IN THE UNITED STATES PATENT AND TRADEMARK OFFICE
`
`Exarniner: DLA.MOND, ALAND
`
`Group Art Unit: 3991
`
`Confirmation No: 2755
`
`)
`
`)
`
`)
`
`)
`
`)
`
`)
`
`In Inter Partes Reexamination of:
`
`BULLET AL
`
`Reexamination Control No. 95/001,453
`
`Patent No. 7,601,662
`
`Issued: October 13, 2009
`
`For: COPPER CHA
`ZEOLITE CATALYSTS
`
`Mail Stoi' foter Partes Reexam
`Central Reexrunination Unit
`Commissioner for Patents
`P.O. Box 1450
`Alexandria, VA 22313-1450
`
`DECLARATION OF STANLEY ROTH, PH.D. UNDER 37 C.F.R. § 1.132
`
`I, Stan Roth, do declare and say as follows:
`
`1. I am currently the research group leader for diesel oxidation catalysts ru1d soot filters for
`
`BASF Corporation, located in Iselin, New Jersey. In 2005, I held the position of research group
`
`leader for NOx control catalysts for Engelhard Corporation, which was subsequently acquired by
`
`BASF Corporation.
`
`2. I received a doctorate degree in Inorganic Chemistry in 1982 from University of Illinois.
`
`I have been involved in the research and development of catalysts since 1986, and since 1995 I
`
`have worked in the areas of research and development of catalysts for automotive emissions, in
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`pruiicular diesel engines.
`
`3. I am fruniliar with United States Patent No. 7,601,662 ("the '662 patent"), which is
`
`directed to a catalyst comprising a zeolite having the CHA crystal structure, a silica to alumina
`
`Exhibit 2001.001
`
`

`
`LY!ter Partes Reexamination No. 95/001,453
`Declaration of Stanley Roth, Ph.D.
`
`ratio of about 15 and an atomic ratio of copper to aluminum exceeding about 0.25, with specific
`
`claims directed to silica to alumina ratios in the range of 15 to 40 and copper to aluminum ratios
`
`in the range of about 0.25 to 0.50. Such catalysts are useful fbr the abaternent of nitrogen oxides
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`in lean bum engines such as diesel engines, particularly by selective catalytic reduction in excess
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`oxygen in the presence of a reductant such as anm1onia.
`
`I understand that the '662 patent
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`presently under reexamination in the United States Patent and Trademark Office, and that all of
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`the claims have been rejected as allegedly being obvious over various cited reforences.
`
`4.
`
`In 2005, I contacted a university professor, whom Engelhard was working with to obtain
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`Department of Energy (DOE) funding for a proposal to study Cu-zeolites for selective catalytic
`
`reduction (SCR) of nitrogen oxides (NOx). Exhibit A attached hereto is a copy of the e-mail
`
`correspondence with the university profi.~ssor on the DOE proposal, with the names of the
`
`professor, DOE review personnel and other personnel redacted. As shown on page 7 of Exhibit
`
`B, the grant proposal was wait-listed because the DOE grant rnonitor concluded that "Cu-
`
`exchanged zeolites lack the hydrothem1al stability needed to be commercially viable for SCR of
`
`NOx vvith ammonia for diesel engines."
`
`5. Afler receiving the infonnation that the grant proposal had been vvait-listed, I wrote back
`
`to the profossor asking if the proposal could be reconsidered. The professor explained that
`
`"some reviewers, and my DOE grant :rii::urnger simply think Cu-exchanged zeolites are far to [sic,
`
`too] unstable to water to be commercially feasible, so they do not want to fund work in the area."
`
`(Exhibit A, at page 5).
`
`6. After w-riting to the professor a second time, the professor quoted the DOE contact as
`
`stating:
`
`"Clarifying the vvater-stability issue, without revealing proprietary
`knowledge, would be a good point to address in a new version. I have
`
`2
`
`Exhibit 2001.002
`
`

`
`Inter Partes Reexamination No. 95/001,453
`Declaration of Stanley Roth, Ph.D.
`
`heard the same negative comment about the prospects for Cu-zeolites from
`several other investigators who presumably are also experts in this area.
`Thus, it is imperative to argue/present evidence that dispels such belief.
`More that the practicality of the concept, such as prospects for large-scale
`commercialization, the BES reviewers will be seeking fur the rationale
`that will lead to new/corrected mechanistic understanding underlying such
`stability (or lack thereof)."
`
`(Exhibit A, page 3 ).
`
`7. The professor further quoted one of the reviewers as stating:
`
`"The structure-property-processing relationships that the PI's describe as
`the scientific goals are meritorious and worthy of support. The Pl's
`weaken their position considerably, hm.vever, by emphasizing the
`technology of SCR in diesel vehides \Vhen in fact propose to study de(cid:173)
`NOx via ammonia over Cu-exchanged mordenite. Moreover, the PI's
`completely side step the issue of catalysts deactivation in the presence of
`water; I believe this to be the primary reason why metal-exchanged
`zeolites have limited application. It is interesting to note that not a single
`metal-zeolite for SCH. was commercialized in the USA in the 1990'2 (see
`John Annor, App. Cat. A, V222, page 407(2001))."
`
`(Exhibit A .. , pages 3-4).
`
`8. The statements made by the DOE contact and reviewers represented the view of many
`
`researchers and those skilled in the art that Cu-zeolites could not be used as catalysts for the SCR
`
`of NOx because of the inability to maintain NOx conversion upon exposure to hydrotherrnal
`
`conditions-namely temperatures in excess of 650° C and R~O of 10%.
`
`Even the recent
`
`literature, recognizing the results achieved in the 1662 patent have called the problem of NOx
`
`reduction in lean burn engines as "daunting". (Exhibit B, first page).
`
`9. The challenge before the invention of the '662 patent was to provide a zeo!ite material
`
`promoted with a metal or metal ion that exhibited high NOx conversion across a wide
`
`temperature range, including temperatures in the range of 200° to 350° C and that maintained
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`high NOx conversion after hydrothennai aging of temperatures above 650° C, and in some cases
`
`3
`
`Exhibit 2001.003
`
`

`
`Inter Partes Reexamination No. 95/001,453
`Declaration of Stanley Roth, Ph.D.
`
`as high as 800° C or 900° C. The researchers at Ford summarized the problem in the research
`
`paper attached as Exhibit C (first page):
`
`Passenger and light duty diesel vehicles will require up to 90% NOx
`conversion over the Federal Test Procedure (FTP) to meet future Tier 2
`Bin 5 standards. This accomplishment is especialiy challenging for low
`exhaust temperature applications that mostly operate in the 200° - 350° C
`temperature regime. Selective catalytic reduction (SCR) catalysts
`.formulated \vith Cu/zeolites have shown the potential to deliver this level
`of perfom1ance fresh, but their perfom1ance can easily deteriorate over
`tirne as a result of high temperature thermal deactivation.
`
`10. Jn 2006, I am aware that Engelhard Corporation provided samples of a Cu-zeo!ite having
`
`the CHA crystal structure deposited on a substrate to Ford Motor Company for SCR testing, and
`
`I understand that this is the material tested and described in Exhibit C, a research paper by Ford
`
`Motor Company entitled "Enhanced Durability of a Cu/Zeolite Based SCR Catlayst. As noted in
`
`Exhibit C (first page), it was believed that Fe-zeolites exhibited superior hydrothermal durability
`
`compared to Cu-zeolites, After testing the samples that were sent to Ford, the Ford researchers
`
`concluded that the material of the '662 patent is "remarkable". (Exhibit C, last page).
`
`In past years, no reported Culzeolite SCR formulation was able to yield
`stable low temperature NOx performance after exposure to hydrothennal
`conditions consisting of 1 hour at 950° C. Within the last year, a
`remarkable Cu/zeolite SCR formulation was identified with high NOx
`conversion in the 200° C - 350° C temperature range.
`
`11. The material claimed in the '662 patent has been sold for use as a SCR catalyst for the
`
`removal of NOx in diesel engines in several difforent automotive manufacturer vehicle
`
`platforms. The material of the '662 patent has met a long-standing and previously unfulfilled
`
`need - a metal zeolite that exhibits both excellent NOx conversion over a wide temperature
`
`range, including the range of 200° to 350° C, and that maintains high conversion after exposure
`
`to hydrothermal conditions. This has allowed auto~notive manufacturers to rneet increasingly
`
`stringent NOx standards that went into effect in 2010.
`
`4
`
`Exhibit 2001.004
`
`

`
`Inter Partes Reexamination No. 95/001,453
`Declaration of Stanley Roth, Ph.D.
`
`12. The Research & Development Council of New Jersey has recob111ized the inventors of the
`
`1662 patent with the 2010 Thomas A.Iva Edison Patent Award in the environmental category,
`
`which recognizes the outstanding work done by New Jersey scientists and inventors by honoring
`
`the most exceptional efforts.
`
`I hereby declare that all statements made herein of my own knowledge are true and that all
`
`statements made herein on infom1ation and belief are believed to be true; and further that these
`
`statements were made with the knowledge that willful fa.lse statements and the like so made are
`
`punishable by fine or imprisonment, or both, under Section 1001 of Title 18 of the United States
`
`Code, and that such willful faise statements may jeopardize the validity of the above-identified
`
`patent.
`
`Dated: January 20, 2011
`
`By:
`
`Respectfully submitted,
`
`5
`
`Exhibit 2001.005
`
`

`
`EXHIBITS TO DECLARATION OF STANLEY ROTH, PH.D. UNDER 37 C.F.R. § 1.132
`
`EXHIBIT A
`
`Exhibit 2001.006
`
`

`
`EXHIBITS TO DECLARATION OF STANLEY ROTH, PH.D. UNDER 37 C.F.R. § 1.132
`
`Stan Roth/RD/ENGELHARD
`
`09/28/2005 02:55 PM
`
`To Jamesllllllllll!llllll!llllll!llllll!llllll!llllll!llllll!llllll-'i'.~1'!>
`cc
`
`Subject RE: proposal on Cu-zeolites for NOx SCRLtn)s.
`
`Jim,
`
`I have been out of the country for the past week. How did we leave this issue of your DOE proposal?
`
`From my perspective you can go ahead as planned in your memo below. Hopefully our discussion has
`been useful. You can modify your introduction to include the comparative zeolite requirements for HC(cid:173)
`SCR and NH3-SCR. Let me know if you require me to slightly modify my 2005 memo to state that
`"Preliminary experimental data shows thermal durability to 800"C"
`
`In the zeolite literature there are probably many examples of structures with hydrothermal durability to the
`700-SOO"C range. The big issue appears to be your DOE reviewers that have experience limited to the
`Cu-ZSM5 HC-SCR example, where catalytic performance quickly died after modest hydrothermal aging.
`
`I understand that you like Mordinite because it's symmetry makes calculations easier. And that many of
`your papers have concerned work on ZSM-5. Is part of the problem with your DOE proposal that you are
`stressing continual work on these zeolites?
`
`Moving forward, I would not really recommend either of these zeolites for the NH3-NOx application. Do
`we want to take our relationship to the next step, and have Engelhard supply you with samples for
`evaluation/modelling. This will of course require confidentiality/secrecy agreements, and in the past it has
`taken months to iron out all the legal implications. In cases were the University requires retention of
`patent rights, Engelhard has declined to participate in potentially useful programs. The alternative is to
`keep the relationship on an informal basis. That limits the relevance of your work to model catalyst
`systems, but also puts no limitations on publication of the results. Let me know you thoughts on this
`subject.
`
`Regards,
`Stan
`
`09/16/2005 05:05 PM
`
`cc:
`Subject:
`
`RE: proposal on Cu-zeolites for NOx SCR
`
`Hi Stan,
`
`Thanks very much for the explanation.
`really clarified the issues for me.
`
`I knew part of it, but what you said
`
`I would like to go ahead and resubmit my proposal mostly as is but with more
`explanation of the stabilization issue, as that was the only major objection
`
`Exhibit 2001.007
`
`

`
`EXHIBITS TO DECLARATION OF STANLEY ROTH, PH.D. UNDER 37 C.F.R. § 1.132
`
`to our proposal, which otherwise was very favorably reviewed.
`
`So, my plan is to change our intro to include solrmlelnlo~f~~~~~~'s data from
`of the I
`11111111111, and some data from (
`Institute.
`
`With your permission, I will also clarify some of the stability issues using
`the info only from your Sept 16 email, and none of your proprietary info.
`
`I would like to also ask if I could reuse the letter you had given me in
`January 2005, but with a current date?
`
`Hopefully that will be enough. The DOE really wants me to resubmit by mid(cid:173)
`September to meet their January review, so I am unfortunately being rushed in
`my revisions.
`
`Thanks again for your help!
`
`Best wishes,
`Jim
`
`James 111111111111111
`Professor
`Department of Chemical and Materials Engineering
`University
`
`(fax)
`
`-----Original Message-----
`From: Stan_Roth@engelhard.com [nk j_ J_ t: o; .''t-':n ___ r-zor.hi<:,:,nqe l hzF···:l, C()H:]
`Sent: Friday, September 16, 2005 12:38 PM
`To: James
`Stan_Roth@engelhard.com
`Cc:
`Subject: RE: proposal on Cu-zeolites for NOx SCR
`
`Jim,
`
`Thank you for these reviewer quotes.
`At last I finally understand where the objections to your proposals are
`comming from.
`
`5-10 years ago there was much effort worldwide on the reaction of HC+NOx,
`oven known as active lean NOx or HC-SCR. There are propably 500+
`literature references to this catalyst concept. There were two main types
`of catalyst used for this reaction:
`(1) Pt-ZSM5 which functioned from 180-250°C but had as it's main weakness
`that the reaction was not selective and produced predominately N20 rather
`than N2.
`(2) Cu-ZSM5 which was had an activity window from 300-500°C, did not
`produce N20, but had as it's main weaknees that the catalyst deactivated
`and could not survive extended hydrothermal treatment over 550°C. The
`mechanism of deactivation was clearly demonstrated to be loss of strong
`
`Exhibit 2001.008
`
`

`
`EXHIBITS TO DECLARATION OF STANLEY ROTH, PH.D. UNDER 37 C.F.R. § 1.132
`
`acid sites in the zeolite that were responsible for coke formantion. The
`reaction pathway involved the seqauential reaction of HC on the acid sites
`to form coke. The reaction of NO on Cu to form N02 and the reaction of N02
`with "coke" to form NO and N2.
`
`NH3-SCR catalysts do not have the same deactivation mechansim because the
`strong acid sites do not play a role in the rate determining step of the
`reaction. Yet it appears as if the reviewers, who are not experts in the
`field, are taking what little they have deard about unrelated chemisty and
`drawing the conclusion that your proposed project is not based on a
`catalyst that can survive under realistic conditions.
`
`How do we go forward?
`
`Regards,
`Stan
`
`P.S. I will be out of the office for the next week visiting
`automotive/truck customers in Europe. We can talk again when I return.
`
`J<a11mm;e~~~~~llllll!llllll!I
`.-.1
`----------------------------~t~? __ : ____________________ .. ~}.:~--~:-~_~:_]_===!~-~~-~~~x~-~~:-~~=-~:_]_9~~-~l_.x~-~:~-~~:~-~-~-~~~~!_l_l
`c
`<c.
`.: • . '._<o'_<:_:l_L'>
`CC:
`Subject: RE: proposal
`on Cu-zeolites for NOx SCR
`09/14/2005 02:55
`PM
`
`Hi Stan,
`
`Here is the latest quote from him:
`Our DOE contact is
`"Clarifying the water-stability issue, without revealing proprietary
`knowledge, would be a good point to address in a new version. I have heard
`the same negative comment about the prospects for Cu-zeolites from several
`other investigators who presumably are also experts in this area. Thus, it
`is imperative to argue/present evidence that dispels such belief. More that
`the practicality of the concept, such as prospects for large-scale
`commercialization, the BES reviewers will be seeking for the rationale that
`will lead to new/corrected mechanistic understanding underlying such
`stability (or lack thereof)."
`
`Also, a quote from one of the reviewers was:
`"The structure-property-processing relationships that the PI's describe as
`the scientific goals are meritorious and worthy of support. The PI's weaken
`their position considerably, however, by emphasizing the technology of SCR
`
`Exhibit 2001.009
`
`

`
`EXHIBITS TO DECLARATION OF STANLEY ROTH, PH.D. UNDER 37 C.F.R. § 1.132
`
`in diesel vehicles when in fact propose to study de-NOx via ammonia over
`Cu-exchanged mordenite. Moreover, the PI's completely side step the issue
`of catalysts deactivation in the presence of water; I believe this to be
`the primary reason why metal-exchanged zeolites have limited application.
`It is interesting to note that not a single metal-zeolite for SCR was
`commercialized in the USA in the 1990'2 (see John Armor, App. Cat. A V222,
`page 4 0 7 ( 2 0 0 1 ) ) . "
`
`I think their major concern is instability of the zeolite, either due
`So,
`to dealumination or inactivation of the Cu. Any help you could provide
`would be greatly appreciated.
`t
`just gave me approval to
`include her latest results presented at DEER 2005 meeting, which helps
`greatly but doesn't specify the metal in the zeolite. So, if you could
`give me any info re. stability of Cu-exchanged zeolites, I would greatly
`appreciate it.
`
`Thanks very much!
`
`Jim
`
`James 111111111111111
`Professor
`Department of Chemical and Materials Engineering
`University
`
`~)
`
`(fax)
`
`-----Original Message-----
`From: Stan_Roth@engelhard.com [mailto:StaD~Roth@0Dgelnar0.com]
`Sent: Wednesday, September 14, 2005 11:34 AM
`To: James 111111111
`Subject: RE: proposal on Cu-zeolites for NOx SCR
`
`Jim,
`
`Is the issue one of your contact at DOE not understanding the fundamental
`hydrothermal stability of zeolites.
`If that is the case I can probably
`pull together some papers/patents that show zeolites can remain stable for
`HC adsorption or acid catalysis after being exposed to high temperatures.
`
`Or is the issue one of stability of Cu in the zeolite matrix, and its
`ability to retain SCR specific activity after exposure to high
`temperatures.
`
`I know some of the DOE people that have been
`Who is your DOE contact.
`involved in funding advanced combustion and catalyst programs.
`Specifically Gurpreet Singh and Kevin Stork.
`
`Regards,
`Stan
`
`Exhibit 2001.010
`
`

`
`EXHIBITS TO DECLARATION OF STANLEY ROTH, PH.D. UNDER 37 C.F.R. § 1.132
`
`JJEaEmBeBs~~~~llllll
`1
`-------------------------------------
`
`·r· .~~ •
`l. \...'
`,,
`
`_: ___ :_:~~~~'.:~>
`Subject: RE: proposal on
`Cu-zeolites for NOx SCR
`09/14/2005 12:45
`PM
`
`cc :
`
`Dear Stan,
`
`The information you present below would make ALL the difference between our
`receiving or not receiving a grant from DOE.
`Some reviewers, and my DOE
`grant manager, simply think Cu-exchanged zeolites are far to unstable to
`water to be commercially feasible, so they do not want to fund work in the
`area.
`
`One option would be for you to verbally share that information with my DOE
`grant officer, but ask him to keep it confidential.
`
`Another option is if I quote the information below but do not name the
`company, but inform the reviewers that DOE has been told.
`
`Please think about this, as without help from you or 111111111111111,
`officer thinks work in this area is useless.
`
`the DOE grant
`
`at 111111111111111, as she has shared
`I am also waiting to hear from
`some exciting data privately with our group, and I am hoping I will be
`allowed to include or refer to it.
`
`Best wishes,
`Jim
`
`James 111111!11!111!1
`Professor
`Department of Chemical and Materials Engineering
`University
`
`~)
`
`(fax)
`
`-----Original Message-----
`
`Exhibit 2001.011
`
`

`
`EXHIBITS TO DECLARATION OF STANLEY ROTH, PH.D. UNDER 37 C.F.R. § 1.132
`
`From: Stan_Roth@engelhard.com [rna :[ :Ltc·: ~:; t: an ___ Fc·t: (J (lenq':: Lha :: d. C':..n1]
`Sent: Wednesday, September 14, 2005 9:29 AM
`To: James 111111111
`Subject: Re: proposal on Cu-zeolites for NOx SCR
`
`Jim,
`
`Under laboratory aging conditions of air + steam we have SCR catalysts
`based on Cu-zeolite that have survived 50h at 800°C without significant
`loss in SCR activity and still exhibit >90% NOx conversion at inlet temp
`>300°C. At lower temperatues the performance drops due to oxidation of NO
`not due to thermal durability of the Cu-zeolite.
`
`This information is confidential to Engelhard and I am uncertain how to
`support your program without disclosure of our product performance. Such a
`catalyst will likely not be in commercial application until 2010.
`
`Is there any way to support your program without disclosure of confidential
`information?
`
`It sounds to me as if DOE has a reviewer who does not have much experience
`with zeolites.
`
`Regards,
`Stan
`
`~J~aEmileBs~~~~llllllll
`I
`-------------------------------------
`T ·~ .. :
`
`lllllllllllllllL.~~-~~-~:_>
`Subject: proposal on
`Cu-zeolites for NOx SCR
`09/06/2005 03:07
`PM
`
`cc:
`
`Dear Stan,
`
`I've been waiting to hear on my DOE proposal,
`I hope all is well with you.
`which was "wait-listed" and although it was close, it was finally not
`approved for funding. The major criticism from one reviewer (and echoed by
`
`Exhibit 2001.012
`
`

`
`EXHIBITS TO DECLARATION OF STANLEY ROTH, PH.D. UNDER 37 C.F.R. § 1.132
`
`the DOE grant monitor) is that Cu-exchanged zeoliteslack the hydrothermal
`stability needed to be commercially viable for SCR of NOxwith ammonia for
`diesel engines.
`
`I greatly appreciate the support letter you wrote for me last year, which
`was helpful, but due to proprietary issues it was not quite strong enough
`to address the reviewers concerns.
`
`DOE has encouraged me to resubmit the proposal in the next 1-2 weeks, if I
`can obtain stronger evidence of the hydrothermal stability of the
`zeolites.
`I am asking
`at 111111111111111 for help and to be able to
`include some of her data, but I would also greatly appreciate it if you
`again give me a letter of support, especially one that directly addresses
`the hydrothermal stability concerns.
`
`I very much want to continue work in this area, but without stronger
`evidence of hydrothermal stability I will not be able to address the
`reviewers concerns and obtain funding from DOE.
`So,
`I would greatly
`appreciate any help you can give, in the form of
`a modified letter from
`last year, and/or any data I can point to.
`
`Thanks very much.
`
`Sincerely,
`
`James 111111111111111111111111111
`
`Professor
`
`Department of Chemical and Materials Engineering
`
`llllllllllllllllllllllllllllllllllllllllllll!University
`
`Exhibit 2001.013
`
`

`
`EXHIBITS TO DECLARATION OF STANLEY ROTH, PH.D. UNDER 37 C.F.R. § 1.132
`
`(fax)
`
`Exhibit 2001.014