IN THE lTr"JITED STATES PATENT AND TRADEMARK OFFICE
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`Examiner: D1Af\·10ND, A.LAND
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`Group A.rt Unit: 3991
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`Confirmation No: 2755
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`Jn Inter Partes Reexamination of:
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`BULLET AL
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`Reexamination Control No. 95i001 ,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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`1'-·foH Stop Intel' Partes Rcexam
`Centra! Reexamination Unit
`Commissioner for Patents
`P,O, Box 1450
`Alexandria, VA 22313-1450
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`SECOND DECLARATION O:F STANLEY ROTH3 PH.U. UNDER 37 CF.R. ~ 1.132
`I, Stan Roth, do declare and say as follows;
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`1.
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`I am currently the research group leader for diesel oxidation catalysts and soot filters for
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`BASF Corporation, located in lselin, New Jersey. I currently have 18 scientists who perfonn
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`research into diesel oxidation catalysts and soot filters reporting to me.
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`Jn 2005,, I held the
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`position of research group leader for NOx control catalysts for Engelhard Corporation, which
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`vvas subsequently acquired by BASF Corporation.
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`2.
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`I received a doctorate degree in Inorganic Chernlstry ln 1982 frorn University of I Uinois.
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`I have been involved in the research and development of catalysts since 1986, and since 1995 1
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`have vvorked in the areas of research and development of catalysts for automotive emissions, in
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`particular diesel engines.
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`3. Since becorning involved m catalyst research and development in 1986, I have taken
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`steps to stay current in the state of art of catalysts, For example, 1 review scientific literature
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`submitted for publication and journals in the area of automotive catalysis. l attend scientific
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`meetings related to general catalysis and meetings specific lo catalysts for automotive emissions.
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`I also am a named inventor in 12 United States patents and applications relating to automotive
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`Exhibit 2013.001
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`inter Partes Reex<-trriination No. 95/00 l ,453
`Second Declaration of Stanley Roth, Ph.D.
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`c<:~talysts. Since ·1975, l have conducted research on zeolite cata!y~;t;:\ and since 1996, 1 have had
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`a special intt~rest in zeoEte catalysts for hydrocarbon and arnm.onia selective cat<:1lytic reduction
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`4. This is 1ny second declaration in the above-·identi:fied reexarninatiorL
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`r prevk~us!y
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`5, I have read United Sta.ks Patent No. 7,60 l ,662 ("the '662 patent''), Thus, as stated in my
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`First Dedan-1tiort, I am familiar vvith the specification and claims of th<,~ '662 patent.
`l understand that the '662 patent ls p:e:;ently under reexamination in the United States
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`6.
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`Patent and Trademark Office. I ft.niher understand that all of the claims have been rejected as
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`alkged!y be1r1g obvious over various cited reforcnr:es.
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`7- The '662 patent genernl!y describes n catalyst comprising an durninosilicate zeolite
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`having the CHA cry~>tal An.Ktrffe. 0 a silica te ,:dnrnina ratio of about 15 and mi. atomic ratio of
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`ratio~> in the range of 15 to 40 a.nd copper to altnJJinurn ratios in the range of <lbout 025 to 0-5(}.
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`The catalysts described and daimed in the '662 patent ztre useful for the abatemem of nitrogen
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`excess oxygen in the presence of a rcductant such as mr:n10nia.
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`8. L have reviewed a nrnnber nf article<:: axid other literature related to zeolite catalysts,
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`induding an article by Dr. Gab.ride Centi entitkd Nature of /\.ctive Species in Copper-Based
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`Cataly~>ts and Their CherriiBtry of Transfonnation of Nitrogen Oxides, in A:pphed Catalysis A:
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`Gencra.L, VoL 132, l 79--259 (1995) C'the Centi A.rtick'') and a book authored by DL Centi,
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`Slglinda Perathoner and Fernucdo Tr1fir6 e.ntHled "Sustainable Indu~:trial Processes," published
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`in 2009 ("the 2009 Centi Book"). 1 have also, once ~~gain, reviev·led a. series of emails related 10 n
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`project I \.Vas pursuing with the Ikpa.rtmer:t of Energy '.<vi th a lmiversity che.mistry professor.
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`Q Based on rny re-,,1ie\v of these articles, th:::.'.se c1na.Us and my g:::.'.neral kno1--v!edge of the stare
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`of the art in zcolJte <.:atalysts from the early ·1990s tn 2007. it is iny npinion that u.n:~olved
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`prubk.rns existed fi·orn at least 1995 to 2007 .in the ust nf zecdite catalysts in automotive
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`a.ppLications. It is my further opinion that frorn ! 995 to 2007 there \vas skepticisrn about i;.vhethe.r
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`concerns abom the hydrothermal s.tabi Lity of these catalysts.
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`The Centi A.rtide
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`Exhibit 2013.002
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`Inter Partes Reexamination No. 95/001,453
`Second Declaration of Stanley Roth, Ph.D.
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`10. One of the articles I reviewed in forming my opinions in this matter was authored by Dr.
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`Gabriele Centi. The article is entJtled Nature of Active Species in Copper-Based Catalysts and
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`Their Chemistry of Transformation of Nitrogen Oxides, in Applied Catalysis A: Genera!, VoL
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`132, 179-259 (1995) ("the Centi Article"). A copy of the Centi Article is attached as Exhibit A.
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`11, I understand that Dr. Centi submitted a declaration in thls reexarnination for the
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`Requester.
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`12. The Centi Artlcie states that "several unresolved problems limit the outlook fr)r
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`successful use of zeoliles in automotive converters." Exhibit A at 183. In my opinion, this
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`reforence in the Centi Article proves that unsolved problerns existed in the use of zeolite
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`catalysts in automotive converters in 1995.
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`13. The Centi Article also states that "fa] lovv hydrothermal stability, in particular, is the
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`n1ore critical weakness of copper-containing zeo!ites." Id The Centi Article also states that
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`"[ c]opper-based catalysts are thus a reforence catalyst fiunily for the investigation of the
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`mechanism of selective reduction of NO, albeit for practical applications their ioY."' hydrothermal
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`stability rnay prevent a commercial use." Id at page 184 (emphasis added). In my opinion,
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`these references in the Centi Article demonstrate that unsolved problems existed in the use of
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`copper based catalysts and that the perceived prob km was a low hydrothermal stability of these
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`catalysts. Further, in my opinion, these references demonstrate skepticism about whether copper
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`-based catalyst could ever be used in automotive applications.
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`14. Furthermore, the Centi Article recognizes that there was interest in Cu-zeolites at least as
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`early as 1990-92, as Dr. Centi indicates that there was increased interest in Cu-zeolites with
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`reference to research papers published in the 1990-92 tirneframe. Exhibit A at page 183, Yet
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`until the invention ofH1e '662 patent, a Cu-zeollte had not been provided for SCR of NOx in
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`vehicles that exhibited hydrothermal stability,
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`The 2009 Centi Book
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`15. I have also revie'vVed sections of a book authored by Dr. Centi, Siglinda Pemthoner and
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`Fernuccio Trifin'; entitled "Sustainable Industrial Processes," published in 2009 C'the 2009 Centi
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`Book"). Excerpts from the 2009 Centi Book are attached as Exhibit B.
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`l 6, The 2009 Centi Book (Exhibit B) at page 380, states:
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`Zeolite systems are very active at low temperatures but they also
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`have disadvantages related to their hydrotberrnal stability and the
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`Exhibit 2013.003
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`Inter Partes Reexamjnation No. 95/001,453
`Second Declaration of Stanley Roth, Ph.D.
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`possibility of inhibition or pcnsornng by diffr~rent compounds.
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`These dnnvbacks drastically limit the industrial applications of
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`these catalysts.
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`In my opinion, this statement rn the 2009 Centi Book confirms that experts Jn the field of
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`catalysts understood that probkms regarding the use of zeolite catalysts, particularly with their
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`perceived hydrothermal stability, rernafried unsolved in 2009.
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`Ln my frJrtber opinion, this
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`statement also demonstrates that experts in the field of catalysts remained skeptical about the
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`ability to use zeolJte cataJysts in any industrial application in 2009.
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`The Department of Energy
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`17. When I submitted iny First Declaration in this matter, I attached a senes of emails
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`relating to a proposed Department of Energy ("DOE") project relating to zeolite catalysts. I have
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`reattached this series of emails to this Declaration as Exhibit C.
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`18. As I stated in my Flrst Declaration, the company I 'Norked for at the tirne, Engelhard, and
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`a university profossor had proposed a project relating to copper zeobte catalysts to the DOE in
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`the 2005 time frame.
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`19. This proposed DOE project \.Vas not approved by the DOE. In my opinion, the proposed
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`DOE project \.Vas not approved because of the skepticisrn regarding the use of zeobte catalysts in
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`the field in 2005. :rvty opinion is based, in parL on the ~views expressed in the Centi Article and in
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`the Centi Book.
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`20. Jv1y opinion is forther based on the advice the DOE gave to the profossor I was v,;orking
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`1Nith. In September 2005, the professor advised rne that:
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`the JTH~or criticism from the revie\.ver (and echoed by the DOE
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`grant monitor) is that Cu-exchanged zeoHtes lack the hydrothennal
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`stability needed to be commercially viable for SCR of NOx \.Vith
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`ammonia for diesel engine~~.
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`Exhibit C at 6-7.
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`21. The professor also noted that one DOE reviewed stated: "I have heard the same negative
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`cominent about the prospects for Cu~zeolites from several other investigators who presumably
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`are also experts in this area.'' Exhibit Cal page 3, Thus, in addition to the DOE reviewer and his
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`colleagues at the DOE, several other investigators were stilt dismissing the conunercial viability
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`of Cu-zeolites due to their lack of hydrothermal stability ln the 2005 time frame.
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`4
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`Exhibit 2013.004
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`Inter Partes Reexamination No. 95/00 l ,453
`Second Declaration of Stanley Roth, Ph.D.
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`22, One of the DOE reviewers also stated that "[i]t is interesting to note that not a single
`metal-zeofae fix SCR was commercialized in the US.A. in the l9901rsl (sec John A1111or, App,
`I arn familiar with the Annor article
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`referenced by the revie'vver, and the article does a full review of catalysts commerciaLized in the
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`USA during the 1990s, but docs not memion any Cu-zeolites. I am also familiar with Dr. Armor
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`and aware that he has a Ph.D. in chemistry, extensive experience in heterogeneous catalysis
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`research, and was the President of the North American Catalysis Society for eight years. This
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`statement indicates that the DOE was still skeptical about the use of z.eolite catalysts in 2005.
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`23. I also note the criticism offered by the project reviewer and the DOE grant monitor
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`reiterates the standing ctiticism noted in the Centi Article and the 2.009 Centi Book.
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`24. I have also reviewed a document submitted in this reexamination by the Requester on or
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`about July 27, 201 L Pages 30 and 31 of this document is attached hereto as Exhibit D. In this
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`document, the Requester characterized these emails as follows;
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`ln addition, Requester notes that in his e-1nail coffespondence attached as
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`Exhibit A of his Declaration to show a11eged "skepticism by experts", Dr.
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`Roth describes these "experts" as "a reviewer who does not have much
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`cxpenencc with
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`zeolites",
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`"not understanding
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`the
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`fundamental
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`hydrothennal stability of zeolites", and "revie\Ners, who are not experts in
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`the field, f'..vho] are taking what little they have deard [sic] about unrelated
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`chemistry and dra'v\rir1g the conclusion that your proposed project is not
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`based on a catalyst that can survive under realistic conditions.n
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`Accordingly, Requester respectfolly submits that the proffered evidence of
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`alleged "~:;econdary considerations'' is not effoctive to rebut an obviousness
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`rejection of claims 1~55 of the '669 patent
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`Exhibit D,
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`25. In my opinion, the Requester has frJcnsed on specific words in the ernail while ignoring
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`the prevailing view of experts in lhe field, such as the views expressed in the emails, in the Centi
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`Article and in the 2009 Centi Book that there were problems and skepticism regarding the use of
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`zeolite catalysts due to their hydrothermal stability problems.
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`5
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`Exhibit 2013.005
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`26. Further, t!w vvords 1 used in the scncs of cnulib '>Vith the university profossm do not
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`Inter Partes Reexarnination No. 95/001,453
`Sccund Declaration of Stanley Roth, Pb . .D.
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`in the 2009 Centi Book. \Vhen 1 stated that the Departrnent of Energy ff)OE; revie\vers were not
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`experts in the field, 1 '-"'iHS referring to the foet that the DOE revit.:\V\.TS were not expe1-b in the
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`particular dew;.:hvation niechanisrns fr_rr zec;Lik catalysts. As described in tny ernail on page 3 of
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`Exhibit D, NB_,-SCR catalysts do not have the same deactivation medrnnisrn as HC-SCR
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`catalysts. J'vfrrny researd.ters in the field of SCR catnJysts do not fully under:::tand the deactivation
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`mecbrnisms for zeolite catalysts. Such deactivation can depend on a variety of factors incl.uding
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`the zeohte structure type, the chemistry of Uw zeollte=· the particular rnetal ion exchanged lnto tbe
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`zcolite ti'amework, m:id the type of reductant mk:d in the SCR reaction. DOE revie\.vers would
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`not be expected to folly understand every nuance of :.his cmnplicated field,
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`27, 1 an1 aiso personally acquainted 'vvhh the DUE reviewer referred to in the series of enrni!s
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`;:JtaclK0d as Exh1bit C, as well as his qualifications, That revie'-;:ver had an extensive background
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`in heterogeneous rnta1ysis.
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`l am aware ti-t=tt the revic<ver had a Ph.D. in chemical engineering
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`reaction engineering and heterogeneot.B catalysis. The DOE revie\ver refoncd to in 1ny E>nrni!s
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`prograrn at the National Science Foundation.
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`28. The only idea I -..vas trying to convey In the series of emails is that a DOE reviewer raxely
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`can be subject tnatter experts in every reaction rnechanism of every research area under thdr
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`managcmem.
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`29. l-Imvevec I know ~;everal DOE reviewers a11d have been invol>..·\Xi ·with the sr:brniss1on of
`DOE research. propos;::.L;, and DOE n::vje\-vers. are knmvkdgeabk in the stat<:.: of the art of
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`sptclfic catalysts. for SCR reactions. The natrn\' of a DOE revie\ver>~' job requires. revinvers to
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`This is evident based on t.he awan.>ness of sev~;rnl revievvers in the e-:nail that no Cu-ztcdite at the
`This \VilS. in vie-..v of their being kno\vkdgeabk 0 r
`the Literature in the Edd and revicvving the ;vork of other prim'1pal investigators ·who also held
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`6
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`Exhibit 2013.006
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`Long Felt Neea'
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`Inter Portes Reex.amlnatio.n No. 95/001,453
`Second Dedarai.1on of :::Hank:y Roth, PL D,
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`temperature NOx catalytic activity and hydrothermal stability, This nred \V~b not n1d until the
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`c<Halyst of the '662 patent \vns invented. Considering tbat the first catalytic converter tor
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`k'l" ,
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`m1ton10 vlies \Vas not cornrnercia.uz.e uritl 1 ':f; ::\ n 1s .my opnuon cd a person or or<.imary s 1 i m
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`~·
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`~
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`the art tb.at HK: period frorn 1992 to 2007 (or at Ieasi. fron1 l 995 to 2007-the date of Dr. Ccnh's
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`article) \Vas a "long" tirne in the field of SCR cmalysts., so that a long felt need existed fr;r the
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`catalyst of the '662 pai.ent
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`31. l have been i.nfonned that in the Action Closing Prosecution, tbe Exarniner concluded
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`r.hat Uw Patent (hvner had not shown that the need \Vas a persistent one tbat \Vas recognized by
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`those of o:dinary skirt in the mt, n.'fr'.rring to the discussion in the Ford fvfot.or Cmnpm:y paper of
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`th;:; futun.: Tier 2 Bin 5 standards t~1r lo\.v exhaust ternperature applications. The reference in. the
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`Ford JVfntor Conrpany 1X1per attm+ed to .my First l.kcbrntion does not at all change the fact that
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`the prnhlem of hydrothermal sta.bifay of Cu .. zeoLites '<-VHS a persistent problem. The interest in
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`Ne)( Us
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`32. The '662 patent cont<tins cla.in1s arncnded (l\tr1ng reexanunat.ion directed to <1 catalyst
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`cornprising an aluminosilicate zcolite having the CHA crystal structure, a si !ica to alumina ratio
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`of about 15to l 50 and an atornic ratio of copper to ahnnirn.nn of a.bout 0,25 to about 1, The
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`dairned features of ~m a!uminosilicate zeolite having the CH/\ crystnl structure, a silic<::. to
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`allunitw ratio of about 15 and I 50 an atomic ratio of copper to ahrn1inu.rn frmn about 0.25 to
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`a.buut 1 aHo;,vs tik catalyst of the '662 pa.tent to satisfy the unsolved prohk1ns and the long feh
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`need, and to overcGinc the ~~kepticisrn in the field by providing a c<1tdyst \.:./itb knv ternperdturc
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`P.-JOx catalytic activity and hydrothennfa! s:tabi Ety,
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`§11deed feer1bac:k fro.lTl <)ur a11to111otive
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`These bern.~fits include
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`the ability·
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`to \Vitbstand
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`hydrothermal aging at ten1peratures 80G "C and higher for extenck.d periods of time of up to 50
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`hours at 800 "C and te.mperatures up to 900 "C for shorter periods of i.ir.ne in hurnid cnvirorm1er1t~-;
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`for shorter periods of tirne \Vithont a significm-.r! l.os~~ of activity, The catalysts :having the clairned
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`7
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`Exhibit 2013.007
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`Jraer Partes Reexmnination No. 95/001,453
`Second Declara.tion of Stanley Rodli Ph.D.
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`Praise
`33, As
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`decL1.rntion 0 Ford researchers consider the ne\V catalyst rernarkable. The K\vak er aL paper
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`attached as Exhibit B to rny first declaration citing the n:mterial in the '662 patent des;:;rHxd
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`alurninosiiicate Cu chalx1zite as having "superior activity and sdectivity," H sbouki not go
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`~lithout notice that the K\vak et al paper was supported by the Depanment of Energy, the entity
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`that ha.d in 2005 considered Cu~zeotites a lost. cause in the search fi.1.r a hydrothermally durable
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`catalyst having exce!knt catalytic activity across a broad temperature range including bdov,r 250
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`34. /\ rnnre recent scientiik paper entitled Sc'.!eetive Catalytic Re:duction of N(h:. by a:r.nnion;,a
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`on Jnetal-exchangcd zcolik catalysts'' (Exhibit E) n.~fers to the '\tunning krnperature st.ability
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`under SCF~ conditions" of Cu-containing ;:dumino~">iiicate zeolite catalysts. Thr. ;662 patent has
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`l hen.:;by declare thm aH statements n1ade herein of n1y uv/n knov'iledge are true <:md that all
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`maternents made he.rein on inforrnation <ind belief are bdkved to be tnw; <1nd fi.rrther that these
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`swterm:.nts were nrnde with the knovdedge that vvmful false statements and the like so made are
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`rnmishable by fine or hnprisonrnent, or both, under Section J 001 of Titre l 8 of the United States
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`Code, and that such 'vvlllful frllse statements may jeopardize the vaEdity of the above-idrntifred
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`patent.
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`Dated: Decen1b:;.T 15, 20l J
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`p., .
`. 5-}·
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`Exhibit 2013.008