DETAILED ACTION
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 .
Claim Rejections - 35 USC § 112
The following is a quotation of 35 U.S.C. 112(b):
(b) CONCLUSION.—The specification shall conclude with one or more claims particularly pointing out and distinctly claiming the subject matter which the inventor or a joint inventor regards as the invention.
The following is a quotation of 35 U.S.C. 112 (pre-AIA ), second paragraph:
The specification shall conclude with one or more claims particularly pointing out and distinctly claiming the subject matter which the applicant regards as his invention.
Claims 1-17 rejected under 35 U.S.C. 112(b) or 35 U.S.C. 112 (pre-AIA ), second paragraph, as being indefinite for failing to particularly point out and distinctly claim the subject matter which the inventor or a joint inventor (or for applications subject to pre-AIA 35 U.S.C. 112, the applicant), regards as the invention.
Claim 1 recites, in relevant part, “wherein the support is a monolith in the form of a powder, in the form of a granular material, or in the form of shaped bodies.” This limitation is indefinite because it is internally inconsistent and renders the metes and bounds of the claim unclear. The term “monolith” ordinarily denotes a single block or unitary body, whereas “powder,” “granular material,” and “shaped bodies” denote different physical forms of the support. As presently written, the claim appears to require the support to be a monolith that is also in the form of a powder, granular material, or shaped bodies.
It is therefore unclear whether Applicant intends to claim a monolithic support, a powdered support, a granular support, shaped support bodies, or any of these alternative support forms. Because the physical form of the support is a material limitation of the claimed hydroformylation process, the above wording does not reasonably apprise one of ordinary skill in the art of the scope of the claimed invention.
Claims 2–17 are rejected for the same reason because they depend, directly or indirectly, from claim 1 and therefore incorporate the indefinite limitation of claim 1.
Claim 4 is further rejected under 35 U.S.C. § 112(b) as being indefinite. Claim 4 depends from claim 3 and recites that “the synthesis gas feed rate is already reduced in b).” The phrase “already reduced” is unclear because the claim does not identify the reference point from which the synthesis gas feed rate has been reduced. Claim 3 recites reducing pressure after and/or during the lowering of temperature in step b), but does not recite increasing or otherwise establishing a synthesis gas feed rate from which a later reduction can be measured. It is therefore unclear whether claim 4 requires reducing the synthesis gas feed rate relative to the normal hydroformylation feed rate, relative to a previously increased synthesis gas feed rate, relative to the feed rate at the beginning of step b), or relative to some other unspecified operating condition.
Appropriate correction may include amending claim 1 to recite that “the support is a monolith, is in the form of a powder, is in the form of a granular material, or is in the form of shaped bodies,” if such alternative support forms are intended. Claim 4 may be clarified by reciting the specific point at which the synthesis gas feed rate is reduced and the reference feed rate from which the reduction is measured, or by amending the dependency if claim 4 is intended to refer back to the increased synthesis gas feed rate recited in claim 2.
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 (i.e., changing from AIA to pre-AIA ) 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, 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.
Claims 1–17 are rejected under 35 U.S.C. § 103 as being unpatentable over Haßelberg et al. (US 11,384,042; hereinafter “US’042”) in view of Paul (US 4,151,209; hereinafter “US’209”) and further in view of Peterson et al. (US 7,446,231; hereinafter “US’231”).
As to claim 1, US’042 teaches a process for hydroformylating C2 to C8 olefins in a reaction zone using a heterogenized catalyst system. US’042 teaches passing a gaseous feed mixture containing C2 to C8 olefins together with synthesis gas over a support composed of a porous ceramic material on which the catalyst system is present in heterogenized form, wherein the catalyst system comprises a metal from Group 8 or 9 of the Periodic Table, at least one organic phosphorus-containing ligand, a stabilizer, and optionally an ionic liquid. US’042 further teaches that the support is in the form of a powder, granular material, or pellets and consists of a carbidic ceramic material, nitridic ceramic material, silicidic ceramic material, or a mixture thereof. See US’042, claim 1; Abstract; col. 2, line 66 through col. 3, line 16.
US’042 teaches that the feed mixture may include C2 to C5 olefins, including ethene, propene, 1-butene, 2-butene, 1-pentene, and 2-pentene, and may include raffinate streams or crude butane. See US’042, col. 3, lines 17–31. US’042 further teaches that the hydroformylation is conducted at 65 to 200°C, preferably 75 to 175°C, and more preferably 85 to 150°C, and at a pressure not greater than 35 bar, preferably not greater than 30 bar, and more preferably not greater than 25 bar. See US’042, col. 3, lines 45–52; claims 9, 10, 12, and 13.
US’042 teaches that the catalyst system comprises a transition metal from Group 8 or 9, especially iron, ruthenium, iridium, cobalt, or rhodium, more preferably cobalt or rhodium, at least one organic phosphorus-containing ligand, and a stabilizer. See US’042, col. 3, lines 53–64. US’042 further teaches that the stabilizer is preferably an organic amine compound containing at least one 2,2,6,6-tetramethylpiperidine unit. See US’042, col. 3, line 65 through col. 4, line 5; claim 3. US’042 teaches an organic phosphorus-containing ligand having the general formula R′—A—R″—A—R′″, wherein R′, R″, and R′″ are organic radicals, R′ and R′″ are not identical, and each A is a bridging —O—P(—O)2— group. See US’042, col. 5, lines 45–56; claim 2.
US’042 teaches that the porous support material is selected from nitridic ceramic, carbidic ceramic, silicidic ceramic, and mixtures thereof; that nitridic ceramics include silicon nitride, boron nitride, and aluminum nitride; that carbidic ceramics include silicon carbide, boron carbide, and tungsten carbide; and that silicidic ceramic is preferably molybdenum silicide. See US’042, col. 6, lines 13–25; claim 4. US’042 teaches that the support preferably consists of a carbidic ceramic and more preferably silicon carbide. See US’042, col. 6, lines 23–25; claims 5 and 6. US’042 further teaches that the catalyst system may be made without ionic liquid and that, in a preferred embodiment, the catalyst system does not comprise any ionic liquid. See US’042, col. 5, lines 19–23; claim 11.
US’042 does not expressly teach the shutdown sequence recited in claim 1, namely: (a) shutting down a feed of the gaseous feed mixture while synthesis gas is still being fed into the reactor; (b) lowering the temperature in the reactor to ambient temperature; and (c) shutting down the synthesis gas feed and keeping the reactor under a synthesis gas atmosphere until the hydroformylation process is restarted.
US’209 teaches that, in rhodium/organophosphorus hydroformylation, progressive catalyst deactivation and ligand loss through byproduct formation are reduced by continuously stripping the reaction medium so that high-boiling organophosphorus byproducts are maintained at a low level. See US’209, Abstract; col. 1, lines 55–68; col. 2, lines 1–20. US’209 further teaches that the carbonyl reaction product may be stripped directly out of the reaction zone in the stream of unreacted synthesis gas exiting from the reaction zone. See US’209, col. 1, lines 23–31. US’209 explains that intensive stripping prevents formation of catalyst poisons and ligand-abstracting species, increases the effective life of the rhodium catalyst, and reduces ligand consumption through formation of organophosphorus byproducts. See US’209, col. 2, lines 21–43. US’209 further teaches that high molecular weight phosphorus-containing byproducts are associated with rhodium deactivation and that high stripping prevents such byproducts from reaching deleterious concentration levels. See US’209, col. 2, line 64 through col. 3, line 20. Claim 8 of US’209 expressly recites continuously stripping the liquid reaction medium during hydroformylation by passing a gas comprising hydrogen and carbon monoxide therethrough.
US’231 teaches stabilizing a hydroformylation process by manipulating a feed flow of a gas comprising carbon monoxide to adjust total pressure and/or vent flow rate. See US’231, col. 4, lines 45–65; claim 1. US’231 teaches that the hydroformylation process is carried out by reacting an olefinic compound with carbon monoxide and hydrogen in the presence of a metal-organophosphorus ligand complex catalyst, preferably a metal-organopolyphosphite ligand complex catalyst. See US’231, col. 6, lines 20–37. US’231 further teaches that reaction control and stability are achieved by adjusting the flow rate of a carbon monoxide-containing inlet gas to maintain target total pressure or target vent flow rate. See US’231, col. 5, lines 55–67. US’231 also teaches that an apparatus for hydroformylation may include means for feeding synthesis gas and means for manipulating the flow rate of synthesis gas and/or a secondary source of carbon monoxide to adjust measured pressure or vent flow. See US’231, claim 23.
It would have been obvious to one of ordinary skill in the art at the time of the invention to modify the US’042 process such that, upon shutdown of a reactor, the olefin-containing gaseous feed mixture is shut down while synthesis gas continues to be fed, the reactor is cooled to ambient temperature, and the synthesis gas feed is then shut down while the reactor remains under a synthesis gas atmosphere until restart.
US’042 already recognizes that catalyst activity can decrease with operating time due to enrichment of high boilers, condensation in pores, coverage or deactivation of active sites, and breakdown of the catalyst system. See US’042, col. 10, lines 20–35. US’209 teaches that synthesis gas or a gas comprising hydrogen and carbon monoxide is useful for stripping hydroformylation reaction media to remove or prevent accumulation of catalyst-deactivating high-boiling organophosphorus byproducts. US’231 teaches that CO-containing gas and synthesis gas flow are known control variables in hydroformylation for stabilizing pressure, vent flow, reaction rate, and temperature.
Thus, one of ordinary skill in the art would have had reason to continue synthesis gas flow after stopping the olefin-containing gaseous feed in US’042’s hydroformylation reactor in order to purge residual olefin, aldehyde product, and high-boiling byproducts from the catalyst-containing support and to maintain the catalyst in a hydroformylation-compatible CO/H2 atmosphere. Continuing synthesis gas during shutdown would predictably provide stripping/purging and stabilization benefits taught by US’209 and US’231, while stopping the olefin feed would stop further hydroformylation conversion and product formation. Lowering the reactor temperature to ambient temperature after stopping olefin feed would have been an ordinary shutdown step to place the reactor in a safe non-operating condition. Thereafter shutting down the synthesis gas feed while keeping the reactor under the synthesis gas atmosphere would have been an ordinary isolation/standby step following the synthesis-gas purge, leaving the reactor filled with the same gas atmosphere used for hydroformylation and catalyst stabilization until restart.
The modification represents the predictable use of a known hydroformylation-compatible purge and stabilization gas, i.e., synthesis gas comprising hydrogen and carbon monoxide, for its known purpose of stripping/purging reaction products and byproducts and stabilizing a rhodium/phosphorus hydroformylation catalyst environment. The substitution of synthesis gas for an inert shutdown atmosphere would have yielded the predictable result of reducing catalyst deactivation and facilitating restart of the reactor.
As to claim 2, US’042 teaches a synthesis gas/feed mixture molar ratio of 6:1 to 1:1, preferably 5:1 to 3:1. See US’042, col. 3, lines 49–52. US’231 teaches manipulating the flow of a gas comprising carbon monoxide, including synthesis gas, to control pressure and vent flow. See US’231, col. 4, lines 45–65; claim 23. It would have been obvious to increase the synthesis gas feed rate when the olefin-containing gaseous feed mixture is shut down in order to maintain purge flow through the reactor and compensate for the discontinued olefin-feed volume while removing residual reactants and products from the catalyst bed.
As to claim 3, US’231 teaches controlling total pressure and vent flow by manipulating carbon monoxide-containing gas flow and synthesis gas flow. See US’231, col. 4, lines 45–65; claim 23. US’042 teaches pressure adjustment, release, evacuation, and purging as ordinary reactor operations in the same reactor/catalyst platform. See US’042, col. 7, lines 31–48. It would have been obvious to reduce pressure in the reactor after and/or during the lowering of temperature as a routine shutdown and purge measure to remove residual volatile components and place the reactor in a controlled standby condition.
As to claim 4, to the extent claim 4 is interpreted as requiring reduction of the synthesis gas feed rate during step b), US’231 teaches manipulating CO-containing gas or synthesis gas flow to control total pressure and vent flow. See US’231, col. 4, lines 45–65; col. 5, lines 55–67; claim 23. It would have been obvious to reduce the synthesis gas feed rate during the cooling step after the initial purge demand has decreased in order to control pressure, avoid unnecessary gas consumption, and transition the reactor toward the final standby atmosphere.
As to claim 5, US’231 teaches controlling total pressure by manipulating the feed flow of carbon monoxide-containing gas and/or synthesis gas. See US’231, claim 23. It would have been obvious to increase pressure in the reactor before shutting down the synthesis gas feed in order to backfill the reactor with the selected synthesis gas atmosphere and leave the reactor at a desired standby pressure until restart.
As to claim 6, US’042 teaches the organic phosphorus-containing ligand having the general formula R′—A—R″—A—R′″, wherein R′, R″, and R′″ are each organic radicals, R′ and R′″ are not identical, and each A is a bridging —O—P(—O)2— group. See US’042, col. 5, lines 45–56; claim 2.
As to claim 7, US’042 teaches that the stabilizer is preferably an organic amine compound containing at least one 2,2,6,6-tetramethylpiperidine unit. See US’042, col. 3, line 65 through col. 4, line 5; claim 3.
As to claim 8, US’042 teaches nitridic ceramic materials including silicon nitride, boron nitride, and aluminum nitride; carbidic ceramic materials including silicon carbide, boron carbide, and tungsten carbide; and silicidic ceramic material including molybdenum silicide. See US’042, col. 6, lines 13–25; claim 4.
As to claims 9 and 10, US’042 teaches that the support preferably consists of a carbidic ceramic and more preferably silicon carbide. See US’042, col. 6, lines 23–25; claims 5 and 6.
As to claim 11, US’042 teaches hydroformylation at a temperature of 65 to 200°C, preferably 75 to 175°C, and more preferably 85 to 150°C. See US’042, col. 3, lines 45–48; claims 9 and 12. The claimed range of 75 to 175°C is expressly taught by US’042.
As to claim 12, US’042 teaches that the pressure during hydroformylation should not exceed 35 bar, preferably 30 bar, and more preferably 25 bar. See US’042, col. 3, lines 48–50; claim 10. US’042’s Example 1 further conducts hydroformylation at 10 bar, which falls within the claimed range of at least 1 bar and not greater than 35 bar. See US’042, Example 1.
As to claim 13, US’042 teaches that, in a preferred embodiment, the catalyst system does not comprise any ionic liquid. See US’042, col. 5, lines 19–23; claim 11.
As to claim 14, US’042 teaches C4 olefin feed materials, including 1-butene and 2-butene, and raffinate streams/crude butane containing butenes. See US’042, col. 3, lines 17–31. US’042’s Example 1 uses a feed mixture containing 1-butene/isobutene, cis-2-butene, and trans-2-butene. See US’042, Example 1.
As to claim 15, US’042 teaches rhodium as a preferred Group 8 or 9 transition metal for the hydroformylation catalyst system. See US’042, col. 3, lines 53–58. US’042’s Example 1 uses Rh(acac)(CO)2 as the rhodium precursor. See US’042, Example 1.
As to claim 16, US’042 teaches hydroformylation at 85 to 150°C. See US’042, col. 3, lines 45–48; claim 12. US’042’s Example 1 further conducts hydroformylation at 120°C, which falls within the claimed range. See US’042, Example 1.
As to claim 17, US’042 teaches hydroformylation pressure not greater than 25 bar as a more preferred pressure. See US’042, col. 3, lines 48–50; claim 13. US’042’s Example 1 further conducts hydroformylation at 10 bar, which falls within the claimed range of at least 1 bar and not greater than 25 bar. See US’042, Example 1.
Accordingly, claims 1–17 would have been obvious over the combined teachings of US’042, US’209, and US’231. US’042 teaches the claimed heterogenized gas-phase hydroformylation catalyst platform and most of the claimed structural and operating limitations. US’209 and US’231 provide the reason to continue or manipulate synthesis gas/CO-containing gas flow during shutdown to purge/strip residual reactants, products, and high-boiling byproducts and to stabilize the hydroformylation catalyst environment. The claimed shutdown sequence is therefore a predictable application of known synthesis gas stripping and CO-containing gas stabilization practices to the same type of hydroformylation process taught by US’042.
Any inquiry concerning this communication or earlier communications from the examiner should be directed to DEBORAH D CARR whose telephone number is (571)272-0637. The examiner can normally be reached Monday-Friday (10:30 am -6:30 pm).
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/DEBORAH D CARR/Primary Examiner, Art Unit 1691
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