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 .
Claim Status
Claims 1, 3, 5, 7, 8, 11, and 17 are amended.
The amendments to claims 1, 3, 5, 7, 8, 11, and 17 overcome the previous 112(b) rejections and claim objections.
Claims 1-20 are pending for examination below.
Response to Arguments
Applicant’s arguments, see Remarks, filed 28 August 2025, with respect to the rejection(s) of claim(s) 1 and 3-20 under USC 103 over Harandi in view of Chen and Joensen have been fully considered and are persuasive. Harandi in view of Chen and Joensen does not provide motivation to recycle at least a portion of the gasoline product as well as passing at least a portion of the aromatization effluent to the oxygenate to gasoline step, as newly amended. Therefore, the rejection has been withdrawn. However, upon further consideration, a new ground(s) of rejection is made in view of a different prior art in view of the amendment.
Applicant's arguments regarding claim 2 have been fully considered, but are not persuasive.
Applicant argues on page 13 of the Remarks that the recycling of benzene specifically to the MTG reactor provides additional technical benefits by being alkylated in the reactor to higher aromatics, thus reducing excessive benzene amounts.
In response, the Examiner respectfully disagrees that this is unexpected based on the teachings of newly cited primary reference Harandi and previously cited secondary reference Kong. Harandi specifically teaches recycling aromatics from the aromatization reactor to the MTG reactor in order to produce additional alkylated aromatics (column 2, lines 52-54), and Kong specifically teaches that the alkylation of benzene to toluene and xylenes will take place in a MTG reactor, which reduces the need for benzene extraction (paragraph [0013]). Also, one of ordinary skill in the art is aware of the regulations which limit the amount of benzene in gasoline. Thus, it is not unexpected that the recycling of benzene would reduce the amount of benzene and produce additional alkylated aromatics, as this is explicitly taught by Harandi and Kong, and the combination is maintained.
Applicant argues on page 14 of the Remarks that Kong does not teach upgrading LPG to produce benzene and then recycling the benzene to the MTG reactor, and instead teaches obviating the upgrading reactor and using LPG directly as a cofeed to the MTG reactor.
In response, the Examiner respectfully disagrees with this interpretation of Kong. While Kong does not teach the aromatization reactor to produce the benzene, this is already taught by new primary reference Harandi. Thus, the argument that the secondary reference doesn’t teach the limitation is moot, as the secondary reference is not needed for this limitation. Further, while Kong is directed to recycling the benzene from the MTG reactor to the MTG reactor, the teaching of Kong is that recycling benzene into the MTG reactor allows the conversion of benzene to other aromatics, and eliminates the need for benzene extraction (paragraph [0013]). Thus, while the source of the benzene in Kong is different, it is the Examiner’s position that the motivation of Kong, which is that the benzene can be specifically recycled to produce additional alkylated aromatics and avoid benzene extraction from the gasoline product, remains relevant to the reaction of Harandi, even if the benzene is produced in the aromatization reactor of Harandi rather than the MTG reactor as in Kong. One of ordinary skill in the art, reading the teaching of Kong in paragraph [0013], would be motivated to recycle any benzene from the process to the MTG reactor, in order to avoid the undesirable accumulation of benzene in the gasoline and to produce other desirable aromatics. Thus, one of ordinary skill in the art would find it obvious to add the step of separating and recycling the benzene from the aromatization product stream of Harandi to the MTG reactor of Harandi, as claimed, because Harandi teaches the presence of benzene in the aromatic product and that the recycling allows alkylation of the aromatics, Kong teaches that benzene is known to specifically be alkylated to other aromatics which are more desirable in gasoline than benzene, and one of ordinary skill in the art is aware that benzene is an undesirable component of gasoline in large quantities and would be motivated to reduce the content.
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, 6, 11, 14, and 15 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) in view of Joensen et al. (US 2009/0071871).
With regard to claims 1, 4, and 15, Harandi teaches a method for producing gasoline (column 1, lines 5-6), comprising the following steps:
a) providing a stream comprising methanol (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 C3-C4 paraffin stream and a C5+ gasoline product stream (column 4, lines 59-66).
c) 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).
d) 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.
Harandi fails to specifically teach recycling a portion of the gasoline effluent to the MTG reactor B in combination with the oxygenate stream.
Joensen teaches a process for conversion of oxygenates to gasoline including a C5+ product (paragraphs [0001] and [0049]). Joensen further teaches that mixing a portion of the gasoline product stream with the oxygenate feed for the gasoline reaction actually increases the average carbon number of the product, lowering the volatility and increasing gasoline yields (paragraph [0050]).
Therefore, it would have been obvious to one of ordinary skill in the art at the time of the invention to recycle a portion of the gasoline product stream by mixing with the oxygenate stream of Harandi, because each of Harandi and Joensen teach producing a C5+ gasoline product from a oxygenate to gasoline reactor, and Joensen teaches that recycling a portion of the product by mixing with the oxygenate feed increases the average carbon number of the product, lowering the volatility and increasing gasoline yields (paragraph [0050]).
With regard to claim 6, Harandi teaches separating a fuel gas stream comprising C2- compounds from the MTG product before the separation of a C3-C4 paraffin stream (column 4, lines 60-65). While Harandi does not explicitly teach the separation includes a deethanizer, it would have been obvious to one of ordinary skill in the art at the time of the invention to use a deethanizer to separate the fuel gas stream, as this is a well known type of column that is well known to be used for the specific separation explicitly taught by Harandi.
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.
With regard to claim 14, 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 distillation section D which separates a gasoline stream from reactor B into a stream comprising gasoline 121, a stream comprising C3-C4 paraffins 122, and a fuel gas C2- stream 112 (Figure 1 and column 4, lines 58-62). While Harandi does not specifically teach that the distillation section D comprises a deethanizer and an LPG splitter, as Harandi teaches producing the same fuel gas stream and LPG (C3-C4) stream, it would have been obvious to one of ordinary skill in the art at the time of the invention to use a deethanizer and an LPG splitter to produce these streams, as these are well known columns that are well known to be used for the specific separations explicitly taught by Harandi.
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).
Claim 2 is rejected under 35 U.S.C. 103 as being unpatentable over Harandi et al. (US 4,835,329) in view of Joensen et al. (US 2009/0071871)as applied to claim 1 above, and further in view of Kong et al. (CN 102746877, machine translation provided).
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.
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 recycling aromatics from the upgrading reactor to the methanol to gasoline reactor in order to alkylate the aromatics, and Kong teaches that specifically recycling benzene eliminates the need for benzene extraction (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) in view of Joensen et al. (US 2009/0071871) 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) in view of Joensen et al. (US 2009/0071871) 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 Chen, because each of Chen 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 7 is rejected under 35 U.S.C. 103 as being unpatentable over Harandi et al. (US 4,835,329) in view of Joensen et al. (US 2009/0071871) as applied to claim 6 above, and further in view of Dupassieux et al. (US 2012/0165581).
With regard to claim 7, Harandi in view of Joensen teaches the process above, where the fuel gas comprises hydrogen (column 4, line 62).
Harandi in view of Joensen 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) in view of Joensen et al. (US 2009/0071871) 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 in view of Joensen 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 in view of Joensen 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) in view of Joensen et al. (US 2009/0071871) 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) in view of Joensen et al. (US 2009/0071871) 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) in view of Joensen et al. (US 2009/0071871) as applied to claim 1 above, and further in view of Ma (CN 105885912, machine translation provided).
With regard to claim 13, Harandi in view of Joensen teaches the method above, where the aromatic hydrocarbons are recycled to the MTG reactor.
Harandi in view Joensen 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 in view of Joensen, because Harandi in view of Joensen 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]).
Conclusion
Applicant's amendment necessitated the new ground(s) of rejection presented in this Office action. Accordingly, THIS ACTION IS MADE FINAL. See MPEP § 706.07(a). Applicant is reminded of the extension of time policy as set forth in 37 CFR 1.136(a).
A shortened statutory period for reply to this final action is set to expire THREE MONTHS from the mailing date of this action. In the event a first reply is filed within TWO MONTHS of the mailing date of this final action and the advisory action is not mailed until after the end of the THREE-MONTH shortened statutory period, then the shortened statutory period will expire on the date the advisory action is mailed, and any nonprovisional extension fee (37 CFR 1.17(a)) pursuant to 37 CFR 1.136(a) will be calculated from the mailing date of the advisory action. In no event, however, will the statutory period for reply expire later than SIX MONTHS from the mailing date of this final action.
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
/YOUNGSUL JEONG/Primary Examiner, Art Unit 1772