Notice of Pre-AIA or AIA Status
The present application, filed on or after March 16, 2013, is being examined under the first inventor to file provisions of the AIA .
Detailed Action
This office action is in response to applicant’s communication filed on 7/2/26. Claims 1-16 and 18-20 are pending. Claims 3, 5-13 and 18-20 remain withdrawn from further consideration. As a result, claims 1-2, 4 and 14-16 are being examined in this Office Action.
Upon further consideration, the 103 rejection over Wulff et al. in view of Lee et al. is withdrawn. However, based on a new search, a new 103 rejection is set forth below.
Objections
Claims 1 and 2 are objected to because of the following informalities:
Claim 1 is objected to because of informal wording. After “as measured by NH3-TPD test,” claim 1 recites a series of clauses that are joined only by commas, without a linking word such as “wherein.” Also, amended claim 1 recites “an optional metallic element,” and then recites “the metallic element is one or more selected from,” without stating that this clause applies only when the metallic element is present. The examiner suggests the following wording: “…as measured by NH3-TPD test, wherein the carrier comprises a matrix and a doping element, wherein the doping element comprises a non-metallic element and optionally a metallic element and does not include sodium or chlorine, wherein the metallic element, when present, is one or more selected from …, and wherein the non-metallic element is one or more selected from ….”
Claim 2 is objected to for a similar reason. Claim 2 joins the clause “the second carrier component is one or more selected from diatomite and titania” with a comma only. The examiner suggests “…, and the second carrier component, when present, is one or more selected from diatomite and titania.” Appropriate correction is required.
Claim Rejections – 35 USC 103
In the event the determination of the status of the application as subject to AIA 35 U.S.C. 102 and 103 (or as subject to pre-AIA 35 U.S.C. 102 and 103) is incorrect, any correction of the statutory basis for the rejection will not be considered a new ground of rejection if the prior art relied upon, and the rationale supporting the rejection, would be the same under either status.
The following is a quotation of 35 U.S.C. 103 which forms the basis for all obviousness rejections set forth in this Office action:
A patent for a claimed invention may not be obtained, notwithstanding that the claimed invention is not identically disclosed as set forth in section 102 of this title, if the differences between the claimed invention and the prior art are such that the claimed invention as a whole would have been obvious before the effective filing date of the claimed invention to a person having ordinary skill in the art to which the claimed invention pertains. Patentability shall not be negated by the manner in which the invention was made.
The factual inquiries for establishing a background for determining obviousness under 35 U.S.C. 103 are summarized as follows:
1. Determining the scope and contents of the prior art.
2. Ascertaining the differences between the prior art and the claims at issue.
3. Resolving the level of ordinary skill in the pertinent art.
4. Considering objective evidence present in the application indicating obviousness or nonobviousness.
This application currently names joint inventors. In considering patentability of the claims the examiner presumes that the subject matter of the various claims was commonly owned as of the effective filing date of the claimed invention(s) absent any evidence to the contrary. Applicant is advised of the obligation under 37 CFR 1.56 to point out the inventor and effective filing dates of each claim that was not commonly owned as of the effective filing date of the later invention in order for the examiner to consider the applicability of 35 U.S.C. 102(b)(2)(C) for any potential 35 U.S.C. 102(a)(2) prior art against the later invention.
Claims 1-2, 4 and 14-16 are rejected under 35 U.S.C. 103 as being unpatentable over Wulff-Doring et al. (referred to as Wulff et al. herein) (US 5916838, pub date June 29, 1999), in view of Verhaak et al. (“The selective hydrogenation of acetonitrile on supported nickel catalysts,” Catal. Lett. 1994, 26, 37-53).
Determination of the Scope and Content of the Prior Art
(MPEP §2141.01)
Wulff et al. teaches catalysts for the amination of alkylene oxides, alcohols, aldehydes and ketones with ammonia or primary or secondary amines, to give organic amines. For example, Wulff et al. aminates monoethanolamine with ammonia to give ethylenediamine. (Wulff et al., abstract; column 4, lines 13-21)
Wulff et al. teaches that cobalt, nickel or a mixture thereof (0.1-6% by weight), ruthenium (0.001-25% by weight) and copper (0-10% by weight) are applied to a porous metal oxide carrier. The carrier is selected from alumina, aluminosilicates, titanium dioxide, zirconium dioxide, magnesium oxide and mixtures thereof. Carriers that consist of alumina are particularly preferred. (Wulff et al., column 2, lines 5-26)
Wulff et al. further teaches that 0-5% by weight of promoters may also be present on the carrier. The promoters are selected from a list that includes lithium, potassium, rubidium, cesium, phosphorus, and mixtures thereof. Wulff et al. teaches that by doping the catalyst carriers with these promoters, the selectivity of the catalyst can be controlled. The promoter content is preferably 0.001-5%, in particular 0.01-3%, by weight. (Wulff et al., column 2, lines 26-42) Phosphorus is a Group VA non-metallic element. Lithium, potassium, rubidium and cesium are Group IA metal elements. Sodium is only one optional member of the promoter list. Thus, Wulff et al. does not require sodium.
Wulff et al. teaches that the carrier is preferably not impregnated with halide compounds, and that the catalyst is preferably halogen-free, in particular with no chlorides. Wulff et al. teaches that impregnation with hydrochloric acid can lead to poorer mechanical properties, and that chlorides can lead to corrosion problems. (Wulff et al., column 3, lines 4-9 and 18-32)
Wulff et al. exemplifies a catalyst made by impregnating alumina extrudates with nickel, cobalt and copper nitrates, and then with a ruthenium nitrate solution. The catalyst contains 2% by weight of ruthenium, 0.79% by weight of nickel, 0.79% by weight of cobalt and 1.6% by weight of copper on alumina. No halide or sodium compound is used. (Wulff et al., Example 4, column 7, lines 32-47)
Wulff et al. seeks amination catalysts with high selectivity to ethylenediamine in the amination of monoethanolamine with ammonia, which also gives aminoethylethanolamine, diethylenetriamine and piperazine. Wulff et al. teaches that its catalysts give higher activity with regard to the formation of primary amination products, and a high yield of ethylenediamine owing to their high selectivity. (Wulff et al., column 1, lines 48-54; column 4, lines 21-27 and 47-50; column 6, lines 43-46)
Verhaak et al. teaches nickel catalysts on inorganic oxide supports, including alumina, aluminosilicate, aluminophosphate, silica and magnesia, used to make amines by hydrogenation. Verhaak et al. teaches that the selectivity of the process is greatly influenced by the nature of the support. Nickel on acidic supports forms the condensation products, diethyl- and triethylamine, while nickel on basic supports is highly selective to the primary amine, ethylamine. (Verhaak et al., abstract; pages 38-39)
Verhaak et al. teaches that the acidity of the catalysts was quantified by temperature-programmed desorption of ammonia (NH3-TPD) in the authors’ earlier work (reference [9]). Verhaak et al. teaches a linear relation between catalyst acidity, as measured by the desorption of NH3, and the selectivity to the primary amine. Verhaak et al. further teaches that the acidity of the catalyst is directly responsible for the condensation reactions that lead to secondary and tertiary amines, and that this acid function is located on the support. (Verhaak et al., abstract; page 38; page 49, Figure 7)
Verhaak et al. teaches that the acidity of an alumina-based support can be modified by covering its acidic sites with increasing amounts of potassium, and that sodium also raises the selectivity to the primary amine. However, Verhaak et al. also teaches that high potassium loadings lower the activity of the catalyst, and that more than 3 wt% potassium “overpromoted the catalyst, leading to a drop in the ethylamine yields.” (Verhaak et al., pages 45-48, Figures 4-6)
Verhaak et al. concludes that “[w]hen the active (transition) metal has been selected, the support can therefore be used to optimize the selectivities.” Verhaak et al. further teaches that “[b]ecause the acidity of the supported nickel catalysts is determined by the properties of the support, modification of the support creates a means to manipulate its acidity.” (Verhaak et al., pages 51-52) Verhaak et al. also teaches that an aluminophosphate support is the most acidic support tested. (Verhaak et al., pages 38 and 45)
Ascertainment of the Difference Between the Scope of the Prior Art and the Claims
(MPEP §2141.02)
Wulff et al. is deficient in the sense that it does not expressly teach a carrier having an ammonia adsorption capacity of 0.25 to 0.65 mmol/g, as measured by NH3-TPD test. Wulff et al. also does not exemplify a carrier doped with phosphorus.
Verhaak et al. cures this deficiency. Verhaak et al. teaches that the acidity of a supported metal catalyst, as measured by NH3-TPD, controls the selectivity to primary amines versus secondary and tertiary amines. Verhaak et al. also teaches that this acidity is determined by the support, and that it can be adjusted by the type and amount of promoter on an alumina-based support. (Verhaak et al., pages 45-49 and 51-52) Thus, Verhaak et al. teaches that the acidity set by the carrier, as measured by NH3-TPD, is a result-effective variable.
Finding of Prima Facie Obviousness Rationale and Motivation
(MPEP §2142-2143)
Therefore, it would be prima facie obvious to one of ordinary skill in the art at the time of the invention to dope Wulff et al.’s alumina carrier with phosphorus, since Wulff et al. names phosphorus as one of the promoters that may be doped into its carrier, at 0.001-5% by weight, to control the selectivity of the catalyst. Selecting one promoter from Wulff et al.’s list is the use of a known element for its known purpose. The phosphorus-doped alumina carrier comprises a matrix (alumina) and a doping element that comprises a non-metallic element (phosphorus).
Since Wulff et al. teaches that the catalyst is preferably halogen-free, in particular with no chlorides, it would be obvious for the doping element not to include chlorine, in order to avoid corrosion problems and to maintain mechanical properties. Since sodium is only an optional promoter in Wulff et al., it would also be obvious for the doping element not to include sodium.
Additionally, it would be prima facie obvious to one of ordinary skill in the art at the time of the invention to optimize the ammonia adsorption capacity of Wulff et al.’s doped carrier to fall within the claimed range of 0.25 to 0.65 mmol/g, in view of Verhaak et al. Both references are directed to supported Group VIII metal catalysts that make amines in the presence of hydrogen. Both references seek high selectivity to the primary amine product and low formation of secondary amine products. Wulff et al. seeks high selectivity to ethylenediamine over aminoethylethanolamine, diethylenetriamine and piperazine. (Wulff et al., column 1, lines 48-54; column 4, lines 47-50) Verhaak et al. seeks high selectivity to ethylamine over diethylamine and triethylamine. (Verhaak et al., pages 38 and 45)
Verhaak et al. teaches that the acidity of the catalyst, as measured by NH3-TPD, controls this selectivity, and that this acidity is determined by the support. Verhaak et al. also teaches that an aluminophosphate support is highly acidic, and that the alkali metal potassium lowers the acidity of alumina-based supports. Wulff et al. already teaches that doping the carrier with promoters controls selectivity, and Wulff et al.’s promoter list includes phosphorus and the alkali metals lithium, potassium, rubidium and cesium, and mixtures thereof. Wulff et al. uses phosphorus only as a dopant, at 0.001-5% by weight, and not as a bulk aluminophosphate support.
Thus, one of ordinary skill in the art would have been motivated to keep Wulff et al.’s phosphorus dopant, which Wulff et al. teaches controls selectivity, and to use it together with an alkali metal promoter such as potassium, to adjust the amounts of these promoters doped into Wulff et al.’s carrier, and to measure the resulting NH3-TPD acidity as taught by Verhaak et al., in order to raise the selectivity to the primary amine. Potassium is a Group IA metal, which is within claim 1’s optional metallic element. Verhaak et al. also teaches that too much promoter lowers the activity and the yield, so the amount would be optimized. Since the art recognizes the acidity set by the carrier, as measured by NH3-TPD, as a result-effective variable, the claimed range would have been reached through routine experimentation. See In re Aller, 220 F.2d 454, 105 USPQ 233 (CCPA 1955); MPEP 2144.05(II). The applicant does not show any unusual and/or unexpected results for this range, as discussed in the Response to Arguments below. Note that the prior art provides the same effect desired by the applicant, an amination catalyst with good product selectivity and stability.
With regard to claim 2, Wulff et al. teaches a carrier that consists of alumina, and also teaches aluminosilicates and titanium dioxide. (Wulff et al., column 2, lines 5-11) The second carrier component of claim 2 is optional.
With regard to claim 4, Wulff et al. teaches 0.1-6% by weight of cobalt and/or nickel and 0.001-25% by weight of ruthenium, which are Group VIII metals. (Wulff et al., column 2, lines 12-23) For example, 6% by weight of cobalt on alumina is about 6.4 g of cobalt per 100 g of alumina. These ranges overlap the claimed range of 5 g to 46 g of active metal per 100 g of the matrix. In the case where the claimed ranges overlap or lie inside ranges disclosed by the prior art, a prima facie case of obviousness exists. In re Wertheim, 541 F.2d 257, 191 USPQ 90 (CCPA 1976); MPEP 2144.05(I).
Further, claim 1 recites that the active metal component comprises at least one metal selected from Group VIII and Group IB metals. Thus, under the broadest reasonable interpretation, copper, a Group IB metal, is part of the active metal component. Wulff et al.’s Example 4 catalyst contains 2% ruthenium, 0.79% nickel, 0.79% cobalt and 1.6% copper, by weight, on alumina. This is 5.18% by weight of active metal, or about 5.5 g per 100 g of alumina, which is within the claimed range. (Wulff et al., column 7, lines 32-47)
With regard to claims 14 and 15, Wulff et al. teaches cobalt, nickel or a mixture thereof as the active metal, and also teaches copper. (Wulff et al., column 2, lines 12-26)
With regard to claim 16, the narrower range of 0.3 to 0.6 mmol/g would have been obvious for the same reasons discussed above for claim 1, since Verhaak et al. teaches that the acidity set by the carrier, as measured by NH3-TPD, is a result-effective variable.
Double Patenting
The nonstatutory double patenting rejection is based on a judicially created doctrine grounded in public policy (a policy reflected in the statute) so as to prevent the unjustified or improper timewise extension of the "right to exclude" granted by a patent and to prevent possible harassment by multiple assignees. See In re Goodman, 11 F.3d 1046, 29 USPQ2d 2010 (Fed. Cir. 1993); In re Longi, 759 F.2d 887, 225 USPQ 645 (Fed. Cir. 1985); In re Van Ornum, 686 F.2d 937, 214 USPQ 761 (CCPA 1982); In re Vogel, 422 F.2d 438, 164 USPQ 619 (CCPA 1970); and In re Thorington, 418 F.2d 528, 163 USPQ 644 (CCPA 1969).
A timely filed terminal disclaimer in compliance with 37 CFR 1.321(c) may be used to overcome an actual or provisional rejection based on a nonstatutory double patenting ground provided the conflicting application or patent is shown to be commonly owned with this application. See 37 CFR 1.130(b).
Effective January 1, 1994, a registered attorney or agent of record may sign a terminal disclaimer. A terminal disclaimer signed by the assignee must fully comply with 37 CFR 3.73(b).
The USPTO internet Web site contains terminal disclaimer forms which may be used. Please visit http://www.uspto.gov/forms/. The filing date of the application will determine what form should be used. A web-based eTerminal Disclaimer may be filled out completely online using web-screens. An eTerminal Disclaimer that meets all requirements is auto-processed and approved immediately upon submission. For more information about eTerminal Disclaimers, refer to http://www.uspto.gov/patents/process/file/efs/guidance/eTD-info-I.jsp.
Claims 1-2, 4 and 16 are provisionally rejected on the ground of nonstatutory obviousness-type double patenting as being unpatentable over claims 1 and 3-4 of copending Application No. 18034101.
The instant claims are directed to a catalyst useful for producing organic amines by catalytic amination, comprising an inorganic porous carrier containing aluminium and/or silicon and a Group VIII or Group IB active metal supported on the carrier. The carrier comprises a matrix and a doping element that comprises a non-metallic element and does not include sodium or chlorine. The carrier has an ammonia adsorption capacity of 0.25 to 0.65 mmol/g, as measured by NH3-TPD test.
Although the claims at issue are not identical, they are not patentably distinct from each other because claim 1 of copending Application No. 18034101 is directed to the same catalyst. Claim 1 of Application No. 18034101 recites a catalyst useful for producing organic amines by catalytic amination, comprising an inorganic porous carrier containing aluminium and/or silicon and a Group VIII or Group IB active metal supported on the carrier, wherein the carrier comprises a matrix and a doping element.
In claim 1 of Application No. 18034101, the doping element is selected from Group IIIA, Group VA, Group VIA and Group VIIA non-metallic elements, excluding chlorine. Thus, this doping element comprises a non-metallic element, and it does not include chlorine or sodium. The optional metallic element of instant claim 1 is not required.
Claim 3 of Application No. 18034101 further recites, as one of its listed characteristics, that the carrier has an ammonia adsorption capacity of 0.3 to 0.6 mmol/g. The specification of Application No. 18034101 states that this capacity is measured by NH3-TPD test. (Specification of Application No. 18034101, page 4, line 16-18) This range lies inside the range of instant claim 1 (0.25 to 0.65 mmol/g), and is the same as the range of instant claim 16 (0.3 to 0.6 mmol/g).
Claim 1 of Application No. 18034101 also recites that the carrier has a Lewis acid content of 85% or more. However, instant claim 1 uses the open term “comprising,” and does not exclude this feature. Thus, the catalyst of claim 1 of Application No. 18034101, having the ammonia adsorption capacity recited as an alternative in claim 3, is a species that falls within the scope of instant claims 1 and 16. A genus claim is anticipated by, and therefore not patentably distinct from, a species claim that falls within it.
With regard to instant claim 2, claim 1 of Application No. 18034101 recites a matrix selected from alumina, silica, molecular sieves, diatomite and aluminosilicates. Selecting alumina, silica, molecular sieves or aluminosilicates from this short list would have been obvious.
With regard to instant claim 4, claim 4 of Application No. 18034101 recites 15 to 37 g of active metal per 100 g of the matrix. This range lies inside the instant range of 5 to 46 g per 100 g of the matrix. It would have been obvious to use the metal amount of claim 4 with the ammonia adsorption capacity of claim 3, since both claims further define the same catalyst of claim 1 of Application No. 18034101.
Accordingly, instant claims 1-2, 4 and 16 are not patentably distinct from claims 1 and 3-4 of copending Application No. 18034101.
This is a provisional obviousness-type double patenting rejection, because the conflicting claims have not in fact been patented.
Claims 14 and 15 are provisionally rejected on the ground of nonstatutory obviousness-type double patenting as being unpatentable over claims 1 and 3 of copending Application No. 18034101, in view of Wulff-Doring et al. (referred to as Wulff et al. herein) (US 5916838, pub date June 29, 1999).
The teachings of Wulff et al. have been discussed previously within this office action.
Instant claims 14 and 15 are directed to the catalyst of instant claim 1, wherein the active metal comprises cobalt and/or nickel (claim 14 also recites palladium and copper).
Claims 1 and 3 of Application No. 18034101 are discussed above. Claims 1 and 3 of Application No. 18034101 recite a Group VIII or Group IB active metal, but do not recite cobalt or nickel. Wulff et al. teaches cobalt, nickel or a mixture thereof as the active metal of an amination catalyst on an alumina carrier. (Wulff et al., column 2, lines 5-19; column 4, lines 13-21)
Thus, it would have been obvious to use cobalt and/or nickel as the Group VIII active metal of claim 1 of Application No. 18034101, since Wulff et al. teaches that these metals are suitable for the same purpose, the amination of alcohols with ammonia.
Accordingly, instant claims 14 and 15 are not patentably distinct from claims 1 and 3 of copending Application No. 18034101 when viewed in light of Wulff et al.
This is a provisional obviousness-type double patenting rejection, because the conflicting claims have not in fact been patented.
Response to Arguments
Applicant’s arguments filed 7/2/26 have been considered. Applicant’s arguments directed to Lee et al. are moot, since the new ground of rejection does not rely on Lee et al. The remaining arguments are not persuasive for the following reasons:
The examiner acknowledges applicant’s argument that all of the promoters disclosed by Wulff et al. are metallic elements, and thus Wulff et al. fails to disclose a non-metallic doping element.
The examiner responds by stating that this is not correct. Wulff et al.’s promoter list includes phosphorus. (Wulff et al., column 2, lines 26-32) Phosphorus is a non-metallic element. Applicant’s own specification lists phosphorus as a non-metallic doping element. (Specification, paragraph [0032]) Thus, Wulff et al. teaches a non-metallic element that may be doped into the carrier to control selectivity.
Reference to applicant’s specification refers to applicant’s PGPub: US 20230390747
The examiner acknowledges applicant’s argument that Table III-2 of the specification shows unexpected results for carriers with an ammonia adsorption capacity of 0.25 to 0.65 mmol/g.
The examiner responds by stating that the data are not persuasive, for the following reasons.
First, the comparative examples do not isolate the ammonia adsorption capacity. Comparative Examples III-1 and III-2 have no non-metallic doping element (calcium only). They also change the metal promoters of the examples they were made from (Examples III-6 and III-9). Comparative Example III-3 uses iron in place of zinc, and much more sulfur (4.25 g versus 0.79 g), than Example III-2. (Specification, paragraphs [0487]-[0489]; Table III-1) Thus, more than one variable changes at the same time.
Second, Example III-12 was made in the same way as Example III-6, except that the pseudo-boehmite powder was undoped. Thus, the Example III-12 carrier lacks the boron of Example III-6 (calcium only). (Specification, paragraph [0486]; Table III-1) Both carriers are within the claimed range (0.28 mmol/g for Example III-12 and 0.44 mmol/g for Example III-6). However, Example III-12 gives only 74.2% conversion and 36.3% hexanediamine selectivity, versus 88.1% and 47.8% for the boron-doped Example III-6. (Specification, Tables III-1 and III-2) Example III-12 is also well below all of the doped Examples III-1 to III-11 (84.9-91.8% conversion). Thus, much of the improvement tracks the non-metallic doping element, and the data do not show that the claimed ammonia adsorption range, by itself, gives the improved results.
Third, the data are not commensurate in scope with the claims. Claim 1 covers any Group VIII or Group IB metal, any carrier containing aluminum and/or silicon, and any non-metallic element from four groups of the periodic table, in any amount. The data show a small number of specific catalysts, tested in one reaction (amination of 1,6-hexanediol) under one set of conditions. See MPEP 716.02(d).
Fourth, an optimum is expected. Verhaak et al. teaches that the amount of promoter on an alumina-based support has an optimum. Low loadings leave the catalyst more acidic and less selective to the primary amine, while loadings above 3 wt% potassium lower the yield. (Verhaak et al., pages 45-48, Figures 4-6) Thus, finding an optimum range for a modified carrier would have been expected, not unexpected. See MPEP 716.02(c).
The examiner acknowledges applicant’s argument that Lee et al. fails to teach or suggest controlling the ammonia adsorption within the claimed range, and that the rejection relies on hindsight.
The examiner responds by stating that this argument is moot as to Lee et al., since the new rejection does not rely on Lee et al. Further, Verhaak et al. teaches that the acidity of the catalyst, as measured by NH3-TPD, controls the selectivity to primary amines, that this acidity is determined by the support, and that it can be adjusted by the type and amount of promoter on the support. (Verhaak et al., pages 45-52) Thus, the reason to optimize the ammonia adsorption capacity of the carrier comes from the prior art, not from applicant’s disclosure.
Conclusion
No claims are allowed.
Any inquiry concerning this communication or earlier communications from the examiner should be directed to Jennifer Cho Sawyer whose telephone number is (571) 270 1690. The examiner can normally be reached on Monday-Friday 9 AM - 6 PM PST.
If attempts to reach the examiner by telephone are unsuccessful, the examiner's supervisor, Renee Claytor can be reached on (571) 272-8394. The fax phone number for the organization where this application or proceeding is assigned is 571-274-1690.
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/JENNIFER C SAWYER/Examiner, Art Unit 1691
/RENEE CLAYTOR/ Supervisory Patent Examiner, Art Unit 1691
