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 .
Continued Examination Under 37 CFR 1.114
A request for continued examination under 37 CFR 1.114, including the fee set forth in 37 CFR 1.17(e), was filed in this application after final rejection. Since this application is eligible for continued examination under 37 CFR 1.114, and the fee set forth in 37 CFR 1.17(e) has been timely paid, the finality of the previous Office action has been withdrawn pursuant to 37 CFR 1.114. Applicant's submission filed on 04 May 2026 has been entered.
Claim Status
Claims 1 and 14 are amended. Claims 21 and 22 are new.
Claims 1-22 are pending for examination below.
Response to Arguments
Applicant’s arguments, see Remarks, filed 04 May 2026, with respect to the rejection(s) of claim(s) 1-22 under USC 103 over Harandi in view of Joensen have been fully considered and are persuasive. Joensen is not needed to teach the newly added limitations of separating and recycling an overhead stream of claim 1 or the apparatus comprising the overhead recycle stream conduit of claim 14, and the phase separator of new claims 21 and 22 is also not addressed by Joensen. Therefore, the rejections have been withdrawn. However, upon further consideration, a new ground(s) of rejection is made in view of a new interpretation of the previously presented prior art in view of the amendments.
Applicant's arguments filed 04 May 2026 with regard to claim 2 being separately patentable have been fully considered but they are not persuasive.
Applicant argues on pages 10-11 of the Remarks that Kong does not disclose separating a benzene stream and recycling it to an MTG reactor, and that even if benzene recycling was generally known, that does not render obvious the claimed configuration of separating and recycling.
In response, the Examiner agrees that Kong does not explicitly teach separating and recycling benzene, but notes that the teaching does not have to be explicit in a reference to render obvious the claims. Harandi teaches recycling at least a portion of an aromatics containing stream to the methanol to gasoline reactor (column 4, lines 44-45 and Figure 1). Kong teaches a method for preparing gasoline from methanol (Title). Kong further teaches that recycling benzene to the gasoline reactor converts the benzene to other aromatic such as toluene and xylene, thus eliminating the need for benzene extraction from the gasoline product (paragraph [0013]). One of ordinary skill in the art understands that benzene is an undesirable aromatic in gasoline processes due to restrictions on the amount, and for clarification the Examiner will add the citation of US 2010/0300930 to Clark, which states that benzene content in gasoline is controlled by regulations to be very low levels (paragraph [0005]).
Thus, between Clark and Kong, one of ordinary skill in the art would have sufficient motivation to remove benzene from the aromatics before combining the aromatics with the gasoline from the methanol reactor to form a gasoline product as taught by Harandi (column 10, lines 16-20). Therefore, it would have been obvious to one of ordinary skill in the art at the time of the invention to separate only benzenes and recycle the benzenes to the methanol to gasoline reactor as taught by Harandi (all aromatics including benzene) and Kong (specifically benzene aromatics) in order to reduce the benzene content and eliminate the need for benzene extraction to meet known gasoline regulations as taught by Clark.
Applicant also argues on page 11 of the Remarks that the rejection relies on hindsight because the rationale does not point to the claimed solution among many alternatives.
In response, the Applicant has not pointed out specifically any other alternatives proposed by the combination of Harandi and Kong, now as evidenced by Clark, as discussed above. Further, In response to applicant's argument that the examiner's conclusion of obviousness is based upon improper hindsight reasoning, it must be recognized that any judgment on obviousness is in a sense necessarily a reconstruction based upon hindsight reasoning. But so long as it takes into account only knowledge which was within the level of ordinary skill at the time the claimed invention was made, and does not include knowledge gleaned only from the applicant's disclosure, such a reconstruction is proper. See In re McLaughlin, 443 F.2d 1392, 170 USPQ 209 (CCPA 1971). The prior art teaches combining aromatics with the gasoline (Harandi), recycling aromatics to a methanol to gasoline reactor (Harandi and Kong), that recycling to the methanol to gasoline reactor specifically benzene forms other aromatics and reduces the benzene content such that benzene extraction from the gasoline product is not needed (Kong) and that it is known that benzene content in gasoline is strictly regulated. Thus, one of ordinary skill in the art is capable of determining that recycling specifically benzene by separating the benzene from the aromatics provides the most benefit to the process by forming additional useful aromatics and reducing the undesirable benzene content, without undue experimentation and with a reasonable expectation of success.
Claim Objections
Claim 3 is objected to because of the following informalities:
With regard to claim 3, the claim recites “optionally a WHSV is 1-6”. Conditions should always include units, and the units for WHSV are typically written as “h-1” or “hr-1”. Applicant’s choice should be added to the claim and to the specification when referring to the WHSV.
Appropriate correction is required.
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, 4, 11, 15, and 21 are rejected under 35 U.S.C. 103 as being unpatentable over Harandi et al. (US 4,835,329, cited on IDS of 10/20/2023).
With regard to claims 1, 4, 15, and 21, Harandi teaches a method for producing gasoline (column 1, lines 5-6), comprising the following steps:
a) providing a stream comprising methanol (oxygenate instant claim 4) to a reactor B and converting the methanol to gasoline over a catalyst to produce a gasoline product comprising C5+ gasoline and C3-C4 paraffins (column 4, lines 42-66).
b) separating the gasoline product stream in recovery section D to produce a gas stream, a C3-C4 paraffin stream, and a C5+ gasoline product stream (column 4, lines 59-66), where the separation section D further comprises separating a gas 230 overhead from the liquid product gasoline and water in separator 228 (phase separation by condensation, as claimed in instant claim 21) (column 7, lines 25-29).
Harandi does not explicitly teach separating the C3-C4 paraffin stream from the gasoline stream after separating the overhead recycle stream. However, Harandi teaches a step of separating and teaches obtaining the same fractions of a gas recycle stream, a product gasoline stream, and a C3-C4 paraffin stream.
Therefore, it would have been obvious to one of ordinary skill in the art at the time of the invention to separate the streams in the claimed manner, as the claimed separation is merely a selection of an order of steps of obtaining the fractions of Harandi, where selection of the order of steps is prima facie obvious absent any evidence of criticality (MPEP 2144(IV)C).
c) recycling the gas 230 to the reactor as diluent 218 (column 7, lines 29-31 and column 6, lines 56-57) where the diluent is merged with oxygenate feed 214 (Figure 2).
d passing the C3-C4 paraffin stream to an aromatization reactor F comprising a catalyst to form aromatics (column 4, lines 66-68) including BTX (benzene, toluene, and xylene instant claim 15) (column 5, line 14).
e) passing at least a portion of the aromatic effluent 119 from reactor F to the reactor B along with the stream comprising methanol (column 4, lines 44-45 and Figure 1).
Harandi describes the aromatization reaction in detail (column 7, line 42-column 8, line 3, and Figure 3). There is no oxygenate stream described as being provided to the aromatization reactor. Thus, step iii does not comprise co-feeding an oxygenate stream to the reactor, as claimed.
With regard to claim 11, Harandi teaches the aromatization reactor comprises a temperature of 300-750°C and a pressure of 350 kPa (3.5 bara), which overlaps the range of 500-600°C, rendering the range prima facie obvious, and is within the range of 3-25 bar absolute of instant claim 11.
Claim 2 is rejected under 35 U.S.C. 103 as being unpatentable over Harandi et al. (US 4,835,329) as applied to claim 1 above, and further in view of Kong et al. (CN 102746877, machine translation provided) as evidenced by Clark et al. (US 2010/0300930).
With regard to claim 2, Harandi teaches recycling aromatics from the aromatization to the methanol to gasoline reactor (column 4, lines 44-45) where the recycled aromatics are alkylated (column 2, lines 51-53).
Harandi does not specifically teach separating benzene from the aromatization product and recycling the benzene stream to the reactor.
Kong teaches a method for preparing gasoline from methanol (Title). Kong further teaches that recycling benzene to the gasoline reactor converts the benzene to other aromatic such as toluene and xylene, thus eliminating the need for benzene extraction from the gasoline product (paragraph [0013]). One of ordinary skill in the art understands that benzene is an undesirable aromatic in gasoline processes due to restrictions on the amount, as evidenced by Clark in paragraph [0005].
Therefore, it would have been obvious to one of ordinary skill in the art at the time of the invention to separate the benzene from the product of the aromatization of Harandi and recycle the benzene to the methanol to gasoline reactor, because Harandi in teaches combining at least a portion of the aromatics with the gasoline product to form a gasoline and also teaches recycling aromatics from the upgrading reactor to the methanol to gasoline reactor in order to alkylate the aromatics, Clark evidences that there are restrictions on levels of benzene in a gasoline product, and Kong teaches that specifically recycling benzene to the methanol to gasoline reactor eliminates the need for benzene extraction by allowing the benzene to form other aromatics (paragraph [0013]).
Claims 3, 16, 17, and 18 are rejected under 35 U.S.C. 103 as being unpatentable over Harandi et al. (US 4,835,329) as applied to claim 1 above, and further in view of Tabak (US 4,433,185).
With regard to claims 3, 16, and 17, Harandi teaches that the catalyst for the MTG reactor is HZSM-5 (instant claims 16 and 17) (column 4, line 59). Harandi further teaches the conditions of the methanol to olefins reaction are disclosed in 4,433,185 to Tabak, which is incorporated by reference into Harandi (column 6, lines 16-19). Tabak teaches that gasoline mode comprises a temperature of 285-375°C and pressure of 400 to 3000 kPa (4-30 bar absolute) (column 4, lines 50-54). This is within the range of 280-400°C and overlaps the range of 15-25 bar absolute of instant claim 3, rendering the ranges prima facie obvious.
With regard to claim 18, Harandi teaches the ZSM-5 catalyst further comprises Zn (column 9, lines 7-9).
Claims 5, 19, and 20 are rejected under 35 U.S.C. 103 as being unpatentable over Harandi et al. (US 4,835,329) as applied to claim 1 above, and further in view of Juttu et al. (US 6,784,333).
With regard to claims 5, 19, and 20, Harandi teaches the method above, comprising the aromatization of light paraffins to aromatics.
Harandi does not teach adding sulfur compounds to the feed.
Juttu teaches a method for aromatization of light alkanes having 2-6 carbon atoms (Abstract). Juttu further teaches a ZSM-5 zeolite comprising germanium and platinum provides the benefits of constant selectivity to aromatics (column 3, lines 37-40 and 55-62) and that the catalyst contains platinum sulfide, provided by adding a sulfur compound which is H2S (instant claim 19) to the feed in an amount of 10 ppm to 0.1 wt% (1000 ppm) (column 5, lines 13-25). This is identical to the range of 10-1000 ppm of instant claim 5 and overlaps the range of 10-100 ppm of instant claim 20, rendering the range 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 sulfided catalyst of Juttu in the process of Harandi, because each of Harandi and Juttu teaches aromatization of light paraffins to aromatics over an ZSM-5 catalyst, and Juttu teaches that the catalyst which has been sulfided provides the benefits of constant selectivity to aromatics (column 3, lines 37-40).
Claim 6 is rejected under 35 U.S.C. 103 as being unpatentable over Harandi et al. (US 4,835,329) as applied to claim 1 above, and further in view of Rajagopalan et al. (US 2020/0231880, cited on IDS of 10/09/2023).
With regard to claim 6, Harandi teaches separating a recycle stream from the product gasoline (column 7, lines 27-29) and also teaches separating a fuel gas stream comprising C2- hydrocarbons (column 4, lines 69-62)
Harandi does not specifically teach separating the product gasoline in a deethanizer after separating the recycle gas to generate the fuel gas stream.
Rajagopalan teaches a method for methanol to gasoline conversion (Abstract). Rajagopalan teaches that the process comprises separation of the methanol to gasoline product to produce a recycle gas 129 and a hydrocarbon product 125 (paragraph [0018]), followed by separating the hydrocarbon product 125 in a deethanizer 370 to produce a C2- (fuel gas) stream (paragraph [0019], Fig. 3). Thus Rajagopalan teaches that the claimed configuration is a known and suitable configuration for separating recycle gas and C2- (fuel gas) from a methanol to gasoline product stream.
Therefore, it would have been obvious to one of ordinary skill in the art at the time of the invention to use a deethanizer after separating the recycle gas in Harandi, because each of Harandi and Rajagopalan teach separating fuel gas and a recycle gas stream from a methanol to gasoline product, Harandi does not teach the specific components used, and Rajagopalan teaches that the deethanizer is known and suitable for separating the fuel gas stream (paragraph [0019], Fig. 3).
Claim 7 is rejected under 35 U.S.C. 103 as being unpatentable over Harandi et al. (US 4,835,329) as applied to claim 6 above, and further in view of Dupassieux et al. (US 2012/0165581).
With regard to claim 7, Harandi teaches the process above, where the fuel gas comprises hydrogen (column 4, line 62).
Harandi does not teach hydroisomerization of the gasoline product comprising C5+ hydrocarbons and passing the fuel gas stream to the hydroisomerization step, or that the fuel gas stream also comprises a sulfur compound.
Dupassieux teaches a process for hydroisomerization of gasoline cuts (paragraphs [0013] and [0118]) comprising contacting the feed with a hydroisomerization catalyst which is a sulphurized catalyst (paragraph [0130]). Dupassieux additionally teaches recycling a gas comprising hydrogen and an added sulfur compound to the hydroisomerization in order to keep the catalyst in sulfurized condition (paragraph [0159]). Dupassieux also teaches the hydroisomerization improves cold properties of fuels (paragraph [0013]).
Therefore, it would have been obvious to one of ordinary skill in the art at the time of the invention to perform hydroisomerization by adding a sulfur compound to the fuel gas and passing it to the hydroisomerization step as the hydrogen, because Harandi teaches producing a C5+ gasoline cut (column 4, line 60) and a fuel gas stream comprising hydrogen (column 4, lines 61-62), and Dupassieux teaches hydroisomerization with a sulfided catalyst, recycling a gas comprising hydrogen and an added sulfur compound to the hydroisomerization to maintain the catalyst in the sulfided state (paragraph [0159]), and that the hydroisomerization improves the cold properties of fuels (paragraph [0013]).
Claim 8 is rejected under 35 U.S.C. 103 as being unpatentable over Harandi et al. (US 4,835,329) as applied to claim 1 above, and further in view of Chen et al. (US 2011/0301394) and Bazzani et al. (US 2008/0172931).
With regard to claim 8, Harandi teaches the process above. Harandi further teaches separating a stream comprising C4- compounds including olefins and paraffins from the aromatization product (column 7, lines 44-45 and column 8, lines 1-2).
Harandi fails to teach separating toluene from the aromatization product and adding the toluene to the gasoline stream produced from the MTG reactor B.
Bazzani teaches that adding toluene to a gasoline stream is known to increase the octane number (paragraph [0002]).
Therefore, it would have been obvious to one of ordinary skill in the art at the time of the invention to separate a toluene stream from the aromatization product of Harandi and add the toluene to the gasoline product, because Bazzani teaches that adding toluene to a gasoline pool increases the octane number (paragraph [0002]).
Claims 9 and 10 are rejected under 35 U.S.C. 103 as being unpatentable over Harandi et al. (US 4,835,329) as applied to claim 1 above, and further in view of Dittrich et al. (US 2019/0040324).
With regard to claims 9 and 10, Harandi teaches the aromatization catalyst comprises ZSM-5 (column 7, line 46).
Harandi does not specifically teach the catalyst also comprises 0.1 to 10 wt% metallic and/or oxide zinc.
Dittrich teaches a method for aromatization of LPG hydrocarbons (paragraph [0001]). Dittrich further teaches that a desirable catalyst is ZSM-5 comprising zinc (paragraph [0059]).
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 Dittrich in the process of Harandi because Harandi teaches a ZSM-5 catalyst can be used and Dittrich teaches that ZSM-5 comprising zinc is a suitable catalyst for the aromatization reaction.
Harandi in view of Dittrich fails to teach the amount of zinc or that it is metallic or oxidic zinc. However, one of ordinary skill in the art is aware that metals added to zeolite catalysts are used in the oxide form, absent any explicit statement to the contrary. Also, the amount of zinc is a result-effective variable which would affect the reaction rate and the desired products, and thus can be optimized. Therefore, it would have been obvious to one of ordinary skill in the art at the time of the invention to optimize the amount of zinc to be within the range of 0.1 to 10 wt%, 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 12 is rejected under 35 U.S.C. 103 as being unpatentable over Harandi et al. (US 4,835,329) as applied to claim 1 above, and further in view of Mitchell Jr. (US 3,879,486).
With regard to claim 12, Harandi teaches the aromatization reactor F.
Harandi fails to teach that the reactor is an electrically heated reactor.
Mitchell Jr. teaches conversion of light alkanes to aromatics (Abstract). Mitchell Jr. further teaches that electrically heated reactor is used for the reaction (column 9, lines 53-54).
Therefore, it would have been obvious to one of ordinary skill in the art at the time of the invention to use an electrically heat reactor for Harandi, because each of Harandi and Mitchell Jr teach reaction of light alkanes to aromatics in a reactor, and Mitchell Jr. teaches that electrically heated reactors are known and suitable for such reactions (column 9, lines 53-54).
Claim 13 is rejected under 35 U.S.C. 103 as being unpatentable over Harandi et al. (US 4,835,329) as applied to claim 1 above, and further in view of Ma (CN 105885912, machine translation provided).
With regard to claim 13, Harandi teaches the method above, where the aromatic hydrocarbons are recycled to the MTG reactor.
Harandi fails to teach the use of a buffer tank before recycling.
Ma teaches a method for conversion of methanol to gasoline (paragraph [0002]). Ma further teaches that heavy hydrocarbons including aromatics are recycled to the process (paragraph [0055]), by being separated, passed to a buffer tank, and then being recycled (paragraph [0050]).
Therefore, it would have been obvious to one of ordinary skill in the art at the time of the invention to use a buffer tank in the process of Harandi, because Harandi teaches recycling aromatics to the MTG reaction, and Ma teaches that it is known to pass heavy hydrocarbons including aromatics to a buffer tank before recycling (paragraph [0050]).
Claims 14 and 22 are rejected under 35 U.S.C. 103 as being unpatentable over Harandi et al. (US 4,835,329) as applied to claim 1 above, and further in view of Rajagopalan et al. (US 2020/023188, cited on IDS of 10/09/2023).
With regard to claims 14 and 22, Harandi teaches a system for producing gasoline (column 1, lines 5-6), comprising the following components (Figures 1-3):
a) a methanol to gasoline reactor B (column 4, line 48) comprising a fixed bed of catalyst (column 6, line 50), a separator 228 (column 7, line 25), and a recycle compressor 236 (column 7, line 30). The reactor converts the methanol to gasoline to produce a gasoline product comprising C5+ gasoline and C3-C4 paraffins (column 4, lines 42-66).
b) a separation unit 228 (product separator) which separates a recycle gas stream 230, a product gasoline stream 232 and a water stream 234 (phase separator as claimed), where the recycled gas stream 228 passes through the recycle compressor 236 to the oxygenate feed stream 214 (Figure 2 and column 7, lines 27-31). Harandi further also teaches separating a C2- fuel gas stream and an LPG stream from the gasoline effluent (column 4, lines 60-65).
c) reactor F for aromatization (Figure 1) comprising a catalyst (column 7, line 46). There is no teaching or showing of a conduit for an oxygenate feed to the reactor F, as claimed. The reactor F converts the feed to form aromatics (column 4, lines 66-68) including BTX (benzene, toluene, xylene) (column 5, line 14).
d) a conduit 119 for recycling at least a portion of the aromatics from the reactor F to the reactor B (Figure 1 and column 4, lines 45-48).
Harandi does not specifically teach the separation of the C2-, LPG, and product gasoline streams from the methanol to gasoline effluent is performed in a downstream distillation unit comprising a de-ethanizer and LPG-splitter.
Rajagopalan teaches methanol to gasoline conversion (Abstract). Rajagopalan teaches an apparatus comprising a methanol to gasoline reactor 110 which produces an effluent 115 which is passed into product separator 120 to produce a water stream, a hydrocarbon liquid stream 125, and a recycle gas stream (phase separator instant claim 22) (paragraph [0018, Figure 3). Rajagopalan further teaches separating the hydrocarbon product 125 stream in a deethanizer 370 to produce a C2- (fuel gas) stream and a C3+ stream 375, where stream 375 is then passed to a stabilizer (LPG-splitter) to produce a C3-C4 stream 341 and a product gasoline stream 345 (paragraph [0019]). Thus Rajagopalan teaches that the claimed configuration is a known and suitable configuration for separating recycle gas, C2-, LPG, and gasoline from a methanol to gasoline product stream.
Therefore, it would have been obvious to one of ordinary skill in the art at the time of the invention use the apparatus of Rajagopalan to produce the C2- fuel gas stream, LPG stream, recycle gas stream, and product gasoline stream of Harandi, because each of Harandi and Rajagopalan teach separating a recycle gas stream, a C2- stream, an LPG stream, and a product gasoline stream from a methanol to gasoline product, Harandi does not teach the specific apparatus components used, and Rajagopalan teaches that the deethanizer and stabilizer (LPG splitter) are known and suitable for separating the desired components (paragraph [0019], Fig. 3).
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
/Renee Robinson/Primary Examiner, Art Unit 1772
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