UNITED STATES PATENT AND TRADEMARK OFFICE BEFORE THE PATENT TRIAL AND APPEAL BOARD UMICORE AG & CO. KG, Petitioner

Transcription

1 UNITED STATES PATENT AND TRADEMARK OFFICE BEFORE THE PATENT TRIAL AND APPEAL BOARD UMICORE AG & CO. KG, Petitioner Patent No. 8,404,203 Issue Date: March 16, 2013 Title: PROCESS FOR REDUCING NITROGEN OXIDES USING COPPER CHA ZEOLITE CATALYSTS PETITION FOR INTER PARTES REVIEW OF U.S. PATENT NO. 8,404,203 PURSUANT TO 35 U.S.C. 312 and 37 C.F.R Case No. IPR

2 Table of Contents I. Mandatory Notices (37 C.F.R. 42.8)... 1 A. Real Party-in-Interest (37 C.F.R. 42.8(b)(1))... 1 B. Related Matters (37 C.F.R. 42.8(b)(2))... 1 C. Counsel (37 C.F.R. 42.8(b)(3))... 2 II. Payment of Fees Incurred in Connection with this Petition (37 C.F.R )... 2 III. Requirements for IPR (37 C.F.R )... 2 A. Grounds for Standing (37 C.F.R (a))... 2 B. Identification of Challenge (37 C.F.R (b)(1)-(3)) and Relief Requested (37 C.F.R (a)(1))... 2 C. Claim Construction (37 C.F.R )(b)(3)) A process for the reduction of oxides of nitrogen contained in a gas stream in the presence of oxygen [C]atalyst [Z]eolite having the CHA crystal structure... 8 IV. Overview of the 203 Patent... 9 V. How Challenged Claims are Unpatentable (37 C.F.R (b)(4)-(5)) A. Ground 1: Claims 1, 14, 15, 17-22, 26, and 27 are obvious under 35 U.S.C. 103(a) over Maeshima in view of Breck B. Ground 2: Claims 2-13, 16, 23-25, and are obvious under 35 U.S.C. 103(a) over Maeshima, Breck, and Patchett C. Ground 3: Claims 1, 14, 15, 17-22, 26, and 27 are obvious under 35 U.S.C. 103(a) over Dedecek in view of Breck i-

3 D. Ground 4: Claims 2-13, 16, 23-25, 28, 30, and 31 are obvious under 35 U.S.C. 103(a) over Dedecek, Breck, and Patchett VI. PURPORTED SECONDARY CONSIDERATIONS VII. CONCLUSION ii-

4 LISTING OF EXHIBITS Exhibit 1101 Exhibit 1102 Exhibit 1103 Exhibit 1104 Exhibit 1105 Exhibit 1106 Exhibit 1107 Exhibit 1108 Exhibit 1109 Exhibit 1110 Exhibit 1111 Exhibit 1112 Exhibit 1113 Exhibit 1114 Exhibit 1115 U.S. Patent No. 8,404,203 to Bull et al. U.S. Patent No. 4,046,888 to Maeshima et al. U.S. Patent No. 4,503,023 to Breck, deceased et al. U.S. Patent No. 6,709,644 to Zones et al. U.S. Patent Application Publication No. US 2006/ to Patchett et al. U.S. Patent Application Publication No. US 2005/ to Patchett et al. Dedecek et al., Siting of the Cu+ Ions in Dehydrated Ion Exchanged Synthetic and Natural Chabasites: a Cu+ Photoluminescence Study Microporous and Mesoporous Materials, Vol. 32, pp (1999). Expert Declaration of Johannes A. Lercher, Ph.D Excerpts from File History of U.S. Patent No. 8,404,203 to Bull et al. and Reexamination No. 95/001,453 U.S. Patent No. 4,961,917 to Byrne U.S. Patent No. 5,516,497 to Speronello et al. Ishihara et al., Copper Ion-Exchanged SAPO-34 as a Thermostable Catalyst for Selective Reduction of NO with C 3 H 6, 169 Journal of Catalysis (1997) U.S. Patent No. 4,297,328 to Ritscher et al. Chung, S.Y. et al., Effect of Si/Al Ratio of Mordenite and ZSM- 5 Type Zeolite Catalysts on Hydrothermal Stability for NO Reduction by Hydrocarbons, Studies in Surface Science and Catalysis, vol. 130, pp (2000) Declaration of Dr. Frank-Walter Schütze -iii-

5 Pursuant to 35 U.S.C and 37 C.F.R. 42, real party-in-interest Umicore AG & Co. KG ( Umicore or Petitioner ) respectfully requests inter partes review ( IPR ) of claims 1-31 of U.S. 8,404,203 ( the 203 patent ) to Ivor Bull et al., which was filed June 8, 2009 and issued March 26, According to U.S. Patent and Trademark Office ( US PTO ) assignment records, the 203 patent is currently assigned to BASF Corporation ( Patent Owner ). There is a reasonable likelihood that Petitioner will prevail with respect to at least one claim challenged in this Petition. I. Mandatory Notices (37 C.F.R. 42.8) A. Real Party-in-Interest (37 C.F.R. 42.8(b)(1)) Petitioner, Umicore, along with parent Umicore S.A. (also referred to as Umicore NV ) and its wholly owned subsidiaries Umicore USA Inc., Umicore Autocat Canada Corp., and Umicore Autocat USA Inc. are the real parties-in-interest. B. Related Matters (37 C.F.R. 42.8(b)(2)) Petitioner is not aware of any existing related matters. Petitioner is concurrently filing IPR Petition No. IPR , which also relates to the 203 patent. This petition focuses on primary prior art references that disclose aluminosilicate CHA catalysts with copper to aluminum atomic ratios within the claimed range, and secondary references that disclose and provide the motivation to modify the primary reference catalysts to use silica to alumina mole ratios within the claimed range. The petition focuses on the reverse: There, the primary prior art reference discloses aluminosilicate CHA catalysts (that are specifically intended for use -1-

6 in internal combustion engines) that have a silica to alumina mole ratio within the claimed range. The secondary reference discloses and provides a motivation to modify those catalysts by adding copper, resulting in a copper to aluminum atomic ratio within the claimed range. C. Counsel (37 C.F.R. 42.8(b)(3)) Lead Counsel: Elizabeth Gardner (Reg. No. 36,519) Back-up Counsel: Richard L. DeLucia (Reg. No. 28,839) Electronic Service information: egardner@kenyon.com; rdelucia@kenyon.com Post and Delivery: Kenyon & Kenyon LLP, One Broadway, New York, NY Telephone: Facsimile: II. Payment of Fees Incurred in Connection with this Petition (37 C.F.R ) The US PTO is authorized to charge the filing fee and any other fees incurred by Petitioner to the deposit account of Kenyon & Kenyon LLP: III. Requirements for IPR (37 C.F.R ) A. Grounds for Standing (37 C.F.R (a)) Petitioner certifies that the 203 patent (Exhibit 1101) is available for IPR and that Petitioner is not barred or estopped from requesting an IPR challenging the patent s claims on the grounds identified in this petition. B. Identification of Challenge (37 C.F.R (b)(1)-(3)) and Relief Requested (37 C.F.R (a)(1)) Petitioner requests inter partes review of and challenges claims 1-31 of the

7 patent, and requests that each of the claims be found unpatentable and cancelled. This petition explains in detail the reasons why claims 1-31 are unpatentable under the relevant statutory grounds, and includes a description of the relevance of the prior art and an identification of where each claim element is found in the prior art. Detailed claim charts are provided, and additional explanation and support for each ground of challenge is set forth in the attached Declarations of Dr. Johannes A. Lercher (Ex. 1108) and Dr. Frank-Walter Schütze (Ex. 1115). Petitioner relies on the following references: (1) U.S. 4,046,888 ( Maeshima, Exhibit 1102); (2) U.S. 4,503,023 ( Breck, Exhibit 1103); (3) U.S. App. 2006/ ( Patchett, Exhibit 1105); and (4) Dedecek et al., Siting of the Cu+ Ions in Dehydrated Ion Exchanged Synthetic and Natural Chabasites: a Cu+ Photoluminescence Study Microporous and Mesoporous Materials, Vol. 32, pp (1999) ( Dedecek, Exhibit 1107). The 203 patent makes a facial claim of priority back through U.S. App. Nos. 12/480,360 and 12/038,423 to U.S. Prov. App. 60/891,835, which was filed February 27, While Petitioner does not concede that the 203 patent is entitled to claim the benefit of any of these applications, for purposes of this petition it is assumed that the patent has an effective filing date of February 27, Maeshima issued September 6, Breck issued March 5, Patchett published on February 23, Dedecek published in Thus, all of these references are prior art under 35 U.S.C. 102(b). -3-

8 Petitioner requests that claims 1-31 be cancelled on the following grounds: Ground 1: Claims 1, 14, 15, 17-22, 26, 27 are obvious under 35 U.S.C. 103(a) over Maeshima in view of Breck Ground 2: Claims 2-13, 16, 23-25, and are obvious under 35 U.S.C. 103(a) over Maeshima and Breck in further view of Patchett Ground 3: Claims 1, 14, 15, 17-22, 26, 27 are obvious under 35 U.S.C. 103(a) over Dedecek in view of Breck Ground 4: Claims 2-13, 16, 23-25, and areobvious under 35 U.S.C. 103(a) over Dedecek and Breck in further view of Patchett C. Claim Construction (37 C.F.R (b)(3)) The terms of a claim subject to IPR have their broadest reasonable construction in light of the specification of the patent in which it appears. 37 C.F.R (b). Claim terms are to be given their plain meaning unless it is inconsistent with the specification. In re Zletz, 893 F.2d 319, 321 (Fed. Cir. 1989). Petitioner contends that certain of the terms of the 203 patent s claims are indefinite and render the claims invalid under 35 U.S.C However, because indefiniteness cannot be raised herein, Petitioner proposes the following in rendering the broadest reasonable constructions: -4-

9 1. A process for the reduction of oxides of nitrogen contained in a gas stream in the presence of oxygen The preamble of independent claims 1 and 26 of the 203 patent states that the claims are directed to a process for the reduction of oxides of nitrogen contained in a gas stream in the presence of oxygen. (Ex. 1101, 23:9-11, 24:29-31.) A preamble will not be limiting if it simply recites the purpose of the claimed subject matter and the body of the claim does not depend on the preamble for completeness. See in re Hirao, 535 F.2d 67, 70 (CCPA 1976). The preamble of claims 1 and 26 provides antecedent basis for the term the gas stream that appears later in the claim. In view of this, while the preamble may be a claim limitation, the preamble is readily understood and can simply be afforded its plain and ordinary meaning. Despite the straight-forward language of the preamble, Petitioner anticipates that Patent Owner may argue that the 203 patent s claims are limited to processes that have very specific performance characteristics. For instance, during prosecution the Patent Owner attempted to argue that the catalysts of the 203 patent purportedly have the ability to maintain NOx conversion across a broad temperature range after exposure to hydrothermal conditions. (Ex. 1109, 203 file history, 1/24/2011 Amend., at p. 22.) It also argued that the catalysts exhibit high NOx conversion in the low temperature range of 200 o C to 350 o C. (Id. at pp ) Likewise, the Patent Owner argued that it is not enough for a catalyst to simply have some activity in the reduction of oxides of nitrogen. Instead, the claimed process purportedly -5-

10 requires excellent activity at temperatures below 350 o C that is maintained after hydrothermal aging. (Id., 5/1/12 Amend., at p. 13.) The Patent Owner went on to argue that the claims require not only the subject matter which is literally recited, but also any properties which are inherent in the subject matter and are disclosed in the specification. (Id. at pp (citing In re Antonie, 559 F.2d 618 (CCPA 1977) and In re Goodwin, 576 F.2d 375 (CCPA 1978)).) The 203 patent s claims should be interpreted to require only what they state, namely, a process for the reduction of oxides of nitrogen. The claims cannot properly be limited to only processes employing materials that exhibit excellent activity, including activity over a wide range of temperatures or resistance to hydrothermal aging. There is nothing in the claims that requires this type of performance. And, the 203 patent s specification does not define any claim term to require this functionality, or disclaim coverage of materials that do not possess these characteristics. In fact, the specification indicates that the materials of the patent do not need to have excellent activity. For instance, Example 1 employs the claimed zeolite, SAR, and Cu/Al ratio. (Ex. 1101, 203 patent, 10:48-50, Table 1.) Yet, this catalyst did not show enhanced resistance to thermal aging. (Id. at 11:21-26.) The prosecution history of the 203 patent itself also serves to confirm that the claims cannot be limited to only processes with excellent performance. When originally filed, the 203 patent included claims explicitly requiring that the catalyst prevent thermal degradation and maintain NOx conversion after hydrothermal -6-

11 aging. (Ex. 1109, 203 patent file history, at 11/19/09 Prelim. Amend., pp. 4-5.) Other claims required that the NOx conversion of the catalyst at about 200 o C after hydrothermal aging be at least 90% of the NOx conversion of the catalyst at about 200 o C prior to hydrothermal aging, or that the catalyst be able to reduce at least about 90% of nitrogen oxides over the temperature range of about 250 o C to 450 o C. (Id. at p. 5) These claims were repeatedly rejected as not described or enabled. (Id., 2/26/10 Office Action, at pp. 3-4; 2/1/12 Office Action, at pp. 5-6; 7/18/12 Office Action, at pp. 2-4.) In response, the Patent Owner cancelled the claims and proceeded with claims requiring only a process for the reduction of oxides of nitrogen without any performance requirements. (Id., 5/1/12 Amend., at p. 4.) Any argument on the part of the Patent Owner that the 203 patent s claims must be limited to processes that exhibit excellent activity across a wide range of temperatures and a high hydrothermal stability is also wrong as a matter of law. The two cases cited during prosecution In re Antonie and In re Goodwin simply stand for the proposition that it may be possible to rebut a prima facie case of obviousness by showing that selection and optimization of a particular claimed range produced unexpectedly good results. In re Antonie, 559 F.2d at 620. This does not mean, however, that performance characteristics allegedly possessed by embodiments in the specification should be read into the claims. Further, as discussed in Section VI below, the 203 patent s specification fails to provide any basis for the contention that -7-

12 use of the zeolites in the claimed range produces unexpected results. (See Ex. 1108, Lercher Dec. at ) 2. Catalyst All of the 203 patent s claims call for a catalyst. This claim term is indefinite, as it is defined as having various metrics and characteristics set forth in the body of the claim, but it is unclear whether those recited features (such as mole ratios and atomic ratios) are those of the zeolite alone, or whether they are of the entire catalyst in its broadest sense, which would include a combination of the zeolite and binder, as well as the various substrates on which the zeolite is deposited. (Ex. 1101, 203 patent, at 2:59-3:5.) Accordingly, because these two possibilities overlap in scope, with neither being necessarily broader than the other, the broadest reasonable interpretation of the catalyst would embrace both a zeolite alone and the zeolite in combination with a binder well and substrate on which the zeolite and binder are deposited. (See Ex. 1108, Lercher Dec. at ) 3. [Z]eolite having the CHA crystal structure All of the claims of the 203 patent require a zeolite having the CHA crystal structure. The patent s specification provides that the CHA crystal structure is defined by the International Zeolite Association. (Ex. 1101, 203 patent, 1:60-61.) According to that definition, zeolites with this particular crystal structure are also known as chabazite. (Ex. 1108, Lercher Dec. at ) -8-

13 IV. Overview of the 203 Patent The 203 patent relates to zeolite catalysts having the CHA crystal structure. (Ex. 1101, 203 patent, 1:17-19.) These catalysts incorporate copper to facilitate their use in gas exhaust treatment systems to reduce nitrogen oxides. (Id. at 1:19-22.) The 203 patent acknowledges that both aluminosilicate zeolites and copper promoted zeolites useful as nitrogen oxide reducing catalysts were known in the prior art. (Ex. 1101, 1:34-37.) It was also known that zeolites can be used as part of a selective catalytic reduction, or SCR, process to catalyze the selective reaction of ammonia with nitrogen oxides to form nitrogen and water. (Id. at 8:38-41.) The 203 patent s claims purport to be an advantage over the acknowledged prior art due to recited ranges of mole ratios of silica to alumina (the SAR ) and atomic ratios of copper to aluminum (the Cu/Al ratio ). Independent claims 1 and 26 requires a SAR from about 15 to about 100 or 150, and a Cu/Al ratio from about 0.25 to about 0.50 or 1. The remaining claims are all dependent. The 203 patent also provides that its catalytic materials can be used as part of an exhaust gas treatment system used to treat exhaust gas streams, especially those emanating from gasoline or diesel engines. (Id. at 1:62-65.) In this regard, the specification discusses disposition of its catalysts on various prior art substrates, including wall flow or flow through honeycomb substrates. (Id. at 2:41-45.) Various other prior art components of an exhaust gas treatment system are also discussed, including an oxidation catalyst, a soot filter, and a device to add a -9-

14 reductant like ammonia to an exhaust stream. (Id. at 5:65-6:5; 21:58-22:67.) V. How Challenged Claims are Unpatentable (37 C.F.R (b)(4)-(5)) A. Ground 1: Claims 1, 14, 15, 17-22, 26, and 27 are obvious under 35 U.S.C. 103(a) over Maeshima in view of Breck. Maeshima relates to materials for use in a process wherein the concentration of nitrogen oxides is reduced by catalytic reduction. (Ex. 1102, Maeshima, at 1:8-10.) This entails contacting the gaseous mixture with a catalyst in the presence of ammonia to reduce the nitrogen oxides selectively. (Id. at 2:4-8.) Maeshima s process is meant to be operable at a temperature range of 200 o C to about 500 o C. (Id. at 2:48-49, 3:20-32.) [A] crystalline aluminosilicate can be used as the catalyst. (Id. at 3:33-35.) Chabazite is provided as an example of a suitable zeolite catalyst. (Id. at 4:6-12.) Maeshima states that the zeolite catalysts employed in its process should have a SAR ratio greater than 2. (Id. at 3:67-4:3.) Further, at least one metal cation having an activity of reducing nitrogen oxides can be incorporated into the zeolite via ion exchange. (Id. at 3:35-38.) Copper is identified as an active metal that can be used for this purpose. (Id. at 4:51-54.) According to Maeshima, zeolite catalysts should be ion exchanged with an active metal in the amount of 60% to 100%. (Id. at 4:44-54.) Maeshima also explains that the catalyst should be impregnated with active metals in the amount of 2% to 10% by weight. (Id. at 6:1-18.) And, an example that includes 3% copper by weight is provided. (Id. at 9:10-12.) -10-

15 Breck sets forth methods for preparing zeolites that have substantially greater SiO 2 /Al 2 O 3 ratios than the heretofore known zeolite species. (Ex. 1103, Breck, at 1:9-17.) [C]habazite is identified as an [e]specially preferred zeolite species. (Id. at 4:60-63.) Breck also provides a specific example, designated LZ-218, of a chabazite catalyst with a SAR ratio greater than 8, preferable in the range of 8 to 20. (Id. at 18:3-15.) LZ-218 is one of the preferred zeolite catalysts with the CHA crystal structure set forth in the 203 patent. (Ex. 1101, 203 patent, 4:33-35.) Breck explains that its high silica zeolites are very stable, can be ion-exchanged, and can be used in catalytic processes just like lower silica precursors. (Ex. 1103, Breck, at 47:44-47.) Maeshima and Breck together teach all the limitations required by claims 1, 14, 15, 17-22, 26, and 27 of the 203 patent. Maeshima relates to catalysts for use in a SCR process to reduce nitrogen oxides in an oxygen containing gaseous stream. (Ex. 1102, Maeshima, at 1:8-10, 2:4-8.) Thus, it discloses the process for the reduction of oxides of nitrogen contained in a gas stream in the presence of oxygen of claims 1 and 26. Next, Maeshima describes use of a chabazite (id. at 4:6-12), which is a zeolite catalyst having the CHA crystal structure as the claims require. This catalyst must also have certain proportions of silica, alumina, and copper. Claim 1 requires a SAR from about 15 to about 100 and a Cu/Al ratio from about 0.25 to about 0.5. Claim 26 requires a SAR from about 15 to about 150 and a Cu/Al ratio from about 0.25 to about 1. While Maeshima discusses the use of zeolites with a SAR greater than 2, as shown by Breck, it was well known in the prior art that the -11-

16 SAR of a zeolite like chabazite could be beneficially increased. Breck provides an example of chabazite with a SAR in the range of 8 to 20. Incorporation of Breck s chabazite zeolite into Maeshima results in a catalyst with the claimed proportions of silica, alumina, and copper. A SAR of 20 is within the claimed range. With respect to the Cu/Al ratio, Maeshima states that when adding copper to zeolite catalysts, the ion-exchange rate should be from 60% to 100%. Applying a 100% ion-exchange rate 1 to Breck s chabazite catalyst with a SAR of 20 will produce a material with a Cu/Al ratio of 0.5. (See Ex. 1108, Lercher Dec. at ) A 60% ion-exchange rate produces a Cu/Al ratio of 0.3. (See id.). These Cu/Al ratios are within the claimed ranges. The catalysts would also respectively be 4.65% and 2.82% Cu by weight, which is in the acceptable range of 2% to 10% specified by Maeshima. (See id. at ) And, if 3% Cu by weight is used (this is the amount of copper used by an example in Maeshima), the Cu/Al ratio of the resulting material will be 0.3. (See id. at ) 1 The maximum amount of copper that can be incorporated into chabazite via ion exchange is 1 mole of Cu per mole of Al 2 O 3. (See Ex. 1108, Lercher Dec. at 101.) Thus, at a 100% ion-exchange rate, the atomic ratio of Cu/Al will be 0.5. (See id. at 104.) -12-

17 Claims 14 and 26 require adding a reductant to the gas stream. Claims 15 and 27 specify that this reductant be ammonia or an ammonia precursor. Maeshima explains that ammonia should be added to a gas stream during the treatment process as a reducing agent. (Ex. 1102, Maeshima, at 2:9-64; 8:32-52.) Claims further limit the SAR and Cu/Al ratio of the claimed catalyst. Claims 17 and 18 respectively require a SAR of about 25 to about 40 or about 30. Claims 19 and 20 respectively require a Cu/Al ratio of 0.30 to about 0.50 or about 0.4. Claim 21 requires both a SAR from about 25 to about 40 and a Cu/Al ratio from about 0.3 to about 0.5, while claim 22 requires a SAR of about 30 and a Cu/Al ratio of about 0.4. Maeshima and Breck s zeolites will have Cu/Al ratios of 0.3 to 0.5, which matches the claimed ranges. The combination of Maeshima and Breck discloses a copper-loaded chabazite zeolite with a SAR of 20. One of ordinary skill in the art would not consider zeolites with a SAR of 25 to 40 or 30 to provide any non-obvious performance benefit over, a zeolite with a SAR of 20. (Id. at Ex. 1108, Lercher Dec. at ) Instead, as evinced by Breck, it was well known in the art that increasing the proportion of silica in a zeolite would increase its stability and resistance to poisoning without compromising its utility as a zeolite. (Id. at 123.) This common knowledge would have motivated those of ordinary skill in the art to use of zeolites with ratios even greater than those explicitly set forth in Breck. (Id. at 124.) The obviousness of the claimed SAR ranges is also confirmed by the 203 patent. While some examples with a SAR of 30 are referenced, the patent nonetheless -13-

18 explains that zeolites having a range of silica to alumina ratio between about 15 and 256 exhibit acceptable low temperature NOx conversion and are within the scope of the invention. (Ex. 1101, 203 patent, at 14:58-63.) One of ordinary skill in the art as of February would have been motivated to utilize Breck s higher silica zeolites with Maeshima s catalytic process to arrive, with a reasonable expectation of success, at the subject matter of the claims. (See Ex. 1108, Lercher Dec. at ) As explained above, while Maeshima discloses all the other required claim limitations, including the use of zeolites with the CHA crystal structure and the claimed proportion of copper in a SCR process, it does not expressly reference zeolites with a SAR within the claimed ranges. Instead, it simply states that crystalline aluminosilicates having SiO 2 /Al 2 O 3 molar ratios of above about 2, including chabazite, are preferred for copper loading and catalyzing the reduction of nitrogen oxides. (Ex. 1102, Maeshima, at 3:67-11.) Breck discloses that the SAR of a chabazite zeolite can be increased to within the claimed range. (Ex. 1103, Breck, 18:3-15.) Further, Maeshima and Breck together provide 2 For purposes of this Petition, one of ordinary skill in the art is assumed to hold at least a Master s degree in chemistry or a related discipline, and have knowledge of the structure and chemistry of molecular sieves like zeolites, including factors that impact their stability and activity. (See Ex. 1108, Lercher Dec. at 69.) -14-

19 one of ordinary skill in the art with motivation to use an increased silica zeolite in Maeshima s process. Maeshima explains that an exhaust gas stream generally contains sulfur oxides and oxygen in addition to nitrogen oxides and it is necessary to perform removal of nitrogen oxides while eliminating influences of these materials. (Ex. 1102, Maeshima, at 2:34-38.) Breck s higher silica zeolites accomplish this. According to Breck, increasing the proportion of silica in a zeolite provides it with increased resistance to acidic agents like sulfur oxides. (Ex. 1103, Breck, at 47:47-52.) And, as an added benefit, Breck s higher silica zeolites are also more thermally and hydrothermally stable. (Id.) Thus, one of ordinary skill in the art in February 2007 would readily appreciate that use of Breck s zeolites would be particularly well suited for use in Maeshima s process. (Ex. 1108, Lercher Dec. at ) They would render Maeshima s process more resistant to sulfur oxides in a gas stream, and would also allow the process to be more effective across a broader temperature range and more resistant to hydrothermal aging. (See id. at 160.) One of ordinary skill in the art would also understand that it would be beneficial to follow Maeshima s instruction to use a 60% to 100% ion-exchange rate when adding copper to Breck s zeolite. It was well known that larger amounts of copper ions, including that achieved by approaching up to a 100% ion-exchange rate, enhance the effectiveness of a zeolite when catalyzing the reduction of nitrogen oxides. (See id. at ) And, Breck s disclosure is itself consistent with this. According to Breck, the chemical composition of LZ-218 expressed in terms of mole ratios of -15-

20 oxides is 0.9±0.1M 2/n O:Al 2 O 3 :xsio 2. (Ex. 1103, Breck, at 18:8-11.) If copper is used as cation M, a Cu/Al ratio of 0.4 to 0.5 will result. (Ex. 1108, Lercher Dec. at 114.) One of ordinary skill in the art would also have every reason to believe that use of Breck s zeolites in Maeshima s process would succeed. (Id. at 163.) In fact, Breck itself explains that increasing the proportion of silica in its zeolites does not detrimentally effect the ability to ion-exchange the zeolites, or the utility of the zeolites in catalytic processes in which lower silica precursors have been employed. (Ex. 1103, Breck, at 47:44-47.) Maeshima and Breck are also in the same technical field (zeolite catalysts and the use of these catalysts) and are directed to solving the same problem (identifying materials that can be effectively used in a process for catalyzing the reduction of nitrogen oxides). (See Ex. 1108, Lercher Dec. at 166.) This would further motivate combination. (Id.) Additionally, the combination of Maeshima and Breck amounts to nothing more than the application of one particular known type of catalytic material with known benefits the high silica chabazite zeolites of Breck in a process that already employs the same type of material Maeshima s process for selectively reducing nitrogen oxides. (Id. at 167.) Thus, use of Breck s zeolites, which had known benefits and applicability to catalytic processes, with Maeshima s process would be considered nothing more than routine optimization and an obvious design choice. (Id. at 168.) -16-

21 Claim charts further identifying the portions of Maeshima and Breck that disclose the limitations of claims 1, 14, 15, 17-22, 26, and 27 are provided below: Claim 1 A 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 catalyst comprising a zeolite having the CHA crystal structure and a mole ratio of silica to alumina from Disclosure in Maeshima and Breck E.g., Maeshima, 1:6-13 ( [T]his invention relates to a process... wherein the concentration of nitrogen oxides is reduced by catalytic reduction. Nitrogen oxides are, of course, generally present in significant quantities in gaseous mixtures such as flue gases. ); 2:4-8 ( [N]itrogen oxides 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. ); see also 2:9-64; 3:20-27; 8: E.g., Breck, 47:44-61 ( The novel zeolite compositions of the present invention are useful in all adsorption, ion-exchange and catalytic processes in which their less siliceous precursors have heretofore been suitably employed. ); see also 1:9-14; 48:7-51:3. E.g., Maeshima, 1:55-63 ( [T]he gaseous mixture is contacted with a zeolite catalyst. );2:4-8 ( [N]itrogen oxides are removed from a gas containing the nitrogen oxides and oxygen by contacting the resulting gaseous mixture with a catalyst. ); see also 1:6-13; 2:9-64; 3:20-27; 7:20-27; 8: E.g., Maeshima, 3:33-35 ( As the catalyst that can be used for practicing the method of the present invention, there [is]...a crystalline aluminosilicate... ); 4:3-11 ( As the crystalline aluminosilicate, there may be used both natural and synthetic zeolites. Suitable natural zeolites are: Chabazite: (Ca, Na 2 ) [Al 2 Si 4 O 12 ].6H 2 O ); see also 1:60-63; 3:44; 3:67-68; 4:36-50; 6:1-4; 7:28-30; 8:1-4; 8:14-17; 8:60-62; 9: E.g., Breck 4:60-63 ( Especially preferred zeolite species are chabazite. ); 18:3-5 ( The novel zeolites denominated LZ- 218 are the more siliceous forms of the prior known zeolite mineral chabazite. ); see also 3:50-64; 11:16-32; 12:3-18; 47:44-61; 48:7-51:3. E.g., Maeshima, 3:68-4:3 ( In the present invention, [crystalline aluminosilicates] having SiO 2 /Al 2 O 3 molar ratios of above -17-

22 about 15 to about 100 and an atomic ratio of copper to aluminum from about 0.25 to about about 2 are preferred. ). E.g., Breck, 1:9-14 ( The present invention relates to novel zeolite compositions... which have substantially greater SiO 2 /Al 2 O 3 molar ratios than the heretofore known zeolite species. ); 3:24-31 ( We have now discovered a method for removing framework aluminum from zeolites having SiO 2 /Al 2 O 3 molar ratios of about 3 or greater and substituting therefor silicon from a source extraneous to the starting zeolite. By this procedure it is possible to create more highly siliceous zeolite species which have the same crystal structure... ); 18:7-15 ( LZ-218 has... [a] chemical composition expressed in terms of mole ratios of oxides: 0.9±0.1M 2 /no:al 2 O 3 :xsio 2 wherein M is a cation having the valence n and x is a value greater than 8, preferably in the range of 8 to ); see also 3:24-31; 47: E.g., Maeshima, 4:44-54 ( A zeolite catalyst having incorporated therein an active metal ion... 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. ); 6:1-18 ( The active metal component [that] reduc[es] nitrogen oxides is supported on the aluminosilicate carrier by the impregnation treatment. Most preferred metals are copper. The amount of the active metal component in the catalyst is a catalytically effective amount, preferably about 2 to about 10% by weight... ); 8:60-9:11 ( Copper-supported zeolite catalyst was prepared carrying 3 wt. % copper. ); see also 5:32-68; 6:66-7:13; 8: E.g., Breck 4:56-60 ( In those instances in which it is desirable to replace original zeolitic cations for others more preferred in the present process, conventional ion-exchange techniques are suitably employed. ); 18:8-11 (noting that the chemical composition of LZ-218 is 0.9±0.1M 2/n O:Al 2 O 3 :xsio 2 ); 47:44-47 ( The novel zeolite compositions of the present invention are useful in all adsorption, ion-exchange and catalytic processes in which their less siliceous precursors have heretofore been suitably employed. ); see also. See also Ex. 1108, Lercher Dec. at

23 Claim 14 claim 1, wherein the process further comprises adding a reductant to the gas stream. Claim 15 claim 14, wherein the reductant comprises ammonia or an ammonia precursor. Claim 17 claim 15, where the mole ratio of silica to alumina is from about 25 to about 40. Claim 18 claim 15, wherein the mole ratio of silica to alumina is about 30 Claim 19 claim 15, wherein the atomic ratio See claim 1. Disclosure in Maeshima and Breck E.g., Maeshima, 1:55-63 ( [T]he gaseous mixture is contacted with a zeolite catalyst in the presence of the minimum amount of ammonia necessary to reduce the nitrogen oxides contained therein. ); 7:20-27 ( [A]mmonia is incorporated in the exhaust gas in an amount not smaller than about 1.2 times, preferably about 1.2 to about 3 times, the stoichiometric amount necessary for reduction of nitrogen oxides contained in the exhaust gas. Then, the resulting gas mixture is contacted with a fixed bed of a zeolite catalyst ); see also 2:4-64; 8: Disclosure in Maeshima and Breck See above discussion of claim 14. Disclosure in Maeshima and Breck See above discussion of claim 15. See above discussion of the mole ratio of silica to alumina from about 15 to about 100 limitation of claim 1. Disclosure in Maeshima and Breck See above discussion of claim 15. See above discussion of the mole ratio of silica to alumina from about 15 to about 100 limitation of claim 1. Disclosure in Maeshima and Breck See above discussion of claim 15. See above discussion of the atomic ratio of copper to -19-

24 of copper to aluminum is from about 0.30 to about Claim 20 claim 15, wherein the atomic ratio of copper to aluminum is about Claim 21 claim 15, wherein the mole ratio of silica to alumina is from about 25 to about 40 and the atomic ratio of copper to aluminum is from about 0.30 to about Claim 22 claim 15, wherein the mole ratio of silica to alumina is about 30 and the atomic ratio of copper to aluminum is about Claim 26 A process for the reduction of oxides of aluminum from about 0.25 to about 0.50 limitation of claim 1. Disclosure in Maeshima and Breck See above discussion of claim 15. See above discussion of the atomic ratio of copper to aluminum from about 0.25 to about 0.50 limitation of claim 1. Disclosure in Maeshima and Breck See above discussion of claim 15. See above discussion of the mole ratio of silica to alumina from about 15 to about 100 limitation of claim 1. See above discussion of the atomic ratio of copper to aluminum from about 0.25 to about 0.50 limitation of claim 1. Disclosure in Maeshima and Breck See above discussion of claim 15. See above discussion of the mole ratio of silica to alumina from about 15 to about 100 limitation of claim 1. See above discussion of the atomic ratio of copper to aluminum from about 0.25 to about 0.50 limitation of claim 1. Disclosure in Maeshima and Breck See above discussion of the process for the reduction of oxides of nitrogen contained in a gas stream in the presence of oxygen limitation of claim 1 and the process further comprises -20-

25 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. Claim 27 claim 26, wherein the reductant comprises ammonia or an ammonia precursor. adding a reductant to the gas stream limitation of claim 14. See above discussion of the contacting the gas stream with a catalyst limitation of claim 1 and the process further comprises adding a reductant to the gas stream limitation of claim 14. See above discussion of the a zeolite having the CHA crystal structure limitation of claim 1. See above discussion of the mole ratio of silica to alumina from about 15 to about 100 limitation of claim 1. See above discussion of the atomic ratio of copper to aluminum from about 0.25 to about 0.50 limitation of claim 1. Disclosure in Maeshima and Breck See above discussion of claim 26. See above discussion of [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 limitation of claim

26 B. Ground 2: Claims 2-13, 16, 23-25, and are obvious under 35 U.S.C. 103(a) over Maeshima, Breck, and Patchett. The combination of Maeshima and Breck discloses all the elements of and renders claims 1, 14, 15, 17-22, 26, and 27 obvious. Claims 2-13, 16, 23-25, and include additional limitations relating to the use of the process of claims 1 and 26 in connection with an internal combustion engine, all of which are disclosed by Patchett. Patchett generally relates to emissions treatment system and method for reducing nitrogen oxides (NOx) emissions in the exhaust stream produced from an internal combustion engine. (Ex. 1105, Patchett, at 1.) The system engages in Selective Catalytic Reduction (SCR) using ammonia (NH 3 ) or an NH 3 precursor to reduce nitrogen oxides. (Id. at 3.) Patchett s system employs an injector for periodically metering ammonia or an ammonia precursor into an exhaust stream. (Id. at 18.) Urea can serve as the ammonia precursor. (Id. at 60.) Downstream from the injector there is a first substrate that includes two catalytic zones on the same substrate. (Id. at 18; see also Fig. 3A) The first zone includes a first SCR catalyst composition. (Id. 18) The second zone includes a NH 3 destruction catalyst. (Id. at 19.) The substrate can be a honeycomb flow-through substrate or, alternatively, a honey-comb wall flow substrate. (Id. at 23.) The SCR catalyst composition can be a copper-exchanged zeolite. (Id. at 21, 69.) Use of such a catalyst provides an effective SCR catalyst operating temperature range of from about 150 to 550 o C. (Id. at 69.) The NH 3 destruction catalyst can be -22-

27 platinum. (Id. at ) Patchett explains that using a zoned SCR-NH 3 destruction catalyst in emission treatment systems results in a space-saving benefit gained by integrating two catalyst functions on a single substrate. (Id. at 56.) An example of a substrate coated with both a copper-exchanged zeolite and platinum is shown in Figure 4. (Id. at Fig. 4; 59.) Patchett s system can also employ a second substrate located downstream of the NH 3 injector but upstream of the first substrate. (Id. at 25; Figs. 3B, 3C.) This second substrate is coated with a second SCR catalyst that can be the same as or different from the SCR catalyst used to coat the first substrate. (Id. at 25.) Use of two substrates coated with SCR catalysts allows the system to account for the different exhaust temperatures throughout the exhaust system. (Id. at 62.) The second substrate can be honey-comb flow-through substrate, an open-cell foam substrate, or a wall flow substrate. (Id.) If a wall flow substrate is utilized, the second substrate acts as a soot filter and can remove greater than 80% of the particulate matter including the soot fraction and SOF (i.e., the soluble organic fraction of the particulate). (Id. at 63.) Patchett notes that additional details regarding an SCR-coated wall flow substrate and its utility in the reduction of NO X and particulate matter have been described in co-pending U.S. patent application Ser. No. 10/634,659. (Id.) This application, which is incorporated by reference, published as U.S. App. 2005/ (attached as Ex. 1106, Patchett 514 ). -23-

28 Patchett s system can also include an oxidation catalyst to remove unburned gaseous hydrocarbons from the exhaust stream. (Ex. 1105, Patchett, at 64.) Use of these various catalyst coated substrates allows Patchett s system to selectively reduce NOx to N 2 while simultaneously providing for at least partial abatement of other components of the exhaust including unburned gaseous hydrocarbons, CO, and the SOF and converting any excess ammonia to N 2 and H 2 O. (Id. at 55; Fig. 3C.) As explained above, Maeshima and Breck disclose the use of a catalyst with the CHA crystal structure, SAR, and Cu/Al ratio required by the claims. They do not, however, specifically mention internal combustion engines, or make explicit reference to various other limitations required by claims 2-13, 16, 23-25, and Patchett explains that copper-exchanged zeolite catalysts like those set forth in Maeshima and Breck can be employed in SCR processes to treat the exhaust of an internal combustion engine such as a diesel engine[s]. (Ex. 1105, Patchett, at 1, 2, 5, 24, 26, 57, 112; Figs. 3A, 3B.) Patchett also discloses the additional limitations of claims 2-13, 16, 23-25, and 28-31, and one of ordinary skill in the art would consider these claims to be obvious over Maeshima, Breck, and Patchett. (See Ex. 1108, Lercher Dec. at ) Claim 2 requires that the gas stream be from an internal combustion engine. Again, Patchett repeatedly explains that its system is specifically designed to treat diesel engine exhaust. (Ex. 1105, Patchett, at Abstract; 1, 24, 26-29; Figs. 3A, -24-

29 3B, 3C.) Claim 2 also requires that the catalyst be disposed on a honeycomb flow through substrate. This is also required by claims 23 and 29. Patchett expressly and repeatedly discloses the use of this particular type of substrate coated with an SCR catalyst. (See id. at 18, 23, 58.) Claim 3 requires that the exhaust stream contain ammonia, and that the flow through catalyst be coated with CuCHA. Patchett describes an SCR process that employs ammonia as a reductant. (See id. at 3, 18, ) And, Patchett notes that its flow-through substrate can be coated with a copper-exchanged zeolite (like that of Maeshima and Breck). (Id. at 21, 69.) Claim 4 requires a flow through substrate with portions coated with Pt and CuCHA. Patchett discloses this limitation. As discussed above, Patchett s system employs a first substrate that can be a flow-through substrate. This substrate has two catalytic zones; an inlet zone suited for the SCR reaction and an outlet zone suited for the destruction (oxidation) of NH 3. (Id. at 54.) The inlet zone is coated with an SCR catalyst, such as a copper-exchanged zeolite. (Id. at 21.) The outlet zone is coated with a NH 3 destruction catalyst, such as platinum. (Id. at 19, 20.) An example of a flow-through substrate coated with both an SCR catalyst like a copper-exchanged zeolite and a NH 3 destruction catalyst like platinum is shown in Figure 4. (See id. at Fig. 4; 59.) According to Patchett, use of this type of zoned SCR-NH 3 destruction catalyst in emissions treatment systems is a space-saving benefit gained by integrating two catalyst functions on a single substrate. (Id. at 56.) -25-

30 Claim 5, like claim 2, requires that the gas stream be from an internal combustion engine. The claim also requires that the catalyst be disposed on a honeycomb wall flow substrate. Claim 24 and 30 also require use of this type of substrate. Again, Patchett relates to the treatment of the exhaust emitted by an internal combustion engine. While some of Patchett s embodiments employ a flowthrough substrate to form the SCR catalyst coated first substrate, Patchett also notes that a honeycomb wall flow substrate can alternatively be used. (Id. at 23.) Claim 6 depends on claim 5 and requires that the exhaust gas stream further comprises ammonia. Additionally, the wall flow substrate must be coated with CuCHA. As discussed above, Patchett discloses both a SCR process that employs ammonia, and a first substrate (which can be a wall flow substrate) coated with a copper-exchanged zeolite. Claim 7 requires that at least a portion of the wall flow substrate be coated with Pt and CuCHA to oxidize ammonia in the exhaust gas stream. Again, as noted above, Patchett describes a system that employs a first substrate (which can be wall flow substrate) with two catalytic zones. The first zone is coated with an SCR catalyst such as a copper-exchanged zeolite. The second zone is coated with a NH 3 destruction catalyst such as platinum. (Id. at 19-21, 23, 54, 56.) Claim 8 requires both that the gas stream be from an internal combustion engine and that a catalyzed soot filter be used. Patchett s system includes a second substrate upstream from the first substrate discussed above. (Id. at 25; -26-

31 Figs. 3B, 3C.) This second substrate can be coated with the same SCR catalyst as the first substrate. (Id. at 25.) Further, the second substrate can be a wall flow substrate allowing the system [to] remove greater than 80% of the particulate matter including the soot fraction and the SOF. (Id. at 63.) Thus, Patchett s system can employ a catalyzed soot filter. Patchett also incorporates by reference another application filed by the same group of inventors that further describes [a]n SCR-coated wall flow substrate and its utility in the reduction of NOx and particulate matter. (Id. ) This other reference details an emission treatment system having a soot filter coated with a material effective in the Selective Catalytic Reduction (SCR) of NOx by a reductant, e.g., ammonia. (Ex. 1106, Patchett 514, at 1, 9, 43-44, 47, 68, 74.) Claim 9 requires that the catalyzed soot filter be upstream of a nitrogen oxide reducing catalyst. Patchett describes systems that include both an upstream catalyzed soot filter (which it refers to as a second substrate ) and another substrate with a nitrogen oxide reducing SCR catalyst (which it refers to as a first substrate ) downstream of the soot filter. (See Ex. 1105, Patchett at 25, 26-29; Figs. 3B, 3C.) Claim 10 requires that the catalyzed soot filter be downstream of a nitrogen oxide reducing catalyst. As noted above, Patchett explains that its system includes an upstream second substrate and a downstream first substrate. Both of these substrates are coated with a nitrogen oxide reducing SCR catalyst. (Id. at 25.) Patchett also explains that the downstream first substrate can be a wall flow -27-

32 substrate, and that this type of substrate acts as soot filters. (Id. at 23, 63.) This is all claim 10 requires. Further, even if Patchett disclosed only the use of an upstream soot filter, reversing the order of Patchett s catalyst coated substrates such that the catalyzed soot filter was located downstream would have been nothing more than an obvious design choice. (See Ex. 1108, Lercher Dec. at 214.) Claims 11, 12, and 13 respectively require use of diesel oxidation catalyst, a diesel oxidation catalyst upstream of a nitrogen oxide reducing catalyst, and both a diesel oxidation catalyst and a catalyzed soot filter upstream of a nitrogen oxide reducing catalyst. Claims 25 and 31 require a similar arrangement of catalysts. Patchett discloses use of the claimed oxidation catalyst, catalyzed soot filter, and a second SCR catalyst arranged in series in this order to treat an exhaust gas stream. (See Ex. 1105, Patchett at 63-64, Fig. 3C.) Claim 16 and 28 require the use of urea as a reductant. Patchett employs urea. (See id. at 3, 60.) One of ordinary skill in the art as of February 2007 would have been motivated to use the high silica, copper promoted zeolites with the CHA crystal structure set forth in Maeshima and Breck as part of Patchett s SCR system to arrive, with a reasonable expectation of success, at the claimed subject matter. (See Ex. 1108, Lercher Dec. at ) As explained above, Patchett describes the use of a copper-exchanged zeolite as a catalyst in an SCR process to reduce nitrogen oxides in diesel engine exhaust. The only difference between Patchett and the subject matter of the claims is that Patchett does not specifically reference zeolites with the CHA crystal -28-

33 structure or the specifically claimed proportions of silica, alumnia, and copper. Patchett does, however, identify the characteristics of the zeolite that should be employed. For instance, Patchett explains that the zeolite should, among other things, be resistant to sulfur poisoning and sustain a high level of activity for the SCR process even when subjected to high temperatures and hydrothermal conditions. (Ex. 1105, Patchett at 66.) Copper is preferably present in an amount of about 1 to 5 percent by weight. (Id. at 65.) Patchett also cites to other references that include examples of [s]uitable SCR catalyst compositions. (Id.) The zeolites in these references have a SAR greater than 10. (See, e.g., Ex. 1110, U.S. 4,961,917 to Byrne at Abstract, 2:26-35; Ex. 1111, U.S. 5,516,497 to Speronello et al at Abstract, 6:3-7:3.) Maeshima and Breck describe this very type of catalytic material. The zeolites of Maeshima and Breck can have a SAR of up to 20 (see Breck, Ex. 1103, at 18:3-20), include approximately 2-10% copper by weight (see Maeshima, Ex. 1102, at 6:13-17), and provide improved resistance to sulfur oxides and enhanced thermal and hydrothermal stability (Ex. 1103, Breck, at 47:44-53). Thus, as of February 2007, one of ordinary skill in the art would be directed to the catalytic material of Maeshima and Breck when attempting to implement Patchett s process. (See Ex. 1108, Lercher Dec. at ) Put another way, there were known benefits to the use of Maeshima s and Breck s zeolites, including higher thermal and hydrothermal stability and resistance to poising by materials like sulfur oxides. (See Ex. 1103, Breck, at 47:47-52.) -29-