DETAILED ACTION
The present application, filed on or after March 16, 2013, is being examined under the first inventor to file provisions of the AIA .
Election/Restrictions
Applicant’s election without traverse of Group I, claims 1-12 in the reply filed on 16 December 2025 is acknowledged. Claims 13-19 are withdrawn from further consideration pursuant to 37 CFR 1.142(b) as being drawn to a nonelected invention, there being no allowable generic or linking claim.
Specification
The disclosure is objected to because of the following informalities: The instant specification provides contradictory information as to the yield of alkylated aromatics from the process, and thus makes it impossible to determine what is included in the scope of the term “alkylated aromatics” in the claim. Table 1 on page 11 refers to Example 1 with Catalyst 1, and recites there is a yield of 24.1 wt% C7-C10 aromatics from the process. One of ordinary skill in the art would expect that these are all C6 aromatic rings with alkyl substituents, and thus the yield of the “total alkylated aromatics” from the Table is at least 24.1 wt%. However, paragraph [0062] on page 11 also refers to Example 1 with Catalyst 1, but recites that there is a yield of only 19.5 wt% “total alkylated aromatics”. There cannot be two different yields of alkylated aromatics from the same Example, and it is unclear how the total of “19.5 wt%” recited in paragraph [0062] can be obtained from the data provided in the Table. Thus, it is unclear what the scope of the term “alkylated aromatics” is in the application as filed, because the term “alkylated aromatics” clearly cannot include all the alkylated aromatics produced by the process but there is no further explanation of which aromatics are included. See also the 112(b) rejection for claim 1, step e) recited below. Appropriate correction is required.
Claim Interpretation
Claim 1 recites “A single step catalytic process for the production of alkylated aromatics using CO2 and methylcyclohexane…” and then recites “steps” a)-e). It is the Examiner’s interpretation that “steps” a) and b) are recitation of the formation of the catalyst and “steps” c)-e) are merely explicit recitations of the reactions taking place during the contacting of the CO2 and methylcyclohexane with the catalyst formed in steps a) and b). Thus, it is the Examiner’s interpretation that the recitations c)-e) together make up the “single step” catalytic process of claim 1, where c), d), and e) are all simultaneous reactions that take place when the methylcyclohexane and CO2 are contacted with the reduced metal functionalized zeolite catalyst to produce the desired alkylated aromatics.
Claim Objections
Claims 1 and 3 are objected to because of the following informalities:
With regard to claim 1, the claim recites the following issues:
in step c) “WHSV (weight hourly space velocity)”. The use of parentheses in in the claim is improper and in this case unnecessary because one of ordinary skill in the art understands the acronym WHSV.
In step d) “reacting CO2 with H2, which was obtained from methylcyclohexane”. This should be “the CO2” and “the H2” for antecedent basis purposes, as there is not additional CO2 or H2 added to the process.
In step e) “reacting toluene with the alkylating species”. This should be “reacting the toluene” and “the active alkylating species” for antecedent basis purposes.
With regard to claim 3, the claim recites “mix xylenes”. The term should be “mixed xylenes” for consistency with the terms of the art.
Appropriate corrections are required.
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 1-12 are 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.
With regard to claims 1, 4, 7, and 9, the claims each recite “zeolite (HZSM-5)”. A broad range or limitation together with a narrow range or limitation that falls within the broad range or limitation (in the same claim) may be considered indefinite if the resulting claim does not clearly set forth the metes and bounds of the patent protection desired. See MPEP § 2173.05(c). In the present instance, the claims each recite the broad recitation “zeolite”, and the claims also each recite “(HZSM-5)” which is the narrower statement of the range/limitation. The claim(s) are considered indefinite because there is a question or doubt as to whether the feature introduced by such narrower language is (a) merely exemplary of the remainder of the claim, and therefore not required, or (b) a required feature of the claims, especially due to the presence of parentheses around “HZSM-5”, as parentheses should only be used to indicate reference numbers.
For purposes of examination, claim 9 explicitly recites that the zeolite is HZSM-5, thus the “(HZSM-5)” language in claims 1, 4, 7, and 9 will be interpreted as optional and not required.
With regard to claim 1, the claim recites in step c) “a mixture of CO2 and N2 (CO2/N2=1/3 vol/vol)…” The use of parentheses for the specific ratio is indefinite because it is not clear whether the specific ratio is optional or required, as parentheses should only be used to indicate reference numbers.
For purposes of examination, the Examiner will consider the language in parentheses is optional, and thus the step only requires a mixture of CO2 and N2.
Also with regard to claim 1, the claim recites in step e) reacting toluene…to produce aromatic hydrocarbons, and alkylated aromatic hydrocarbons.” A broad range or limitation together with a narrow range or limitation that falls within the broad range or limitation (in the same claim) may be considered indefinite if the resulting claim does not clearly set forth the metes and bounds of the patent protection desired. See MPEP § 2173.05(c). In the present instance, the claim recites the broad recitation “aromatics”, and the claim also recites “alkylated aromatics” which is the narrower statement of the range/limitation. The claim(s) are considered indefinite because there is a question or doubt as to whether the feature introduced by such narrower language is (a) merely exemplary of the remainder of the claim, and therefore not required, or (b) a required feature of the claims. Further, it is unclear whether any unreacted toluene is considered a produced aromatic and/or alkylated aromatic hydrocarbon, as the toluene is produced from the methylcyclohexane during the single step process but is not, as written, produced during the part of the reaction which corresponds to step e).
For purposes of examination, the instant specification provides contradictory information as to the yield of alkylated aromatics from the process, and thus makes it impossible to determine what is included in the scope of the term “alkylated aromatics” in the claim. Table 1 on page 11 refers to Example 1 with Catalyst 1, and recites there is a yield of 24.1 wt% C7-C10 aromatics from the process. One of ordinary skill in the art would expect that these are all C6 aromatic rings with alkyl substituents, and thus the yield of the “total alkylated aromatics” from the Table is at least 24.1 wt%. However, paragraph [0062] on page 11 also refers to Example 1 with Catalyst 1, but recites that there is a yield of only 19.5 wt% “total alkylated aromatics”. Thus it is unclear what the scope of the term “alkylated aromatics” is in the application as filed, because the term “alkylated aromatics” clearly cannot include all the alkylated aromatics produced by the process but there is no further explanation of which aromatics are included. As such, the Examiner will give the broadest reasonable interpretation “alkylated aromatic” referring to any aromatic hydrocarbon that has an alkyl substituent, and any toluene present in the product will be considered to be a produced alkylated aromatic.
With regard to claim 5, the claim recites “wherein metal precursors are hexachloroplatinic acid hexahydrate, chromium nitrate nonahydrate, zinc nitrate hexahydrate and magnesium nitrate hexahydrate for Pt, Cr, Zn, and Mg, respectively.” It is unclear from the phrasing what the nexus of this claim is with claims 1 and 4 upon which it depends. Claim 4 requires metal precursors, but it is unclear whether the metal precursors in claim 5 are the same metal precursors. Further, it is unclear whether the claim is intending to require all four metals and all four specific precursors, or if the claim is only saying if each metal is present, this is the precursor to use. For example, does claim 5 require that zinc nitrate hydrate be used for the catalyst, or is it saying that if zinc is used for the catalyst, the metal precursor is zinc nitrate hexahydrate? Thus, the claim is indefinite.
For purposes of examination, there is no other claim that requires four metals for the catalyst. Thus, the claim will be considered as optional, such that if the metal is present, the specified precursor must be used, but not requiring that all four metals must be present.
With regard to claim 8, the claim as amended recites “most preferred alkaline earth metal”. The phrase "most preferred" renders the claim indefinite because it is unclear whether the limitations following the phrase are part of the claimed invention. See MPEP § 2173.05(d).
For purposes of examination, the Examiner will consider the claim phrasing originally presented that the alkaline earth metal is Mg, thus claim 8 requires Mg.
With regard to claims 2, 3, 6, and 10-12, the claims are rejected as being dependent on a rejected base claim.
The following is a quotation of 35 U.S.C. 112(d):
(d) REFERENCE IN DEPENDENT FORMS.—Subject to subsection (e), a claim in dependent form shall contain a reference to a claim previously set forth and then specify a further limitation of the subject matter claimed. A claim in dependent form shall be construed to incorporate by reference all the limitations of the claim to which it refers.
The following is a quotation of pre-AIA 35 U.S.C. 112, fourth paragraph:
Subject to the following paragraph [i.e., the fifth paragraph of pre-AIA 35 U.S.C. 112], a claim in dependent form shall contain a reference to a claim previously set forth and then specify a further limitation of the subject matter claimed. A claim in dependent form shall be construed to incorporate by reference all the limitations of the claim to which it refers.
Claims 10 and 12 are rejected under 35 U.S.C. 112(d) or pre-AIA 35 U.S.C. 112, 4th paragraph, as being of improper dependent form for failing to further limit the subject matter of the claim upon which it depends, or for failing to include all the limitations of the claim upon which it depends.
With regard to claim 10, the claim recites “wherein the methylcyclohexane is used as an in-situ source of H2.” However, claim 1 already recites that methylcyclohexane is a hydrogen atom donor, that reacting methylcyclohexane produces hydrogen, and that the process is a single-step process. Thus, it is already clear from claim 1 that methylcyclohexane is a source of H2 and that it must be in-situ to be a single step, and claim 10 does not further limit claim 1.
With regard to claim 12, the claim recites “wherein the catalytic process is a single step process.” However, as amended, claim 1 already requires that the process is a “single-step catalytic process”. The language of claim 12 adds no further limitation to the language of claim 1. Thus, claim 12 does not further limit claim 1.
Applicant may cancel the claim(s), amend the claim(s) to place the claim(s) in proper dependent form, rewrite the claim(s) in independent form, or present a sufficient showing that the dependent claim(s) complies with the statutory requirements.
Claim Rejections - 35 USC § 103
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 1-3 and 10-12 are rejected under 35 U.S.C. 103 as being unpatentable over Wang et al. (CN 110015940, machine translation provided herein) in view of Radadia (Microfluidics for Biochemical and Chemical Reactions) and Korelitz et al. (US 3,211,799).
With regard to claims 1 and 12, Wang teaches a process for conversion of methylcyclohexane in the presence of CO2 to aromatics including toluene (Abstract) comprising the following steps:
a) and b) preparing a metal on ZSM-5 catalyst (metal functionalized zeolite), placing the catalyst in a reactor, and reducing the catalyst under a flow of H2 at a temperature of 300-600°C (paragraph [0025]) and for 5 hours (paragraphs [0028]-[0029]). These amounts overlap the range of 450-500°C and is within the range of 5 to 6 h of instant claim 1, rendering the temperature range prima facie obvious.
c) introducing methylcyclohexane and CO2 into the reactor (paragraph [0029]) at a temperature of 200-500°C and a pressure of 0.1 to 2 MPa (1 to 20 bar) (paragraph [0026]). These overlap the ranges of 300-400°C and 20-30 bar of instant claim 1, rendering the ranges prima facie obvious. Wang further teaches the reaction dehydrogenates methylcyclohexane to toluene and produces hydrogen (paragraphs [0014] and [0020]).
d) and e) Wang further teaches that the product includes alkylated aromatic hydrocarbons including xylenes (paragraph [0037]). Methylcyclohexane and CO2 are added and the products are produced within the reactor with no additional steps or reactors present, thus the process is a single step process (instant claims 1 and 12) as claimed.
Wang fails to teach i) a fixed bed micro-reactor, ii), the presence of N2 in the reaction feed and ratio of CO2/N2, iii) the WSHV of the reaction step, or iv) that the CO2 reacts with the H2 to produce an active alkylating species or that toluene is reacting with the alkylating species.
With regard to the micro-reactor i), Wang teaches a fixed bed reactor (paragraph [0026]) but fails to specify the reactor is a microreactor. Radadia teaches that microreactors for chemical reactions are preferred for improved safety and greater reaction control in chemical reactions (page 3).
Therefore, it would have been obvious to one of ordinary skill in the art at the time of the invention to use a fixed bed microreactor, as claimed, in the process of Wang, because Wang teaches a fixed bed reactor and Radadia teaches that microreactors are preferred for reactions because of improved safety and greater reaction control (page 3).
With regard to the N2 and ratio of CO2/N2 ii), Korelitz teaches a process for alkylation of aromatic hydrocarbons (column 1, lines 10-11). Korelitz teaches that diluent gases such as nitrogen can be used in the alkylation process in a ratio of diluent:alkylating agent of 2-10:1 (column 5, lines 10-13). This range of 2-10:1, when flipped to match the claimed ratio of CO2:N2, is equivalent to a range of 1:2-10, which encompasses the ratio of CO2:N2 of 1:3 of instant claim 1, rendering the ratio prima facie obvious.
Therefore, it would have been obvious to one of ordinary skill in the art at the time of the invention to add the diluent to the process of Wang in the claimed amount, because each of Wang and Korelitz teach a process comprising alkylation of an aromatic hydrocarbon, one of ordinary skill in the art understands the purpose of a diluent in a process, and Korelitz teaches it is known to use a diluent in a similar process comprising alkylation of an aromatic hydrocarbon in an amount which encompasses the claimed amount.
With regard to the WHSV iii), Wang teaches a volume HSV of 100-1000 h-1 (paragraph [0026]). Due to a lack of information about the catalyst and volume of the reactor, the Examiner is unable to convert this to WHSV. However, one of ordinary skill in the art is well aware that the space velocity of the reaction is a process parameter which is known to affect the conversion of the reactants, and thus can be optimized. Therefore, it would have been obvious to one having ordinary skill in the art to have determined the optimum value of an WHSV of between 2-3 h-1 as claimed through routine experimentation in the absence of a showing of criticality. See MPEP 2144.05(II).
With regard to the reactions iv), Wang teaches the same process comprising the same feed including methylcyclohexane and CO2, for the same purpose of producing H2 from the methylcyclohexane and producing aromatic hydrocarbons. Wang further teaches the same catalyst and similar conditions for the process. Therefore, one of ordinary skill in the art would reasonably expect that the process of Wang functions in the claimed manner by producing an active alkylating species from the CO2 and alkylating the toluene with this active alkylating species to produce aromatic hydrocarbons, as claimed, absent any evidence to the contrary.
With regard to claims 2-3, Wang in view of Radadia and Korelitz does not specifically teach the yield of the process. However, Wang in view of Radadia and Korelitz teaches a similar process starting with a similar feed of CO2 and methylcyclohexane run at similar conditions and with a similar ZSM-5 metal functionalized catalyst to produce a similar product comprising toluene along with other aromatics (see above). Therefore, one of ordinary skill in the art would reasonably expect a similar result of yield of 25.7-28.6 wt% aromatics, 19.5-21 wt% alkylated aromatics, 9-9.5 wt% xylenes, 5.6-6.1 wt% toluene, and 0.6-1.5 wt% benzene, as claimed in instant claims 2-3, absent any evidence to the contrary.
With regard to claims 10 and 11, Wang teaches that the methylcyclohexane is the hydrogen source (in-situ source) and teaches that the reaction does not use high-purity hydrogen (molecular H2) (paragraph [0020])
Claims 4 and 5 are rejected under 35 U.S.C. 103 as being unpatentable over Wang et al. (CN 110015940, machine translation provided herein) in view of Radadia (Microfluidics for Biochemical and Chemical Reactions) and Korelitz et al. (US 3,211,799) as applied to claim 1 above, and further in view of Ge et al. (US 2014/0316177).
With regard to claims 4 and 5, Wang teaches producing the metal functionalized zeolite by b) adding an aqueous solution of chloroplatinic acid hexahydrate (instant claim 5) to a support and c) drying for 10 hours and calcining for 4 hours to form a support (paragraph [0028]). These are within the ranges of 10-12 hours drying and 4-5 hours calcining of instant claim 4. Wang further teaches the drying temperature of 120°C and calcining temperature of 550°C (paragraph [0028]). These are not within the ranges of 100-110°C and 450-500°C of instant claim 4, however, they are considered to be substantially close. A prima facie case of obviousness exists where the claimed ranges or amounts do not overlap with the prior art but are merely close (MPEP 2144.05(I)). Therefore, it would have been obvious to one of ordinary skill in the art at the time of the invention to use the claimed ranges as Wang teaches amounts which are substantially close to the claimed ranges and a prima facie case of obviousness exists where amounts are close to the claimed ranges, absent evidence of criticality or unexpected results of the ranges.
Wang fails to teach the step b) which is incipient wetness impregnation by dropwise addition to the support.
Ge teaches a method for synthesis of a catalyst comprising platinum on ZSM-5 (page 13, claim 44 and paragraph [0139]), which comprises a) dissolving the PtCl compound in water (understood to be distilled water in a lab, absent evidence to the contrary) and b) dropping the solution onto the zeolite (mixing the solution dropwise continuously). Ge further teaches that incipient wetness is an alternative impregnation method to ion exchange (paragraph [0056]), which is what is performed in Wang.
Therefore, it would have been obvious to one of ordinary skill in the art at the time of the invention to use the incipient wetness method of Ge instead of the ion exchange of Wang to produce the catalyst, because Wang and Ge each teach the catalyst comprising Pt and ZSM-5, and Ge teaches that the catalyst is known to be formed by either ion exchange or incipient wetness, as claimed.
Wang in view of Ge does not specifically teach a muffle furnace for the calcining. However, it is well known to use a tube furnace or a muffle furnace for calcination, and thus one of ordinary skill in the art would find it obvious to select the muffle furnace as a known option as Wang and Ge do not explicitly teach the type of furnace used, absent any evidence to the contrary.
With regard to claims 7 and 8, Ge further teaches that the addition of an alkaline earth metal M2 to the catalyst comprising ZSM-5 and Pt improves resistance to coking in a dehydrogenation process (paragraph [0022]). While Ge does not explicitly teach Mg as the alkaline earth metal (instant claim 8), this is merely an obvious selection from the finite list of alkaline earth metals explicitly taught by Ge.
Therefore, it would have been obvious to one of ordinary skill in the art at the time of the invention to add the alkaline earth metal to the catalyst of Wang, because Wang and Ge each teach processes comprising dehydrogenation over a Pt and ZSM-5 catalyst, and Wang teaches that adding an alkaline earth metal provides improved resistance to coking (paragraph [0022]).
Claim 6 is rejected under 35 U.S.C. 103 as being unpatentable over Wang et al. (CN 110015940, machine translation provided herein) in view of Radadia (Microfluidics for Biochemical and Chemical Reactions), Korelitz et al. (US 3,211,799), and Ge et al. (US 2014/0316177) as applied to claim 4 above, and further in view of Ou et al. (US 7,902,414).
With regard to claim 6, Wang in view of Ge teaches the process for producing the zeolite catalyst above.
Wang in view of Ge fails to teach the use of the catalyst as extrudates.
Ou teaches a process conversion of toluene in the presence of carbon dioxide and hydrogen to para-xylene (Abstract) where the catalyst is Mg modified ZSM-5 (column 8, lines 34-36). Ou further teaches the catalyst can be used after incipient wetness impregnation in the form of extrudates (column 6, lines 3-7).
Therefore, it would have been obvious to one of ordinary skill in the art at the time of the invention to use the catalyst of Wang in view of Ge in the form of extrudates, because each of Wang and Ou teaches ZSM-5 modified with metals for conversion of toluene to xylenes in the presence of carbon dioxide, Wang in view of Ge is silent regarding the form of the catalyst, and Ou teaches it is known to use the catalyst after incipient wetness impregnation in the form of extrudates (column 6, lines 3-7).
Ou fails to teach the size of the extrudates. However, one of ordinary skill in the art understands that the size of the extrudate would affect the flow and conversion of the reactants during the process. Thus, the size is a process parameter, and can be optimized. Therefore, it would have been obvious to one having ordinary skill in the art before the effective filing date of the invention to optimize the extrudate to have a diameter of 1.2-1.5 mm and a length of 5 to 10 mm, as claimed, because it has been held that discovering an optimum value of a result effective variable involves only routine skill in the art. See MPEP 2144.05(II).
Claim 9 is rejected under 35 U.S.C. 103 as being unpatentable over Wang et al. (CN 110015940, machine translation provided herein) in view of Radadia (Microfluidics for Biochemical and Chemical Reactions) and Korelitz et al. (US 3,211,799) as applied to claim 1 above, and further in view of Drake et al. (US 6,013,849).
With regard to claim 9, Wang teaches that the ZSM-5 catalyst is HZSM-5 and comprises Pt and Ni (4th period d-block metal) (paragraphs [0016], and [0028])
Wang is silent regarding the silica-alumina ratio and surface area of the zeolite. Thus, one of ordinary skill in the art would look to related art to determine suitable ranges for these properties.
Drake teaches that it is known that ZSM-5 zeolites for hydrocarbon conversion can have a silica-alumina ratio of about 12:1 to about 100:1 (column 2, lines 23-25 and 33) and a surface area of 50-700 m2/g (column 4, lines 22-23). These overlap the ranges of 30-80 and 405-435 of instant claim 9, rendering the ranges prima facie obvious.
Therefore, it would have been obvious to one of ordinary skill in the art at the time of the invention to use the amounts of Drake in the catalyst of Wang, because Wang and Drake each teach ZSM-5 zeolites, Wang is silent regarding the properties claimed, and Drake teaches that suitable silica-alumina ratios and surface area ratios for ZSM-5 in hydrocarbon conversion reactions overlap the claimed ranges (column 2, line 33 and column 4, lines 22-23).
Conclusion
Any inquiry concerning this communication or earlier communications from the examiner should be directed to ALYSSA L CEPLUCH whose telephone number is (571)270-5752. The examiner can normally be reached M-F, 8:30 am-5 pm, EST.
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/Alyssa L Cepluch/Examiner, Art Unit 1772
/IN SUK C BULLOCK/Supervisory Patent Examiner, Art Unit 1772