Inter Partes Reexamination No. 95/001,453
`Second Declaration of Ahmad Moini, Ph.D.
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`IN THE UNITED STATES PATENT AND TRADEMARK OFFICE
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`Examiner: DIAMOND, ALAND
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`Group Art Unit: 3991
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`Confirmation No: 2755
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`In Inter Partes Reexamination of:
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`BULLET AL.
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`Reexamination Control No. 95/001,453
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`Patent No. 7,601,662
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`Issued: October 13, 2009
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`For: COPPER CHA
`ZEOLITE CATALYSTS
`Mail Stop Inter Partes Reexam
`Central Reexamination Unit
`Commissioner for Patents
`P.O. Box 1450
`Alexandria, VA 22313-1450
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`SECOND DECLARATION OF AHMAD MOINI, PH.D., UNDER 37 C.F.R. § 1.132
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`I, Ahmad Moini, do declare and say as follows:
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`1. I am a Senior Research Associate for BASF Corporation, the successor in interest to
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`Engelhard Corporation and BASF Catalysts LLC (BASF), the owner of United States patent number
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`7,601,662 ("the '662 patent"). I received a B.S. in Chemistry from Eastern Washington University in
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`1982 and a Ph.D. in Chemistry from Texas A&M University in 1986. I have been a scientist at
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`BASF Corporation. I am a co-inventor of the subject matter described and claimed in the '662
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`patent.
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`2. I have been involved in heterogeneous catalyst research for more than 20 years, first as a
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`researcher at Mobil Research and Development Corporation, and later at BASF Corporation. I am a
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`named inventor on 33 granted United States patents, some of which pertain to zeolites for use as
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`automotive catalysts.
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`3. I submitted a first declaration in this matter on February 9, 2011. I have been asked to
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`conduct several experiments to compare the catalytic performance of the catalysts claimed in the
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`'662 to the performance of catalysts that have been considered the closest prior art in this
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`reexamination. I have reviewed the '662 patent, the Office Action dated November 16, 2010, the
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`Action Closing Prosecution dated November 18, 2011, including the documents cited in the actions,
`1
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`Exhibit 2011.001
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`

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`as well as additional documents cited in this second declaration. I have read Dr. Lercher's
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`Inter Partes Reexamination No. 95/001,453
`Second Declaration of Ahmad Moini, Ph.D.
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`declaration and Exhibit C-4.
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`Dedecek Samples
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`4.
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`It is my understanding that the Examiner finds that with respect to the rejections based on
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`Dedecek in view of Chung, the closest prior art is two examples from Dedecek, one being the natural
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`CuCHA zeolite having a Cu/Al atomic ratio of 0.38 (the sixth entry in Table 2 on page 66) and other
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`being the synthetic CuCHA zeolite having a Cu/Al atomic ratio of 0.32 (the eleventh entry in Table
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`2 on page 66). I have been asked to recreate these examples from the Dedecek reference.
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`Natural CHA Sample:
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`5. For the natural CuN atCHA example, the Dedecek reference started with natural chabazite
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`from North Korea having the chemical composition 63.89% Si02, 17.48% Ah03, 8.37% Fe20 3,
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`5.15% K20, 3.10% CaO, 1.21 %, MgO, 0.40% Ti02 and 0.39% Na20. However, due to import
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`restriction under the United States Department of Treasury Office of Foreign Assets Control, we are
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`not able to obtain natural chabazite samples from North Korea. Accordingly, I obtained a sample of
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`natural chabazite zeolite sample from a mine in Bowie, Arizona as an indirect comparison to the
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`CuN atCHA sample in Dedecek. The Bowie sample is comparable to the one from North Korea in
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`terms of the metal oxides content other than silica or alumina. The chemical composition of the
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`Bowie sample, determined by X-ray Fluorescence, was 64.74% Si02, 21.54% Ah03, 9.84% Na20,
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`1.37% Fe20 3,0.93% K20, 0.59% MgO, and other residual components. The primary phase of this
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`material was determined to be Chabazite, with secondary mineral phases present, as would be
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`expected by a natural material.
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`6. Per the example preparation in Dedecek, the CuNatCHA sample was equilibrated three times
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`with 0.5M NaCl (20 ml of solution per 1 g zeolite) for 2 hours, and a fourth was carried out
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`overnight. These equilibration times varied from Dedecek' s procedure, but it is understood that, with
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`this type of alkali equilibration, the key parameter is the number of exchanges rather than the total
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`exchange time. After the ion exchange, the Na-chabazite was washed with distilled water and dried
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`at room temperature. The powder from the NaCl treatment was subjected to two Cu acetate
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`treatments, under the same conditions described in Dedecek et al., Table 2, entry on row 6. The final
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`product was washed thoroughly with distilled deionized water. Elemental analysis revealed 65.13%
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`2
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`Exhibit 2011.002
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`Si02, 17.45% Ah03 , 8.91 % CuO, 4.52% Na20, 3.31 % Fe20 3 , 0.66% K20, 0.44% MgO. Based on
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`Inter Partes Reexamination No. 95/001,453
`Second Declaration of Ahmad Moini, Ph.D.
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`these data, the Cu/Al ratio was 0.32.
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`Synthetic sample:
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`7. A sample of synthetic Chabazite was synthesized according to the procedure referenced in
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`Dedecek et al. Zeolite Y (CBV-600) was mixed with KOH solution and reacted at 95°C for 92
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`hours. The resulting product was washed thoroughly with distilled deionized water. The formation
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`of Chabazite product was confirmed by XRD.
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`8. The chabazite powder was subjected to four NaCl equilibrations. The first three treatments
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`were for two hours, while the fourth was carried out overnight. These equilibration times varied
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`from Dedecek' s procedure, but it is understood that, with this type of alkali equilibration, the key
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`parameter is the number of exchanges rather than the total exchange time. The resulting powder
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`was washed thoroughly with distilled deionized water.
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`9. The powder from the NaCl treatment was subjected to two Cu acetate treatments, under the
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`same conditions described in Dedecek et al., Table 2, entry on row 11. The final product was
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`washed thoroughly with distilled deionized water. Elemental analysis revealed 58.47% Si02,
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`22.16% Ah03 , 11.4% CuO, 5.17% K20, 2.57% Na20. Based on these data, the Cu/Al ratio was
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`0.33.
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`NOx Conversion Testing:
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`10. The natural and synthetic samples made in accordance with paragraph 5-9 above were tested
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`for fresh and aged NOx conversion. Each catalyst sample was disposed on a 1 inch diameter X 3
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`inch long cellular ceramic core having a cell density of 400 cells per square inch and a wall thickness
`of 6 mil at a catalyst loading that was in the range of 2.28 and 2.52 g/in3
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`. They were then tested for
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`nitrogen oxides selective catalytic reduction efficiency and selectivity by adding a feed gas mixture
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`of 500 ppm of NO, 500 ppm of NH3 , 10% 0 2, 5% H20, balanced with N2 to a steady state reactor
`containing the catalyst core at a space velocity of 80,000 hr- 1 across a 150 °C to 460 °C temperature
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`range.
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`11. The samples were then hydrothermally aged at 850 °C for six hours. The samples were then
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`each tested again for NOx conversion using the same parameters as for fresh. A plot of the fresh and
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`3
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`Exhibit 2011.003
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`Inter Partes Reexamination No. 95/001,453
`Second Declaration of Ahmad Moini, Ph.D.
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`aged conversion is shown below for the natural chabazite:
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`100 -----------------------------------------------------------------------------------------------------------------------------------------------------,
`/
`-------
`I
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`90+--~~~~~~~~~~---=-~-------~~~~~
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`80+--------------------~--------1
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`~ 60 - r - - - - - - - - - - - - - - - - - - - - - - - - - - - - j
`0
`'iii
`~ 50 - r - - - - - - - - - - - - - - - - - - - - - - - - - - - - j
`g
`• 1-- Natural Chabazite, fresh I
`5 40 H-a- Natural Chabazite, aged c - - - - - - - - - - - - - - - - - - - - - j
`z
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`100
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`150
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`200
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`350
`300
`250
`Temperature (Deg C)
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`400
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`450
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`500
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`12. As shown in the plot, after aging, the NOx conversion of the natural chabazite was destroyed
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`across the entire temperature range. This material would not be a material of interest as an ammonia
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`SCR catalyst, as the fresh conversion is useless if the catalyst can not survive hydrothermal aging
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`and maintain high conversion over a temperature range of 200 to 450 °C. The excellent fresh and
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`aged performance of the catalyst claimed in the '662 patent is quite unexpected in comparison to
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`these results.
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`4
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`Exhibit 2011.004
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`Inter Partes Reexamination No. 95/001,453
`Second Declaration of Ahmad Moini, Ph.D.
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`13. A plot of the fresh and aged conversion of the synthetic sample prepared according to
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`paragraphs 7-9 is shown below:
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`100 .................................................................................................................................................. .
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`75~-~~~~~~~~~~~~----1---=-~s~yn~th-e~tic~C~h~ab-az~it-e,~fre-s~h
`-a- Synthetic Chabazite, aged
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`100
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`150
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`200
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`350
`300
`250
`Temperature (Deg C)
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`400
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`450
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`500
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`14. This material showed extremely poor fresh and aged conversion. Aging destroyed the NOx
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`conversion of the material. It should be noted that both the fresh and aged samples show negative
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`NOx conversion at approximately 450°C. Instead of converting NOx to nitrogen, these samples
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`produce NOx at these temperatures. This would not be a material of interest as an ammonia SCR
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`catalyst. The excellent fresh and aged performance of the catalyst claimed in the '662 patent is quite
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`unexpected in comparison to these results.
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`Zones Example 1
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`15. I have reviewed the Zones reference, which discloses only one working example. Examples
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`1-4 show synthesis of a SSZ-62 sample which was then calcined and underwent NH4 exchange, and
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`ultimately to the proton form, H+ -CHA with a silica to alumina ratio of 22.
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`16. I located data for an H+-CHA sample that was tested for NOx conversion using ammonia
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`SCR. The testing was performed by disposing the catalyst on a 1 inch diameter X 3 inch long
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`cellular ceramic core having a cell density of 400 cells per square inch and a wall thickness of 6 mil
`at a catalyst loading of 2.13 g/in3
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`.
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`17. The sample was tested for nitrogen oxides selective catalytic reduction efficiency and
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`selectivity by adding a feed gas mixture of 500 ppm of NO, 500 ppm of NH3 , 10% 0 2, 5% H20,
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`balanced with N2 to a steady state reactor containing the catalyst core at a space velocity of 80,000
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`5
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`Exhibit 2011.005
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`hr- 1 across a 190 °C to 600 °C temperature range. A plot of the NOx (solid line) and NH3 (dashed
`line) conversion is shown below:
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`Inter Partes Reexamination No. 95/001,453
`Second Declaration of Ahmad Moini, Ph.D.
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`100
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`90
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`80
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`70
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`60
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`~
`9.......
`> 50
`c
`0
`0
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`40
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`30
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`20
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`10
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`0
`1 00
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`I-NO Conv. [%]
`1- NH3 Conv. [%]
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`I
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`/ / /
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`//
`/y
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`---=----- ....- -
`- ~
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`1 50
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`200
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`250
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`300
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`350
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`400
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`450
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`500
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`550
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`600
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`temperature [ 0C]
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`18. The catalyst exhibited essentially no fresh NOx conversion until about 475 °C. As the
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`catalyst exhibited no fresh NOx conversion in the temperature range of interest, the sample was not
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`aged and tested, as doing so would be pointless. The excellent fresh and aged performance of the
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`catalyst claimed in the '662 patent is quite unexpected in comparison to these results.
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`Yuen Example 3
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`19. The sample prepared in accordance with the Zones reference would also be representative of
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`Example 3 in Yuen and a suitable indirect comparison of Example 3 of Yuen. In fact, conversion of
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`the H+ form in the Yuen example would be expected to perform worse than Zones, because the silica
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`to alumina ratio in Yuen is very high, and at a silica to alumina ratio of 166 versus 30 for the sample
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`tested, lower NOx conversion would be expected.
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`Hydrocarbon SCR Testing
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`20. I was asked to provide data pertaining to hydrocarbon SCR for Cu-SAP0-34 and/or Cu-SSZ-
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`13 samples. One of my colleagues provided data from a separate research program for HC SCR for
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`6
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`Exhibit 2011.006
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`

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`Inter Partes Reexamination No. 95/001,453
`Second Declaration of Ahmad Moini, Ph.D.
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`hydrocarbon SCR using Cu-SAP0-34 for pellet samples run in a microreactor at a space velocity of
`40,000-50,000 hr- 1
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`It has been my experience that use of hydrocarbon SCR data on a material is
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`.
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`irrelevant to predict ammonia SCR behavior on the same material. Different hydrocarbon reductants
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`behave differently on the same material. The Halasz article, attached as Exhibit C-4 to Dr. Lercher' s
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`declaration, is irrelevant to the '662 invention because there is no hydrothermal aging data. It is an
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`overgeneralization to conclude from Halasz that if a catalyst worked with one reductant, it would
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`work with a different reductant. Halasz only tests ammonia at 573 K, which is above the low
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`temperature region of interest in the '662 patent. Propane and propene had significantly different
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`performance as reductants over the same catalyst. Three sample runs were performed using
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`propylene reductant, a simulated gasoline exhaust gas reductant (containing 41.3 % isooctane; 38 %
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`m-xylene; 11.4% 1-octene; 9.3% n-octane) and a simulated diesel exhaust gas reductant (containing
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`37.8% m-xylene; and 62.2% n-octane). Propylene reductant is only of academic interest because
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`hydrocarbon SCR is viewed as an attractive option when a hydrocarbon gas on-board the vehicle can
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`be used as a reductant. Propylene would require an additional reservoir and injector. Thus, samples
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`tested with the simulated diesel and gasoline exhaust are of much greater interest as real world
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`examples of reductants. Samples were tested as fresh and aged at temperatures of 700 °C and 800
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`°C for different Cu-SAP0-34 samples, as compared to Cu-ZSM-5. The best results for a Cu-SAP0-
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`34 sample, with 4.37% CuO, appear in paragraphs 21-23. For these data, the negative conversion
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`values shown are simply an artifact of the very low NOx conversions, which are calculated from
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`inlet and outlet NOx values.
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`21. For propylene, the conversions were as follows:
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`200 °CFresh
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`400 °C Fresh
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`Cu-ZSM-5
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`Cu-SAP0-34
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`-7.4%
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`5.9%
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`39.8%
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`3.2%
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`22. For simulated gasoline, the conversions were as follows:
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`200 °CFresh
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`400 °C Fresh
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`Cu-ZSM-5
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`Cu-SAP0-34
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`-0.8%
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`6.2%
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`32.9%
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`-1.9%
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`23. For simulated diesel, the conversions were as follows:
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`200 °CFresh
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`400 °C Fresh
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`Cu-ZSM-5
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`-2.9%
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`40.5
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`7
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`Exhibit 2011.007
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`

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`Inter Partes Reexamination No. 95/001,453
`Second Declaration of Ahmad Moini, Ph.D.
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`Cu-SAP0-34
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`0.4%
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`-1.5
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`24. For the aged samples, the performance for SAP0-34 was worse for simulated gasoline and
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`diesel, with the exception of one sample that had 2% conversion at 400 °C for simulated gasoline.
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`The catalytic activity in terms of NOx conversions for Cu-SAP0-34 using simulated gasoline and
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`diesel reductants was so poor, these materials were not pursued as commercial catalysts.
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`Further Examples in Accordance with the '662 patent
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`25. I was asked to provide additional Examples representative of the '662 invention. I obtained
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`the following data from a colleague, from a study pertaining to various silica to alumina mole ratio
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`aluminosilicate zeolites and containing varying ratios of Cu/ Al. The samples were prepared
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`similarly to the Examples in the '662 patent All zeolites samples were calcined and ammonium
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`exchanged to reduce Na content to levels typically lower than 0.01 wt% Na20. The ammonium
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`form was then copper exchanged in an aqueous solution of copper acetate to provide the reported
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`compositions. Samples were prepared into pellets 0.5 to 1 mm long by 2 mm in diameter. Samples
`were aged in 10% H20, 10% 0 2, balance N2 at a space velocity of 12,500 h- 1 for 6 hours at 850 ° C.
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`This study involved only hydrothermally aged NOx conversion, which is the parameter of interest to
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`BASF's customers. An inlet gas mixture was formed containing 500 ppm NO, 500 ppm NH3 , 10%
`0 2, 5 % H20 and balance He at a space velocity of 80,000 h- 1
`200 °C and 450 °C.
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`. NOx conversion was measured at
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`Silica/ Alumina
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`Cu/Al Aged NOx conversion 200 °C
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`450 °C
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`Sample 1 14.4
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`Sample 2 18.2
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`Sample 3 24.2
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`Sample 4 49.2
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`0.24
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`0.25
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`0.27
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`0.32
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`9%
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`68%
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`70%
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`56%
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`57%
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`75%
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`80%
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`63%
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`The data above shows that at just below the claimed silica to alumina ratio, aged NOx conversion at
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`200 °C was unacceptably low. For the sample 2, the aged conversion improved. Sample 4 showed
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`lower conversion than samples 2 and 3. Additional experiments with varying Cu/Al ratio and
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`exchange conditions was not conducted, but Sample 4 could be optimized with further
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`experimentation.
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`8
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`Exhibit 2011.008
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`

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`Inter Partes Reexamination No. 95/001,453
`Second Declaration of Ahmad Moini, Ph.D.
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`I hereby declare that all statements made herein of my own knowledge are true and that all
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`statements made herein on information and belief are believed to be true; and further that these
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`statements were made with the knowledge that willful false statements and the like so made are
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`punishable by fine or imprisonment, or both, under Section 1001 of Title 18 of the United States
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`Code, and that such willful false statements may jeopardize the validity of the above-identified
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`patent.
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`Dated: December 18, 2011
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`By:
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`Ahmad Moini, Ph.D.
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`Respectfully submitted,
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`9
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`Exhibit 2011.009