662 patent)
`1. Claims 1–8 and 30 obvious over Zones and Maeshima
`2. Claims 12–24 and 32–50 obvious over Zones, Maeshima, and Patchett
`
`IPR2015-01125 (’662 patent)
`1. Claims 1, 2, 5, 6, and 30 obvious over Maeshima and Breck
`2. Claims 12–24 and 32–38 obvious over Maeshima, Breck, and Patchett
`3. Claims 1, 2, 5, 6, and 30 obvious over Dedecek and Breck
`4. Claims 12–24 and 32–38 obvious over Dedecek, Breck, and Patchett
`
`IPR2015-01123 (’203 patent)
`1. Claims 1, 14, 15, 17–22, 26, and 27 obvious over Zones and Maeshima
`2. Claims 2–13, 16, 23–25, and 28-31 obvious over Zones, Maeshima, and Patchett
`
`IPR2015-01124 (’203 patent)
`1. Claims 1, 14, 15, 19, 20, 26, and 27 obvious over Maeshima and Breck
`2. Claims 2–13, 16, 23–25, and 28–31 obvious over Maeshima, Breck, and Patchett
`3. Claims 1, 14, 15, 19, 20, 26, and 27 obvious over Dedecek and Breck
`4. Claims 2–13, 16, 23–25, and 28–31 obvious over Dedecek, Breck, and Patchett
`
`2
`
`
`
`’662 Patent – Claim 1
`
`1. A catalyst comprising: an aluminosilicate zeolite
`having the CHA crystal structure and a mole ratio of silica
`to alumina from about 15 to about 150 and an atomic ratio
`of copper to aluminum from about 0.25 to about 1, the
`catalyst effective to promote the reaction of ammonia with
`nitrogen oxides to form nitrogen and H2O selectively.
`
`IPR2015-1121, Ex. 1001,
`662 patent
`
`3
`
`
`
`’203 Patent – Claim 26
`
`26. A process for the reduction of oxides of nitrogen
`contained in a gas stream in the presence of oxygen
`wherein said process comprises adding a reductant to the
`gas stream and contacting the gas stream containing the
`reductant with a catalyst comprising a zeolite having the
`CHA crystal structure and a mole ratio of silica to alumina
`from about 15 to about 150 and an atomic ratio of copper
`to aluminum from about 0.25 to about 1.
`
`IPR2015-1123, Ex. 1001,
`203 patent
`
`4
`
`
`
`Prior Art as of 2007
`
`“Both synthetic and natural zeolites and their use in promoting certain
`reactions, including the selective reduction of nitrogen oxides with
`ammonia in the presence of oxygen are well known in the art.”
`(IPR2015-1121, Ex. 1001,
`662 Patent at 1:26-29)
`
`Q. Now, in 2007, zeolites with the CHA crystal structure were also known,
`is that true?
`A. Zeolites with a CHA crystal structure were known.
`
`(IPR2015-1121, Ex. 1019,
`Tsapatsis Depo. at 110:19-22)
`
`5
`
`
`
`Prior Art as of 2007
`
`Q. And it was also known how you could go about making a zeolite with
`the CHA crystal structure that has different silica-to-alumina ratios,
`correct?
`A. Correct.
`Q. So as of 2007, one of ordinary skill in the art would have been aware of
`more than just natural chabazite with a silica-to-alumina ratio in the
`range of two to eight, is that true?
`A. That's true.
`Q. So they would have been aware also of synthetic zeolites with a CHA
`crystal structure, correct?
`A. Yes.
`Q. And some of those synthetic zeolites with the CHA crystal structure
`would have a silica-to-alumina ratio in the range of 30 to 50, true?
`A. I believe this is true.
`Q. So that was a known material in 2007?
`A. Yes.
`
`(IPR2015-1121, Ex. 1019,
`Tsapatsis Depo. at 112:2-22)
`
`6
`
`
`
`Prior Art as of 2007
`
`“[E]xchanging metal ions into the zeolite framework can make a zeolite
`active for the SCR of NOx.”
`
`(IPR2015-1121, Ex. 2018,
`Tsapatsis Dec. at ¶ 94)
`
`Q. Now, you have also told us in [your] declaration that not only was it
`known, but it was well known that metals can be introduced into the
`zeolite by replacing some of the cations in the zeolite with metal
`cations such as Cu2+ or iron 3+ or any suitable alternative metal ion, is
`that right?
`A. Yes.
`Q. So that was a well-known concept in 2007?
`A. Yes.
`
`(IPR2015-1121, Ex. 1019,
`Tsapatsis Depo. at 113:24-114:9)
`
`7
`
`
`
`Prior Art as of 2007
`
`Q. Now, as of 2007, one of ordinary skill in the art could go to references
`relating to standard ion-exchange techniques, including those that are
`set forth in the '662 patent itself, in order to incorporate copper into a
`zeolite, is that true?
`A. Yes.
`Q. So as of 2007, there were standard ion-exchange techniques that were
`available to those of ordinary skill in the art, correct?
`A. Correct.
`Q. And you've also explained to us in [your] declaration that a 60 to 100
`percent ion-exchange ratio range is a well-known point that a zeolite
`can be ion-exchanged with a metal, is that true?
`A. That's true.
`Q. So one of ordinary skill in the art as of 2007 would have known that a
`60 to 100 percent ion-exchange ratio range is a well-known point that
`you could use to incorporate copper, for instance, into a zeolite, true?
`A. Yes, to any zeolite, true.
`
`(IPR2015-1121, Ex. 1019,
`Tsapatsis Depo. at 114:23-115:19)
`
`8
`
`
`
`Prior Art as of 2007
`
`Q. And one of ordinary skill in the art as of 2007 would know that a 100
`percent ion-exchange ratio corresponds to a copper-to-aluminum
`atomic ratio of 0.5, true?
`A. Yes.
`
`…
`Q. And one of ordinary skill in the art would also understand that a 50
`percent ion-exchange ratio would correspond to a copper-to-aluminum
`ratio of 0.25, is that true?
`A. That's true.
`Q. So a range of copper-to-aluminum ratios of 0.25 to 0.5 would be
`understood by one of ordinary skill in the art as of 2007 to correspond
`to ion-exchange rates in the range of 50 to 100 percent, is that true?
`A. Yes.
`
`(IPR2015-1121, Ex. 1019,
`Tsapatsis Depo. at 115:24-117:15)
`
`9
`
`
`
`Prior Art as of 2007
`
`Q. And was it also known in 2007 that a higher silica-to-alumina ratio and
`a smaller amount of aluminum may impart more structural stability to a
`zeolite? Was that known in 2007?
`THE WITNESS: What was known in 2007 is that when you make a material
`with less aluminum, meaning higher silica-to-alumina ratio, it can
`withstand steaming or high-temperature steam exposure, high-
`temperature steam exposure for longer time without losing its
`crystallographic structure and exhibiting absorption properties and
`surface-area properties with respect to its -- which correspond to its
`pore structure.
`
`(IPR2015-1121, Ex. 1019,
`Tsapatsis Depo. at 125:12-126:1)
`
`10
`
`
`
`Zones
`
`The present invention relates to crystalline zeolite SSZ-62
`that has the CHA crystal structure, a mole ratio greater than
`10 of silicon oxide to aluminum oxide and has a crystallite
`size of 0.5 micron or less. The present invention also relates
`
`IPR2015-1121, Ex. 1004,
`Zones at 1:7-15
`
`11
`
`
`
`Zones
`
`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
`less. The zeolite may contain
`size of 0.5 micron or
`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 sto-
`ichiometric excess of oxygen. In a preferred embodiment, the
`gas stream is the exhaust stream of an internal combus-
`tion engine.
`
`IPR2015-1121, Ex. 1004,
`Zones at 1:7-15
`
`12
`
`
`
`Zones
`
`f
`
`1
`
`I
`
`Reaelien I"I'I'uthIJIre
`
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`I
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`"\hrl uh“:
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`Hm munuw 2."
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`,
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`
`.
`
`(I
`
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`.
`r am; < II
`.I... um
`
`,
`
`Fume“ “.1
`mu» m w. 'r,
`
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`
`
`
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`. (I; mun :m.
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`mum” w.
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`, I...
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`ll
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`‘
`,
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`. H-N“ilmtl1l'J'l'
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`4mm. ..I-
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`Inn-”mm run: “I mum In
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`(“lull-1‘ xxx. 2 ,
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`I
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`,
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`
`Humane.
`
`M mes-[0,
`l l JR: 1:55 If. 3 J
`
`.-
`I.
`
`u.
`
`[HIE—em
`1 {3—1-5
`
`Preferred
`
`n. 12—”. 1e
`’l—EU
`
`-
`
`I dim thnl :V
`
`-
`
`.
`-
`'
`A, I. mam .n M.- .-a.. .\.
`A n
`ml“,
`4. mm .
`u...“ m
`«.1. w rum-4 A
`Im 'Jt\u m.
`
`mam \I I. “m. an . w rum: Mm
`.4
`mm «;
`u....v....-1. "I...“ )I \l
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`l Dru?)
`rum “mum.
`tur-
`I. mm .I
`ngulm t N n .I
`.I zlmu' MI «I
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`I
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`"_' “f""m 2.1.1353?”
`.
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`
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`
`-
`
`wk. m m
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`that” any "(nan
`il‘nwr'A-rih"l:|w.h
`‘l
`I. nun“ -r
`
`-
`
`.
`
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`
`-
`
`mp Mummy mr My],
`n . mJIb-ul 3 kn:
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`.-
`.
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`-
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`
`Emfi I15!
`Hun _‘ -I F,
`
`IPR2015-1121, Ex. 1004,
`|PR2015-1121, Ex. 1004,
`Zones at Table 1
`
`Zones at Table 1
`
`13
`
`
`
`Zones
`
`Metals may also be introduced in the zeolite by replac-
`ing some of the cations in the zeolite with metal cations via
`standard ion exchange techniques (see, for example, U.S.
`
`IPR2015-1121, Ex. 1004,
`Zones at 4:25-27
`
`14
`
`
`
`Maeshima
`
`Nitrogen oxides are, of course, generally present in
`significant quantities in gaseous mixtures such as flue
`gases. Different methods have been used in the treat-
`these gas mixtures. One type of treatment in-
`ment of
`volves the catalytic reduction of the nitrogen oxides. As
`two methods are
`processes for catalytic reduction,
`known in the art: (1) a non-selective reduction method
`in which carbon monoxide, hydrogen or a lower hydro-
`carbon is used as the reducing agent, and (2) a selective
`reduction method in which ammonia is used as the
`reducing agent. The latter catalytic reduction method
`(using ammonia) is advantageous in that the amount of
`the reducing agent used can be reduced and nitrogen
`oxides can be removed at a high ratio. Accordingly,
`
`IPR2015-1121, Ex. 1002,
`Maeshima at 1:11-24
`
`15
`
`
`
`Maeshima
`
`invention, nitrogen oxides
`According to the present
`are removed from a gas containing the nitrogen oxides
`and oxygen by contacting the resulting gaseous mixture
`with a catalyst in the presence of ammonia to reduce the
`nitrogen oxides selectively.
`
`IPR2015-1121, Ex. 1002,
`Maeshima at 2:4-8
`
`16
`
`
`
`Maeshima
`
`As the catalyst that can be used for practicing the
`method of the present invention, there can be men-
`(2) a product
`tioned (1) a crystalline aluminosilicate,
`obtained by exchanging an alkali metal ion in a crystal-
`line alumino-silicate with at least one metal cation hav-
`ing an activity of reducing nitrogen oxides, and (3) a
`supported catalyst
`formed by supporting, by the im-
`pregnation treatment, an active metal component capa-
`ble of reducing nitrogen oxides on a carrier obtained by
`removing an alkali metal
`ion from a crystalline alumino-
`silicate.
`
`IPR2015-1121, Ex. 1004,
`Maeshima at 3:33-43
`
`17
`
`
`
`Maeshima
`
`The crystalline aluminosilicates are classified accord-
`ing to pore diameter and SiO2 /Al2O3 molar ratio. In the
`present invention, those having pore diameters in the
`range of about 3-15 A and SiO2 /Al2O3 molar ratios of
`above about 2 are preferred. As the crystalline alumino-
`silicate, there may be used both natural and synthetic
`zeolites.
`
`Suitable natural zeolites are:
`
`.7H2O
`Mordenite: (Ca, K2, Na2) [AlSi5O12] 2
`Erionite: (K2, Na2, Ca) [AlSi3O8] 2
`.6H2O
`Natrolite: Na2[Al2Si3O10] .2H2O
`Chabazite: (Ca, Na2) [Al2Si4O12] .6H2O
`Faujasite: Na2Ca [Al2Si4O12] 2
`.16H2O
`
`IPR2015-1121, Ex. 1002,
`Maeshima at 3:67-4:12
`
`18
`
`
`
`Maeshima
`
`A zeolite catalyst having incorporated therein an
`active metal ion is prepared by contacting a crystalline
`aluminosilicate with an aqueous or organic solution of
`an active metal compound according to a customary
`method. The ion exchange ratio is not particularly criti-
`cal, but it is generally preferred that the ion exchange
`ratio be about 60 to about 100%.
`As the active metal, there is employed at least one
`member selected from copper, cobalt, nickel, vanadium,
`molybdenum, chromium,
`tungsten, manganese, plati-
`num, silver and iridium.
`
`IPR2015-1121, Ex. 1002,
`Maeshima at 4:44-54
`
`19
`
`
`
`Breck
`
`to novel
`invention relates in general
`The present
`their pre-
`zeolite compositions and to the method for
`paration. More particularly it relates to zeolite composi-
`tions topologically related to prior known zeolites but
`which have substantially greater SiO2/Al2O3 molar
`ratios than the heretofore known zeolite species and
`
`IPR2015-1121, Ex. 1003,
`Breck at 1:9-14
`
`20
`
`
`
`Breck
`
`Since stability quite obviously is, in part at least, a
`function of the SiO2/Al2O3 ratio of zeolites, it would
`appear to be advantageous to obtain zeolites having
`higher proportions of SiO4 tetrahedra by direct synthe-
`sis techniques and thereby avoid the structural changes
`inherent
`in framework aluminum extraction. Despite
`
`IPR2015-1121, Ex. 1003,
`Breck at 3:9-14
`
`21
`
`
`
`Breck
`
`The naturally-occurring or synthetic zeolites used as
`starting materials in the present process are compositions
`well-known
`in
`the
`art. A comprehensive
`review
`…
`ployed. Especially preferred zeolite species are zeolite
`Y, zeolite rho, zeolite W, zeolite N-A, zeolite L, and the
`mineral and synthetic analogs of mordenite clinoptilolite,
`chabazite, offretite and erionite.
`fluorosilicate
`
`IPR2015-1121, Ex. 1003,
`Breck at 3:9-14
`
`22
`
`
`
`Breck
`
`The novel zeolites denominated LZ-218 are the more
`siliceous forms of the prior known zeolite mineral cha-
`bazite and the structurally related synthetic zeolite R,
`zeolite G, and zeolite D, and are prepared therefrom
`using the present process for silicon substitution. LZ-
`218 has, in the dehydrated state, chemical composition
`expressed in terms of mole ratios of oxides:
`0.9±0.1M2/nO:Al2O3:xSiO2
`wherein M is a cation having the valence "n" and "x"
`has a value of greater than 8, preferably in the range of
`8 to 20, and the characteristic crystal structure of chaba-
`zite as indicated by an X-ray powder diffraction pattern
`
`IPR2015-1121, Ex. 1003,
`Breck at 18:3-16
`
`23
`
`
`
`Breck
`
`invent-
`the present
`The novel zeolite compositions of
`tion are useful
`in all adsorption, ion-exchange and cata-
`lytic processes in which their less siliceous precursors
`have heretofore been suitably employed.
`In general,
`because they are more highly siliceous than their pre-
`cursors they are not only more thermally and hydro-
`thermally stable than those prior known materials but
`also have increased resistance toward acidic agents such
`as mineral and organic acids, SO2, SO3, NOx and the
`like. These new zeolites are thus highly useful as selec-
`
`IPR2015-1121, Ex. 1003,
`Breck at 47:44-53
`
`24
`
`
`
`Dedecek
`
`attention
`attract
`ions
`containing Cu
`Zeolites
`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]. The Cu+
`ions were sug-
`gested [13]
`to be catalytic centres in NO and
`N2O decompositions. The essential question is the
`
`IPR2015-1121, Ex. 1007,
`Dedecek at 63
`
`25
`
`
`
`Dedecek
`
`performed
`chabasite was
`of
`synthesis
`The
`according to the procedure of Gaffney [28]. Zeolite
`...
`Potassium hydroxide. The batch composition was
`The
`0.17Na2O:2.0K2O:Al2O3:5.4SiO2:22H2O.
`…
`sedimentary
`natural
`and
`chabasite
`Synthetic
`chabasite from North Korea – chemical composi-
`tion (weight percent 63.89% SiO2, 17.48% Al2O3,
`8.37% Fe2O3, 5.15% K2O, 3.10% CaO, 1.21%
`MgO, 0.40% TiO2 and 0.39% Na2O [the XRD
`
`IPR2015-1121, Ex. 1007,
`Dedecek at 64
`
`26
`
`
`
`Dedecek
`
`Cu2+-chabasite samples with Cu concentrations
`varying from 0.20 to 7.60 wt% were prepared by
`the
`ion
`exchange
`of Na-, Ca-, Cs-
`and
`Ba-chabasites with aqueous solutions of Cu ace-
`tate. The pH of Cu-acetate-chabasite solutions
`
`IPR2015-1121, Ex. 1007,
`Dedecek at 64-65
`
`27
`
`
`
`Dedecek
`
`
`Table 3
`
`Chemical compositions of Cu“-chabasim
`
`Zeolile'
`
`Cu/Al
`
`Me/Al“
`
`Na~CHABIN
`Na-CHABIS
`CuNa-CHAB/N
`CuNa-CHAB/N
`
`Cqu-CI-[AB/N
`CuBa-CHAB/N
`CuCa-CHAB/N
`CuCa—CHAB/S
`
`0.09
`0.10
`0.03
`
`0.04
`0.19
`0.41
`
`0.43
`0.94
`0.40
`0.25
`0.22
`0. l7
`0. 12
`0.08
`0.99
`0.34
`
`0.68
`0.5 l
`0.26
`0.03
`0.03
`0.08
`0.06
`
`Dedecek at 66
`
`‘ N: natural sedimentary chabasitc; S: synthetic chabasile.
`“ Me/Al is Cs/Al for Cqu-chabasite and Ba/AI for CuBa-chabasite.
`
`IPR2015-1121, Ex. 1007,
`|PR2015-1121, Ex. 1007,
`Dedecek at 66
`
`28
`
`
`
`Patchett
`
`IPR2015-1121, Ex. 1005, Patchett at Fig 3C
`(as annotated at Ex. 1008, Lercher Dec. at ¶ 220)
`
`29
`
`
`
`1989 Byrne Reference
`
`“[F]lowing 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.”
`
`(IPR2015-1121, Ex. 1010,
`Byrne at 4:61-5:1)
`
`Q. So would someone of ordinary skill in the art as of February 2007 think
`that 2,000 parts per million by volume of sulfur dioxide in exhaust gas
`is an incredibly high amount of sulfur dioxide?
`A. This is a high amount of sulfur dioxide.
`Q. And is this an amount that one of ordinary skill in February 2007 would
`never expect to see in the exhaust gas of a vehicle driving around on
`the roads in the United States?
`A. That is correct.
`
`(IPR2015-1121, Ex. 1019,
`Tsapatsis Depo. at 153:3-13)
`
`30
`
`
`
`’662 Patent – Claims 9 and 10
`
`9. The catalyst of claim 2, wherein the
`catalyst contains ion-exchanged copper and non-
`exchanged copper.
`
`10. The catalyst of claim 9, wherein the NOx
`conversion performance of the catalyst at about
`200o C. after aging is at least 90% of the NOx
`conversion performance of the catalyst at about
`200o C. prior to aging.
`
`IPR2015-1121, Ex. 1001,
`662 patent
`
`31
`
`
`
`Example 1 of the ’662 Patent
`
`EXAMPLE 1
`EXAMPLE 1
`
`A CuCHA powder catalyst was prepared by mixing 100 g of
`A CuCHA powder catalyst was prepared by mixing 100 g of
`+-form CHA, having a silica/alumina mole ratio of 30,
`NH4
`+-form CHA, having a silica/alumina mole ratio of 30,
`NH4
`with 400 mL of a copper(II) sulfate solution of 1.0 M. The pH
`with 400 mL of a copper(II) sulfate solution of 1.0 M. The pH
`was adjusted to 3.5 with nitric acid. An ion-exchange reaction
`was adjusted to 3.5 with nitric acid. An ion-exchange reaction
`+-form CHA and the copper ions was carried
`between the NH4
`+-form CHA and the copper ions was carried
`between the NH4
`out by agitating the slurry at 80o C. for 1 hour. The resulting
`out by agitating the slurry at 80o C. for 1 hour. The resulting
`
`IPR2015-1121, Ex. 1001,
`662 patent at 10:46-53
`
`32
`
`
`
`Example 1 of the ’662 Patent
`
`IPR2015-1121, Ex. 1001,
`662 patent at Table 1
`
`3333
`
`
`
`Example 1 of the ’662 Patent
`
`Q. So there’s no limitation in claim 1 that excludes example 1
`from the scope of the claim, is that correct?
`A. It says the catalyst – after specifying the silica-to-alumina
`ratio range and the copper-to-aluminum range, it says the
`catalyst effective to promote the reaction of ammonia with
`nitrogen oxides to form nitrogen and water selectively.
`Q. Does that limitation exclude example 1 from the scope of
`claim 1?
`A. This limitation does not exclude.
`Q. So there are no limitations in claim 1 that would exclude
`example 1 from the scope of that claim, true?
`A. With respect to its composition range, no.
`Q. In any way? There’s no limitation in claim 1 that in any way
`excludes example 1 from the scope of the claim, correct?
`A. Correct
`
`IPR2015-1121, Ex. 1019,
`Tsapatsis Depo. at 57:6-25
`
`34
`
`
`
`Example 1 of the ’662 Patent
`
`FIG. 1 is graph showing the NOx conversion and N2O
`make or formation versus temperature for this sample. These
`results are summarized in Table 1. This sample, which did not
`contain soluble copper prior to calcination as indicated by the
`color of the filtrate described above, did not show enhanced
`resistance to thermal aging.
`
`IPR2015-1121, Ex. 1001,
`662 patent at 11:22-25
`
`35
`
`
`
`The ’662 Patent’s Examples
`The ”662 Patent’s Examples
`
`'662 Patent: Examples 1, 1A, 2-9, 12, 13, 16, 17
`
`
`
`|PR2015-1121, EX. 1018
`
`
`
`
`
`
`
`CUM]Raiio
`
`IPR2015-1121, Ex. 1018
`
`36
`
`
`
`The ’662 Patent and “Free” Copper
`
`Q. Now, if you look at claim 1 of the ’662 patent, that patent provides that the
`catalysts have an atomic ratio of copper to aluminum in a particular range, is
`that right?
`A. Yes.
`Q. And there’s no requirement in that claim regarding whether the copper that’s
`present be free, is that correct?
`A. What do you mean by ‘free’?
`Q. Have you read the ’662 patent?
`A. Yes.
`Q. And you’ve seen mention of free copper in the ’662 patent?
`A. So you mean within the context of what’s mentioned in the patent?
`Q. Yes.
`A. Yeah. There’s no specification if the copper is ion-exchanged position or free.
`Q. So claim 1 – for instance, you could fall within the scope of claim 1 if the
`copper on the zeolite is entirely ion-exchanged, is that correct?
`A. Yes.
`
`IPR2015-1121, Ex. 1019,
`Tsapatsis Depo. at 80:13-81:10
`
`37
`
`
`
`The ’662 Patent and “Free” Copper
`
`the catalyst contains ion-ex-
`In a particular embodiment,
`changed copper and an amount of non-exchanged copper
`sufficient to maintain NOx conversion performance of the
`catalyst in an exhaust gas stream containing nitrogen oxides
`after hydrothermal aging of the catalyst. In one embodiment
`
`IPR2015-1121, Ex. 1001,
`662 patent at 2:27-32
`
`38
`
`
`
`The ’662 Patent and “Free” Copper
`
`In a specific embodiment, a catalyst article comprises a
`honeycomb substrate having a zeolite having the CHA crystal
`structure deposited on the substrate, the zeolite having a mole
`ratio of silica to alumina greater than about 15 and an atomic
`ratio of copper to aluminum exceeding about 0.25 and con-
`taining an amount of free copper exceeding ion-exchanged
`copper. In one embodiment, the free copper is present in an
`amount sufficient to prevent hydrothermal degradation of the
`In one or more
`nitrogen oxide conversion of
`the catalyst.
`embodiments,
`the free copper prevents hydrothermal
`degradation of the nitrogen oxide conversion of the catalyst
`upon hydrothermal aging. The catalyst may further comprise a
`
`IPR2015-1121, Ex. 1001,
`662 patent at 2:56-67
`
`39
`
`
`
`The ’662 Patent and “Free” Copper
`
`ratio of copper to aluminum exceeding about 0.25. According to
`one or more embodiments, catalysts and systems utilize
`CuCHA catalysts having ion-exchanged copper and suff-
`icient excess free copper to prevent thermal degradation of
`the catalysts when operated under high temperatures of at least
`about 600o C.,
`for example, about 800o C. and higher, and
`high water vapor environments of about 10% or more.
`
`IPR2015-1121, Ex. 1001,
`662 patent at 5:31-37
`
`40
`
`
`
`The ’662 Patent and “Free” Copper
`
`As “free copper” or soluble copper.” According to one or
`more embodiments, this free Cu is both active and selective,
`resulting in low N2O formation when used in the treatment of
`a gas stream containing nitrogen oxides. Unexpectedly, this
`"free" Cu has been found to impart greater stability in cata-
`lysts subjected to thermal aging at temperatures up to about
`800o C.
`
`IPR2015-1121, Ex. 1001,
`662 patent at 5:46-52
`
`41
`
`
`
`The ’662 Patent and “Free” Copper
`
`Results are summarized in Table 1. This sample, which did not
`contain soluble copper prior to calcination as indicated by the
`color of the filtrate described above, did not show enhanced
`resistance to thermal aging.
`
`IPR2015-1121, Ex. 1001,
`662 patent at 11:22-25
`
`42
`
`
`
`The ’662 Patent and “Free” Copper
`
`To the coating slurry of Example 1 was added copper
`sulphate pentahydrate to bring up the total CuO level to 3.2%.
`The slurry was coated onto monolith and aged and tested for
`that
`the
`SCR NOx as outlined above for Example 1, except
`monolith was calcined at 640o C. The catalytic performance
`was compared with Example 1 in FIG. 1A. The addition of
`copper sulphate into the coating slurry significantly improved
`the hydrothermal stability and low temperature activity.
`
`IPR2015-1121, Ex. 1001,
`662 patent at 11:29-36
`
`43
`
`
`
`The ’662 Patent and “Free” Copper
`
`The slurry preparation, coating and SCR NOx evaluation
`were the same as outlined for Example 1. This example
`contained free copper, and exhibited improved hydrothermal
`stability compared with Example 1.
`
`IPR2015-1121, Ex. 1001,
`662 patent at 11:52-55
`
`44
`
`
`
`The ’662 Patent and “Free” Copper
`
`The slurry preparation, coating and SCR NOx evaluation
`are the same as outlined above for Example 1. As shown in
`FIG. 3, the sample containing more non-exchanged copper
`exhibited higher low temperature activity in addition to
`hydrothermal stability.
`
`IPR2015-1121, Ex. 1001,
`662 patent at 12:2-5
`
`45
`
`
`
`“Hydrothermal Stability” Is Optional
`
`low
`There is a desire to prepare materials which offer
`temperature SCR activity and/or improved hydrothermal
`durability over existing zeolites, for example, catalyst mate-
`rials which are stable at temperatures up to at least about 650o
`C. and higher.
`
`IPR2015-1121, Ex. 1001,
`662 patent at 1:47-51
`
`46
`
`
`
`“Hydrothermal Stability” Is Optional
`
`performance. While the performance of Examples 6, 8 and 9
`was not optimal, it is to be noted that each of the Examples
`was aged at a rather high temperature of 800o C. Not all
`catalysts will experience such high temperatures, and it is
`believed that samples aged at lower temperatures would
`exhibit acceptable performance at a wider acceptable silica/
`alumina ratio. For example, in an exhaust gas treatment sys-
`tem having an SCR catalyst downstream of a catalyzed soot
`filter, the SCR would typically be exposed to high temperatures,
`e.g., exceeding about 700o C.
`If
`the SCR is disposed on
`the CSF, the SCR may experience temperatures as high as
`about 800o C., or higher. According to embodiments of the
`
`IPR2015-1121, Ex. 1001,
`662 patent at 14:41-52
`
`47
`
`
`
`“Hydrothermal Stability” Is Optional
`
`Q. You could also use ammonia SCR to treat the exhaust coming from a power
`plant, correct?
`A. Yes. Correct.
`Q. And claim 1 does not exclude the treatment of an exhaust gas stream coming
`from a power plant, true?
`A. No, it doesn’t.
`Q. Okay. Now, if you were treating the exhaust coming from a power plant, there
`would be no concern that the catalyst would be exposed to temperatures as
`high as 800 to 850 degrees C and 10 percent steam, is that correct?
`…
`A. No, that would not be a concern if the process is designed correctly.
`Q. Okay. And claim 1 extends to circumstances like we’re discussing where
`exposure to the catalyst at temperatures as high as 800 to 850 degrees C and 10
`percent steam is not a concern, true?
`…
`It can include less aggressive conditions.
`
`A.
`
`IPR2015-1121, Ex. 1019,
`Tsapatsis Depo. at 84:14-85:12
`
`48
`
`
`
`“Hydrothermal Stability” Is Optional
`
`is limited to those
`Q. So there’s nothing about claim 1 that
`particular circumstances, SCR disposed on a CSF, true?
`A. Yeah, it is in general about catalytic activity of the chabazite
`material within this range.
`
`IPR2015-1121, Ex. 1019,
`Tsapatsis Depo. at 87:12-17
`
`49
`
`
`
`Obviousness of the Claimed Subject Matter
`
`“[T]he [patent-in-suit’s] claims are not tied to product efficacy, so the
`absence of any particularized discussion of efficacy in the [prior art]
`is immaterial to obviousness of the composition here claimed in light
`of the prior art showing general efficacy for the same use.”
`
`Tyco Healthcare Grp. v. Mut. Pharm. Co., 642 F.3d 1370,
`1374 (Fed. Cir. 2011).
`
`50
`
`
`
`Obviousness of the Claimed Subject Matter
`
`“Appellants argue[d] … that their invention is patentable because of
`unexpectedly improved curing results obtained by their composition.
`In support of this argument, appellants direct[ed the court’s]
`attention to two Rule 132 affidavits in the record.” The court
`disagreed with the appellants and held that “the comparative tests,
`limited to a particular copolymer of butadiene-styrene, are
`insufficient to establish similar superiority for the accelerator with all
`copolymers of butadiene-styrene within the scope of the claim and
`are inadequate to overcome the strong suggestion of obviousness
`inferred from the references.”
`In re Verbanc, 404 F.2d 378, 380-81 (C.C.P.A. 1968)
`
`51
`
`
`
`BASF’s Evidence of “Skepticism”
`
`Copper-based catalysts are active in a wide range
`reactions of transformation of nitrogen oxides and represent
`an useful model system to better understand the fundamental
`aspects of the chemistry and mechanism of reaction of catalytic
`transformation of these pollutants.
`
`IPR2015-1121, Ex. 2012,
`1995 Centi Article at 001
`
`52
`
`
`
`BASF’s Evidence of “Skepticism”
`
`The high activity of copper oxide in the reduction of NO with
`NH3 in the presence of O2 was also recognized early [32].
`Later, copper-zeolites were also found to be highly active in
`this reaction.
`
`IPR2015-1121, Ex. 2012,
`1995 Centi Article at 004
`
`53
`
`
`
`BASF’s Evidence of “Skepticism”
`
`SCR has for more than a decade been mentioned as a
`promising technology to reduce NOx on diesel engines in
`automotive applications.
`
`IPR2015-1121, Ex. 2026,
`2004 Gabrielsson Article at 001
`
`54
`
`
`
`BASF’s Evidence of “Skepticism”
`
`The urea-SCR technology has a great potential to reduce
`NOx from vehicles with diesel engines. Reduction degrees in
`the range of 80-90% have been demonstrated.
`
`IPR2015-1121, Ex. 2026,
`2004 Gabrielsson Article at 007
`
`55
`
`
`
`BASF’s Evidence of “Unexpected Results”
`
`Examples
`2, 3, 4
`
`IPR2015-1121, Ex. 1018
`
`56
`
`
`
`BASF’s Evidence of “Unexpected Results”
`
`“[T]he specification discloses test results of the stabilizing effects of only one 3-
`isothiazolone (and generalized conclusions regarding a few other species) … of
`a claimed subgenus which consists of several hundred compounds.
`...
`Establishing that one (or a small number of) species gives unexpected
`results is inadequate proof, for ‘it is the view of this court that objective
`evidence of non-obviousness must be commensurate in scope with the claims
`which the evidence is offered to support.’”
`
`In re Greenfield, 571 F. 2d 1185, 1189 (C.C.P.A 1978) (emphasis added)
`
`57
`
`
`
`BASF’s Evidence of “Unexpected Results”
`
`IPR2015-1121, Ex. 1001,
`662 patent at 10:46-53
`
`58
`
`
`
`Dr. Schuetze’s Data
`
`Dr. Schuetze’s Data
`
`NOX Conversion % of Fresh Cu-CHA
`
`Sampies at 200 °C
`
`
`
`NOxconversion,%
`
`SAR 30
`
`- - -SAR 27
`
`— —SAR 21
`
`Cu/Al Ratio
`
`Figure 1
`
`NOx Conversion % of Aged Cu—CHA
`_
`Samples With a SAR of 30 at 200 “C
`
`mC
`
`am0
`
`..... SAR 19
`......... SAR 13
`0.40
`0.00
`0.80
`1,00
`1,20
`
`
`
`NOXconversion,% N O
`
`f:u
`
`O
`
`0.00
`
`0.20
`
`0.40
`
`0.50
`
`[3.80
`
`1.00
`
`Cu / Al Ratio
`
`Figure 3
`
`NOx Conversion % of Aged Cu—CHA
`Samples with SARs of 27, 21, 19, and 13 at 200 °C
`100
`
`D:0
`
`fix0
`
`‘2. O
`
`NO
`
`NOXconversion,96
`
`- - - SAR 27
`
`-- -- SAR 21
`
`***** EAR 19
`
`......... SAR 13
`
`
`
`0.130
`
`0.60
`
`0.80
`
`1.00
`
`120
`
`Cu 1‘ Al Ratio
`
`4
`
`F'
`‘gure
`
`IPR2015-1121, Ex. 1015
`|PR2015-1121, EX. 1015
`
`59
`59
`
`
`
`Dr. Schuetze’s Data
`
`Dr. Schuetze’s Data
`
`NOX Conversion % of Fresh Cu-CHA Samples
`with a SAR of 30 at 200°C
`
`NOX Conversion % for Fresh CU-BEA
`Samples Wlth a SAR of 30 at 200 C
`
`§ O
`
`JO
`
`
`
`NO):conversion,%
`
`n.3,
`
`.
`
`r,
`
`.I
`
`A
`
`.
`
`.
`
`0.3
`
`CulAl ratio
`
`Figure 2
`
`Cu / Al ratio
`
`Figurf: 6
`
`IPR2015-1121, Ex. 1015
`
`60
`
`|PR2015-1121, EX. 1015
`
`Be
`5‘
`.Q
`
`Ea):-c
`ou
`
`xDz
`
`
`
`Dr. Schuetze’s Data
`Dr. Schuetze’s Data
`
`NOx Conversion % of Samples with a Cu/AI Ratio of
`
`About 0.45 at 250 0C After Aging
`
`N0conversion94:.
`
`|PR2015-1121, EX. 1015
`
`SAR of zeolite
`
`Figure 5
`
`IPR2015-1121, Ex. 1015
`
`61
`
`
`
`Dr. Lercher’s Analysis of Dr. Schuetze’s Data
`
`IPR2015-1121, Ex. 1008,
`Lercher Dec. at ¶ 311
`
`62
`
`
`
`Dr. Lercher’s Analysis of Dr. Schuetze’s Data
`
`IPR2015-1121, Ex. 1008,
`Lercher Dec. at ¶ 312
`
`63
`
`
`
`BASF’s Evidence of “Commercial Success”
`
`“Evidence of commercial success … is only significant if there is a
`nexus between the claimed invention and the commercial
`success.”
`
`Ormco Corp. v. Align Tech., Inc., 463 F.3d 1299, 1312 (Fed. Cir. 2006).
`
`64
`
`
`
`BASF’s Evidence of “Commercial Success”
`
`“As explained by Dr. Moini, the catalyst is purchased by customers
`because of the pertinent properties of the claimed CuCHA catalyst
`(i.e., excellent activity over a wide temperature range and excellent
`hydrothermal stability in comparison to other known catalysts).”
`BASF Response, Paper 24 at 44-45
`
`65
`
`
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