Inter Partes Reexamination No. 95/001,453
`Declaration of Gary L. Haller, Ph.D.
`
`IN THE UNITED STATES PATENT AND TR.ADEl\fARK OFFICE
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`Examiner: DIAMOND, ALAN D
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`Group Art Unit 3991
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`Confirmation No: 2755
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`In Inter Partes Reexamination of:
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`BULLET AL.
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`Reexamination Control No. 95/001,453
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`Patent No. 7,601,662
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`Issued: October 13, 2009
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`For: COPPER CHA
`ZEOLITE CATALYSTS
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`Mail Stop Inter Partes Reexam
`Central Reexamination Unit
`Commissioner for Patents
`P.O. Box 1450
`Alexandria, VA 22313-1450
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`DECLARATION OF GARY L. HALLER. PH.D. UNDER 37 C.F.R. § l!_U_i
`I, Gary L. Haller, do declare and say as follows:
`
`1. I am the Henry Prentiss Becton Professor of Engineering and Applied Science at Yale
`University with joint appointments in the Departments of Chemical and Environmental Engineering
`and Chemistry. I received a RS. in mathematics from the University of Nebraska at Kearney in
`1962 and a Ph.D. in physical chemistry from Northwestern University in 1966. After a NATO Post(cid:173)
`doctoral Fellowship at Oxford University, I joined the faculty of Yale where I have held a variety of
`administrative posts that include Chair of the Department of Chemical Engineering, Chair of the
`Council of Engineering, and Deputy Provost for Physical Sciences and Engineering. I have been the
`Chair of the American Chernical Society Division of CoHoid and Surface Chemistry, President of
`the Catalysis Society of North America, co-Editor of the Journal of Catalysis, and served on the
`editorial boards of several journals that publish articles relevant to heterogeneous catalysis.
`
`2. My research has involved the molecular understanding of heterogeneous catalysts and
`combines the inorganic chemistry of catalyst synthesis, physical chemist1y of spectroscopic
`characterization of heterogeneous catalysts, and the kinetics and mechanism of simple organic probe
`reactions on heterogeneous catalysts. I am a co-author of about 220 publications, including one co(cid:173)
`authored book and six patents. A copy of my curriculum vitae is attached as Exhibit A.
`
`3. Since 1986, I have been a paid consultant with Engelhard Corporation, the predecessor in
`interest of the patent owner, BASF Catalysts LLC, in the areas of automotive catalysts, including
`treatment of diesel engine exhaust such as reduction of nitrogen oxides. I have been retained by the
`patent owner's counsel as a technical expert in this reexamination. I am being compensated hourly.
`I am not otherwise affiliated with the patent ovvneL
`
`1
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`Exhibit 2010.001
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`

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`Inter Partes Reexamination No. 95/001,453
`Declaration of Gary L. Haller, Ph.D.
`
`~~9-P_~ __ 9-fJ~~~J-~_r_~JJQJ!
`4. The patent ovvner's counsel provided and l have reviewed United States Patent no. 7,601,662
`), the Office Action dated November 16, 2010 ("the Office Action''), and the
`("the '662 patent'1
`references cited in the Office Action. I have also reviewed references cited in this Declaration.
`
`5. I have been asked to provide my opinions on what would have been the view· of a person of
`ordinary skill in the art as of February 2007. I believe that I can accurately describe the perspective
`of such a person. For the purpose of this declaration I have understood that a person skilled in this
`art \Vould have had at least a Master1s degree in chemistry or a related discipline, have knowledge of
`the structure and chemistry of molecular sieves, such as zeolites, factors that impact their
`hydrothermal stability and catalytic activity, including the reduction of oxides of nitrogen.
`
`6. The opinions set forth in this declaration are based on my professional knowledge and
`expertise, as indicated in my curriculum vitae, my review of the '662 patent, the Office Action dated
`November 16, 20 l 0, including the documents cited in the office action, as well as additional
`docun1ents cited in this declaration.
`Zeolite l\1aterials and Hydrothermal Stability
`
`7. Many factors can affect the hydrothermal stability of a zeolite. Zeolite structure (or
`framework) type, the nature of cations associated with tetrahedral aluminum in the zeolite structure,
`hydroxyl density, silica to alumina ratio, stabilizing thermal or chemical treatments, and other fa.ctors
`all have an impact on hydrothermal stability. Predicting hydrothermal stability based on one of these
`factors alone is nearly impossible, and the hydrothermal stability of a particular zeolite will
`ultimately depend more on the framework type and its overall composition than on silica to alumina
`ratio alone. This wiH be addressed in more detail below \Vith respect to the rejection of claims 1-11
`over Dedecek et al. in view of Chung. \Vith respect to the nature of cations associated with
`tetrahedral aluminum in the zeolite structure, and the Office Action quote of the Request for
`Reexamination, that 11the '662 Patent provides absolutely no guidance as to how one of ordinary skill
`in the art would measure the amount of non-exch~mged copper present in the claimed CHA zeolite,"
`the following response is provided. A person of ordinary skill in the aii would be aware of the
`method of X-ray absorption spectroscopy (see C. Marquez-Alvarez, L Rodriguez-Rarnos, A ..
`Guerrero-Ruiz, G. L. Haller, and M. Femandez-Gai«.~ia, Selective Reduction ofNOx with Propene
`under Oxidative Conditions: Nature of the Active Sites on Copper-Based Catalysts, J. A.m. Chem.
`Soc., 1997, 119 (12), pp 2905-2914), that could be used to characterize both exchanged copper as
`well as non-exchanged copper, i.e., XANES and EXAFS analysis of X-ray absorption do not require
`long-range order and detect every atom at the X-ray absorption edge of copper.
`~J:trn,g~!! __ Q~l~J,~-~--A.h~!~m~MJ. .. i!! __ f;,~t-~~-~§t_f;_~§.
`8. The tenninology "reduction of oxides of nitrogen" includes a variety of reactions, including
`adsorption, disproportionation, dissociation and/or oxidizing NO by oxygen, adsorption and/or
`dissociation ofN02, reducing NO by the selective catalytic reduction (SCR) of NO with ammonia in
`the presence of oxygen, reducing NO by the selective catalytic reduction of NO with hydrocarbons
`with and without oxygen present, and reduction of NO \:vith other reducing molecules present in
`exhaust gas such as hydrogen, methane, or CO. See, e.g., Centi G. et aL, Nature of Active Species in
`Copper-Based Catalysts and Their Chemistry of Transformation of Nitrogen Oxides, Applied
`Catalysis A 132 (1995) 179-259 at 185 (Exhibit B, at 185 (Table 1)). The mechanism and the
`reaction conditions of each of these reactions can vary widely, and to say that a particular material
`such as a specific Cu zeolite, such as ZSM-5, is useful for reduction of oxides of nitrogen does not
`2
`
`Exhibit 2010.002
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`

`
`Inter Partes Reexamination No. 95/001,453
`Declaration of Gary L Haller, Ph,D,
`
`mean that the specific zeolite will be effective for each of these reaction types. For example, it is
`\vell known that three-way catalysts, which are effoctive for the abatement of hydrocarbons, carbon
`monoxide and NOx in traditional gasoline powered engines are not effective in lean bum engines
`such as diesel engines.
`
`\Vith respect to reduction of oxides of nitrogen in the presence of a reducing agent, in
`9.
`general, different reducing agents preferentially adsorb on difforent sites in different fom1s and lead
`to different mechanisms of action. In other words, the activity and mechanism of action of a
`particular reducing agent are not good predictors of the reactivity of different reducing agents on a
`particular zeolite catalyst. Alkenes, e.g,, ethene or propene, are particularly effective reducing agents
`for NO on metal exchanged zeolites and it is generally agreed that these al.kenes are preferentially
`adsorbed on acid sites. In contrast, while aimnonia is a base that will adsorb on acid sites, "Ammonia
`readily reacts with copper ions especially in zeolite cavities fonning copper-ammine complexes that
`have been characterized by several techniques such as adsorption measurements [24, 31], X-ray
`diffraction [313], ESR [38, 314-316], IR [38, 315, 317] and X-ray absorption [268] spectroscopies."
`See G. Centi and S. Perathoner, Applied Catalysis A: General 132, 1995, page 216, first sentence in
`section 4.3 (Exhibit C). It is for this reason that NO reduction by hydrocarbons and NO reduction by
`ammonia on Cu zeolites do not generally have parallel behavior and why using the results of
`hydrocarbon reduction of NO is not a good guide to NO reduction by ammonia on the saine Cu
`zeolite, let alone for two different Cu zeolite catalysts when the stmcture type and/or composition of
`the zeolites are different
`1]~_!: __ '..6_6_~J~~t~M.J
`10. The novel invention of the 1662 patent is a catalyst comprising a zeolite having the CHA
`crystal structure, with a silica to alumina ratio greater than about 15 and a copper to aluminum
`atomic ratio greater than about 0.25. More specific claims of the '662 patent are directed to silica to
`alumina ratios in the range of 15 ai1d 40, and/or Cu/Al ratios in the range of about 0.25 to 0.5, A
`review of the '662 patent, including the background, description, Examples and claims reveals that
`there was a longstanding need for catalyst material that had good low temperature conversion of
`NOx at 350 °C and below and that maintained NOx conversion without excessive loss ofNOx
`conversion after hydrothennal aging at high temperatures exceeding 650 °C. As is evident from
`Figure 12 of the 1662 patent, a novel aspect of the invention is not just hydrothermal stability with
`respect to silica to alumina ratio alone, but the particular hydrothemml stability exhibited by Cu(cid:173)
`containing chabazite materials.
`8~1!'.~_ft_Q_!! __ qf __ Cl~!mJ o:f the '662 Patent Over Yuen!Ritscher
`11. Claim. 1 covers a catalyst comprising a zeolite having the CHA crystal structure and a mole
`ratio of silica to alumina greater than about 15 and an atomic ratio of copper to aluminum exceeding
`about 0.25.
`In the Office Action, claim 1 has been re:jected as being unpatentable over Yuen, which
`incorporates by reforence Ritscher. At paragraph 10, Yuen provides a process for the reduction of
`oxides of nitrogen, which involves contacting a gas stream with a molecular sieve having the CHA
`crystal structure having a mole ratio of 50 to 1500 of (1) ai1 oxide selected from silicon oxide,
`germanium oxide, and mixtures thereof to (2) an oxide selected fro:m aluminum oxide, iron oxide,
`titanimn oxide, gallium oxide or mixtures thereof: Taking into account the various combinations
`and without even considering varying weight percentages of oxide (1) and oxide (2), there are three
`possibilities for oxide (1) and fourteen possibilities of oxide (2). Yuen farther says that the
`molecular sieve can contain a metal or metal ions such as cobalt, copper, platinmn, iron, chromimn,
`mai1ganese, nickel, zinc, lanthanum, palladimn, rhodium or mixtures thereof capable of catalyzing
`3
`
`Exhibit 2010.003
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`

`
`Inter Partes Reexamination No. 95/001,453
`Declaration of Gary L. Haller, Ph.D.
`
`reduction of oxides of nitrogen, which may be conducted in tht..~ presence of a stoichiometric excess
`of oxygen. This list includes eleven individual metals and taking into account the different
`combinations of these eleven metals together \.Vith the various combinations of oxide (1) and oxide
`(2), there are nearly three thousand possible materials, taking into account only binary metal
`cornbinations, having the CHA crystal structure described that may be capable of catalyzing the
`reduction of oxides of nitrogen.
`
`12. Yuen appears to be more concerned with providing an improved method to manufacture
`chabazite materials than NOx reduction, as there are no examples in Yuen pertaining to reducing
`nitrogen oxides. In particular, paragraph 0012 makes note of the "advantage of the present invention
`that the reaction is conducted in the presence of hydroxide rather than fluoride" which distinguishes
`it over prior art cited in paragraph 0009. There is no discussion in Yuen of which CHA materials or
`catalyst properties such as which metal ions or amounts are important for the reduction of oxides of
`nitrogen to provide good low temperature conversion below 350 °C. The Office Action focuses on
`Example 3(of16 examples) of Yuen to combine with information in Ritscher. The selection of
`Example 3 appears to be random and no reasoning or infonnation is provided as to why this example
`\.vould provide a catalyst for the reduction of oxides of nitrogen oxides that is best among the 16
`examples.
`
`13. With regard to paragraph 0034 of Yuen, Yuen appears to be interested in the process for
`reducing oxides of nitrogen in the presence of a zeoiite as discussed in Ritscher. In particular, Yuen
`specifies "the catalytic process in the combustion of carbon monoxide and hydrocarbons and the
`catalytic reduction of oxides of nitrogen contained in a gas stream, jj 1 .e., a three-way catalyst not
`involving SCR of oxides of nitrogen by ammonia, Yuen does not indicate that copper ions or the
`catalyst manufacturing techniques in Ritscher are of particular interest because Yuen lists eleven
`different metals/metal ions of interest There is nothing stated in Yuen that chabazite structure
`zeolites would be better at NOx conversion than the zeolites in Ritscher. It could not be predicted
`which of the thousands of materials in Yuen would provide a material with improved properties with
`respect to reduction of oxides of nitrogen and hy(irothermal stability and which metal or metal ion
`would provide such a catalyst
`
`14. According to the Office Action, paragraph 0034 of Yuen describes an example of a process
`for the reduction of oxides of nitrogen with reference to U.S. patent number 4,297,328 (Ritscher).
`Ritscher describes just one exmnple of a process for reduction of oxides of nitrogen-------a three-way
`catalytic process for removing carbon monoxide, hydrocarbons and nitrogen oxides from a gas
`stream. Ritscher appears to prefer ZSM-5 catalysts in his Examples and claims and lists other
`structure types such as ZSM-8, ZSM-11, ZSM-12, Hyper-Y, ultrastabilized Y, silacalite, Beta,
`mordenite, and erioniteo
`
`15. Selective catalytic reduction of oxides of nitrogen in the presence of oxygen or providing
`good lmv temperature conversion ofNOx below 350 °C is not discussed in Ritscher. Ritscher
`provides no info:nnation with respect to providing improved NOx conversion of the zeolites or
`maintaining these properties or structure and surface area stability after hydrothem1al agingo A
`person of skill in the art would not use the information in Ritscher in combination with Yuen
`because the zeolite framework types of interest in .Ritscher and Yuen are dramatically different, and
`the properties of a ZSM-5 zeolite containing a certain amount of copper would not be expected to be
`the same for a zeolite having a different framework type such as chabazite.
`
`16. Furthennore, the catalyst described in Ritscher Example at column 10, lines 28-29 contains
`73% copper by weight, but the catalyst is a mixture of 80 parts of ZSM-5 zeolite and 20 pmis
`4
`
`Exhibit 2010.004
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`

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`Inter Partes Reexamination No. 95/001,453
`Declaration of Gary L Haller, Ph.D.
`
`alumina (col. 10, lines 3-8). The amount of actual copper contained on the zeolite after ion
`exchanging the 80/20 zeolite/alurnina pellets would be difficult to detennine. To say that the
`catalyst is a zeolite that contains 7.3% copper by weight is speculative.
`
`17. It must be noted again that the catalyst in Ritscher is a tln·ee-way catalyst, which is not
`designed to operate in a lean environment at low temperature, e.g., as low as 210 °C-the type of
`environment which the catalyst of the 1662 patent was designed and demonstrated to be active. In
`fact, a close review of the Examples (Table Vat column 7) shows that the aged (4 hours in 10%)
`HzO) samples that were run at stoichiometric redox ratio or in excess oxygen had M_Q_ NOx
`conversion at all. This hardly provides a reason to a person of ordinary skill in the art to use the
`Example in Ritscher and to use a similar amount of copper in Yuen, who states that a catalyst for
`reducing nitrogen oxides in excess oxygen was desired. If anything, the skilled artisan would avoid
`using the information in Ritscher because the NOx conversion of the aged samples in excess oxygen
`was nonexistent
`
`Th~J!d~-~JiQ_~_g_L('.!~:fcrr!-_~_J::ll_Qyer Zones In Vi~~_QfJ§_!!iha:rn
`
`18. The Office Action rejects claims 1-11 of the '662 patent, stating that one of ordinary skill in
`the art would have had a reasonable expectation that loading the chabazite zeolite described in Zones
`using the ion-exchange :method described in Ishihara would have resulted in a copper chabazite that
`would be effective in the conversion of oxides of nitrogen to nitrogen. The Office Action states that
`a person of ordinary skill in the art at the time of priority filing of the '662 patent looking to make a
`copper exchanged zeolite for the reduction of oxides of nitrogen would have been motivated to use
`the ion exchange technique in Ishihara to add copper to the chabazite of Zones because Ishihara used
`and preforred SAP0-34, which is a very well-known silico-alumino phosphate molecular sieve
`having a structure of the chabazite type. I do not agree that this is the case"
`lI~ited_.S.t?.:t~-~--P_?.:t~J!tl~L~~-! __ 6_,_7_i!~,_6.:t4_JZQ_~~~l
`19. Zones relates to a zeolite havhm the CHA crystal structure that can be used for numerous
`processes: separation of gasses including separating carbon dioxide from natural gas (col. 5, lines
`66-67), as catalysts used for the reduction of oxides of nitrogen in a gas stream in the presence of
`oxygen (col. 1, lines 54-66) but the reducing agent is unspecified, converting lower alcohols and
`other oxygenated hydrocarbons to a gasoline boiling point hydrocarbon product (col. 5, lines 18-14),
`and for producing dirnethylamine (col. 5, lines 36-40).
`
`v
`
`•
`
`20. Zones does not present any data or examples pertaining to NOx reduction or suggest that the
`CHA material provides excellent nitrogen oxides reduction at low temperatures or has good
`hydrothermal stability compared to other zeolites. It appears that Zones pertains more to discovery
`of a new zeolite ·vvith a small crystal size and not to an improvement in catalytic reduction of
`nitrogen oxides. No particular significance can be attributed to the statement in Zones that the SSZ-
`62 zeolite was useful for reducing oxides of nitrogen nor what reducing agent might be used under
`any particular conditions, because generally speaking, many of the almost 200 framework types of
`zeolites will exhibit some NOx reduction capability. The important question is whether any
`particular properties or combination of properties would be expected by a person of skill in the art to
`be especially good based on the information in Zones-------and that answer is no. The scientific
`literature and the '662 patent recognized that zeolites promoted with metals could be used for the
`reduction of oxides of nitrogen. The more important question is why would a person of skill in the
`art select one of the many zeoiites available at the time of the '662 patent filing, and then choose the
`selected silica to alumina ratio and choose the amount of copper among the various other metal ions
`
`5
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`Exhibit 2010.005
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`

`
`Inter Partes Reexamination No. 95i001,453
`Declaration of Gary L. HaHer, Ph.D.
`
`(iron, cobalt, nickel, cerium, etc.) that promote the reduction of oxides of nitrogen'? Zones provides
`no information on an amount of copper to be used-~~the passage relied on in the Office Action,
`namely column 5, lines 25-35, as teaching a copper percentage in the range of 0.05%1 to 5% does not
`pertain to a catalyst for reducing oxides of nitrogen, and it does not refer to copper metal. It rders to
`all metals in the Periodic Table (Groups I to VIII), with a preference for Group IA metals (not
`including copper), and this is in reference to a catalyst for the condensation of alcohols.
`
`Ishihara
`
`21. Ishihara et aL describe a copper ion exchanged SAP0-34 catalyst using propene to reduce
`nitrogen oxide. \Vhile SAP0--34 does have the CHA. structure, it does not have the same chemical
`co:rnponents, it is a silico-alumino phosphate of the chabazite type structure and not a alumi_no(cid:173)
`silicate chabazite type structure having a silica to alumina ratio greater than 15 (see B. M. Lok et al.,
`J. Am. Chem. Soc 1984, 106, 6092--6093 (cited in the Office Action and Request)). For the reaction
`of interest in Lok et aL, n-butane cracking, SAP0-34 in this early comparison (see Table II), is
`inferior to chabazite by a factor of 2-70, indicating how different the reaction chemistries are for
`SAP0-34 and a alumino-silicate, both with the CHA structure. A rnore important aspect of the
`structure is the nature of the cation exchange capacity, critical for the ion exchange described in the
`1662 patent. In the alllmino-silicate CHA described in the '662 patent having a silica to alumina ratio
`greater than 15, the cation exchange sites are created by isomorphous substitution of Si by Al, and
`thus, it is important to describe the ratio of copper to potential ion exchange sites resulting frorn Al
`substitution for Si (as Claim l does) as "an atomic ratio of copper to aluminum exceeding about
`0.25." The same considerations apply to claims 3 to 9 of the '662 patent, which claim more specific
`ranges of silica to almnina and Cu/ AL However, the ion exchange sites of silico-alumino
`phosphates, discussed by Ishihara et al., create cation exchange sites by Si substitution for P.
`nsmcoalmninophosphates (SAPO-n) exhibit cation-exchange properties as a result of the
`isomorphous substitution of Pin AlP04 by Si." (see line 8-10, first paragraph of the Introduction to
`Ishihara et al.) This point is repeated throughout Ishihara et aL, (see lines 10-14, column 2, p. 97 of
`Ishihara et al.), "Consequently, all Si atoms added seem to substitute isomorphonsly at the lattice
`position of the P sites but not the Al sites. This is because only one kind of Si bonded with 4 Al
`atoms was recognized in 29Si-MAS NMR spectra.'' Thus, the statement that" .. .Ishihara et al.
`teaches the use of an amount of copper in a CHA structure molecular sieve that would result in a
`copper to aluminum atomic ratio exceeding about 0.25 when used with the CR-'\ zeolite of Zones et
`al." is not correct from a chemical standpoint because Ishihara et al. are discussing a different zeolite
`with a different chemistry, but more impmtantly, a minimum cation exchange ratio would now be
`stated in terms of copper to silicon atomic ratio, not in terms of copper to aluminum cation exchange
`ratio as claimed in 1662 patent.
`22. Furthermore, because the reaction chemistry is different in Ishihara et al. (hydrocarbon used
`as a reducing agent instead of ammonia), the zeolite chemistry is different, and the nature of the
`cation exchange sites are different (associated with Si instead of Al), it cannot be said that the
`SAP0-34, as described by Ishihara et al., would be useful for providing amount of copper in the
`alumino-silicate CHA discussed in the '662 patent. The state1nent in the Office Action that a person
`of ordinary skill "at the time of the priority filing of the Bull '662 patent looking to make a copper
`exchanged chabazite zeolite for the reduction of oxides of nitrogen with the chabazite of Zones '644
`patent would have been motivated to use the ion exchange technique described in Ishihara to add
`copper to the chabazite of Zones 1644 because Ishihara used and preferred SAP0-34, which is a very
`well known silico-·aluminophosphate molecular sieve having a structure of the chabazite type.'' is
`equivalent to saying that MgO, SnAs, UC, LiH, and TiN are ail chernicaHy Like NaCl because they
`all have the same rock salt (NaCl) crystallographic structure.
`23. Putting aside the intent of the '662 patent and using the Hteral constraint of Claim 1, ll ••• an
`atomic ratio of copper to aluminum exceeding about 0.25." it is also necessary to cornpare the actual
`copper to aluminum ratio used by Ishihara et aL, which can be estimated frmn information provided
`
`6
`
`Exhibit 2010.006
`
`

`
`Inter Partes Reexamination No. 95/001,453
`Declaration of Gary L Haller, Ph.D.
`
`in section 2, Experimental: "SAP0-5, 11, and 34, (Si, Al, and P contents: 1.77,12.09, and 10.03
`mmol g- 1
`, respectively)1' and "In the case of SAPO-n, this amount of Cu [3 wt%] corresponds to ca
`75% of the formula ion--exchange capacity, \Vhich is estimated by assuming that all the Si forms ion(cid:173)
`exchange sites." It should be noted that the Si:Al:P ratios given in Ishihara are presumably those in
`the synthesis solution, but they imply are also approximate compositions of the SAPO products.
`Thus, estimated from the information given above results in the atomic ratio of Cu/Al= (0.75 x
`1.77)/12.0 =OJ 0, well below the 0.25 prescribed by Claims 1-11. A second approach is to use the
`"Exchanged amounts of Cu2+ for each type of SAPO--n, ... were estimated to be about 3 wt% from
`ICP analysis." Using the Ai g- 1 given above, and using the 3 wt% Cu to estimate the Cu/Al ratio as
`(0.03 g Cu per g catalyst)/63.546 g/mol Cu)/(0.01209 mol Al per g catalyst)= 0.04. Thus, Ishihara
`approximates a Cu/Al range of 0.04-0.1, the entire range being outside of Claims 1-11. Likewise, at
`4 wt% Cu, where the NO conversion was maximum (see Fig. 4 of Ishihara et aL) would provide a
`Cu/Al atomic ratio of about 0.053-0.13, still outside of Claims 1-11 of the '662 patent.
`24. One .1night also consider other aspects of lshihara et aL that can be differentiated from claims
`1-11 of the '662 patent, apart from the composition of the SAP0-34 catalysts (discussed above) and
`the nature or the reducing agent (propene instead of ammonia). Note also other differences in the
`testing relative to '662, particularly the 3 vol % H20, 2 hours aging (compared to 10 vol % H20, 50
`hours aging in 1662) and testing at a space velocity of 8,500 lf' (compared to 80,000 h- 1
`). Both the
`less severe aging and the lower space velocity should have given the SAP0-34 a comparative
`advantage if SAP0.-34 were catalytically similar to a alumino-silicate CHA, but low temperature NO
`conversion, e.g., around 250 "C, never exceeded 5% after the 800 "C (1073K) aging of SAP0-34
`while for the 1662 patent CHA catalysts conversion is of order 90% at the same temperature (see Fig.
`2, 3, 4 and 7). Thus, even if the person of skill in the art ignored the differences between the
`materials and the reaction types (propene SCR versus ammonia SCR), that would provide little
`reason for a person of ordinary skill in the art to utilize the information in Ishihara et al. to modify
`the zeolite in Zones. If one were to consider crystal structure alone, the extremely poor conversion
`at low temperatures, particularly for the aged samples shown in Figure 5a of Ishihara et al., would
`lead a person skilled in the art that a chabazite structured material would not be a good candidate for
`reduction of oxides of nitrogen at low temperatures or as a material that maintained NOx conversion
`after hydrothermal aging.
`
`In summary, the person of ordinary skill in the art would have no reason to modify the
`25.
`material in Zones as suggested in the Office Action to provide the catalysts in dairns 1-11. The
`chemistry and ion exchange considerations of the materials in Ishihara and Zones are completely
`different, and there would be no expectation of success in using the techniques in Ishihara in the
`rnaterials of Zones. In addition, the copper to aluminum ratios in Ishihara are outside the range of
`claims 1-11 of the '662 patent, and the Office Action fails to explain why one would modify the
`materials in Zones on the basis of weight percent copper based on the weight percent copper in the
`silico--alumino phosphate materials of Ishihara. Alternatively, if a person of ordinary skill in the art
`would consider the modification of the material in Zones based on crvstal structure similarities
`(which they would not), they would be discouraged from making the "modification because the low
`temperature performance of the materials in Ishihara is extremely poor, and the degradation of NOx
`conversion was quite high when exposed to moderate hydrothermal conditions.
`]1t~--R~1~.£-~jQ~ ___ Qf(;J~Jm_~_J:ltQy~rJ1~-~~~~-k __ ~t-~J~_Jg. __ Yt~-~~~-_Qf(]m!Jg
`26. Dedecek et al. never state that chabazite zeolites are useful for the selective catalytic
`reduction ofNOx. Dedececk et al. state: "[z]eolites containing Cu ions attract attention owing to
`their high catalytic activity in NO [1-5] and N 20 decomposition [6] and selective catalytic reduction
`(SCH) ofNO with ammonia [7-9] and hydrocarbons [10-12]. The Cu+ ions were suggested [13] to
`be catalytic centres in NO and N20 decompositions." There is no further information in Dedecek
`about the properties of a chabazite containing copper that is useful or particularly good for reducing
`oxides of nitrogen at low temperatures.
`
`7
`
`Exhibit 2010.007
`
`

`
`Inter Partes Reexamination No. 95/001,453
`Declaration of Gary L. Haller, Ph.D.
`
`27. It is fU.rther stated in the Office Action that "Dedecek et al. teaches a copper to aluminum
`ratio exceeding about 0.25 ... " and, in particular, "Dedecek et al. also discloses zeolites having a
`copper to aluminum atomic ratio of more than 0.25. In particular, Table 2 on p. 66 of Dedecek et al.
`shows naturnl zeolites of a copper to alumimm1 atomic ratio of 0.28, 0.34 and 0.38 and a synthetic
`zeolite having a copper to aluminum atomic ratio of 0.32. See the 4th-6th entries, respectively, and the
`11th entry in Table 2 on p. 66. This statement ignores Table 3 which gives the chemical compositions
`
`of these Cu2+ chabasites. These are not the CuCHA zeolites as claimed and described in the '662
`patent, but CuNa-CHA. Moreover, the examples of natural zeolite also have a Na/Al ratio of 0.08-
`0.17, a K/ Al ratio of about 0.14 and a Fe/Al ratio of 0.31-0.35. That is, these CHA zeolites contain as
`much Fe as they do Cu. Also, the synthetic zeolite with a Cu/Al ratio of 0.32 has a Na/Al ratio 0.26.
`Moreover, none of these examples have a silica to alumina ratio of 15 or greater. The Requestor1s
`Request states at page. 56, 'Then.:fore, the mole ratio of silica (Si02) to alumina (Ah03) of the
`synthetic zeolite is 5.4." A close reading ofDedecek et al., at page. 64, column 2 shows that this is
`the silica to alumina ratio of the starting material, "Zeolite Y (Si/Al= 2.7 [Si02/Ah03 = 5.4]) in
`ammonium fom1 was used as a source material ... !!, so this was the silica to alumina ratio of the
`synthesis solution, not the product No chemical analysis of the final zeolite is given apart from the
`Ca/Al ratio of 0.01 and Na/A-1 ratio of 0.94 (see Table 3, line 2); much of the Na remains after ion
`exchange with copper, i.e., Na/Al ratio is 0.26 after copper exchange, see Table 3, line 13. Thus, no
`example in Dedecek et aL with Cu/Al ratio great than 0.25 has a knovvn silica to alumina ratio except
`for the natural chabasites (which have a silica to alumina ratio of 6.2 but contain cations such as Na+,
`K+ and Fe3+ in addition to copper that in all cases exceed the amount of Cu2*. The statement "Thus,
`with respect to independent claim l of the '662 Patent, Dedecek et aL expressly discloses all of the
`claimed ele:ments, except for the feature involving a silica to alumina mole ratio greater than about
`15." seems an exaggeration in the light of the disclosure of the '662 patent that discloses CHA
`structures with only Cu2+ (and perhaps some unchanged protons) that are labeled CuCHA while
`Dedecek et al. CHA structures in alI cases contain significant portions of the cations as Na (in the
`case of the natural version, K+ and Fe3+, as well) that are labeled CUi."1\JaCHAB to make that
`distinction in composition.
`
`~~-hM_!!g_~L~l~
`28. One ofthe materials in Chung et aL was not a CHA structure but a MFI structure (see Fig. 1).
`After a hydrothermal aging at 800 °C for 6 h with 10% H20, the conversion of this catalyst dropped
`from about 70%1 (fresh) to about 5% at 350 °C (aged), see Fig. 1, hardly a demonstration of useful
`stability under hydrothermal aging that would be relevant to providing an improved zeolite material
`for reduction of oxides of nitrogen and having good hydrothermal stability.
`
`29. The other structure in Chung et al. with variable silica to alumina ratio that was test(:d was of
`the MOR