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 Status
Claims 1-11, 15, 16, 18, 19, and 21 were canceled and claims 12 and 17 were amended in the response filed 12/23/2025. Claims 12-14 and 17 are currently pending.
New Claim Rejections - 35 USC § 112(b)-Necessitated by Amendment
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.
Claim 17 is 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.
Lines 19-21 of claim 17 recite: “a valve located between the catalytic distillation reactor system and the first fractionation column configured for taking the first and second fractionation columns out of service during the second period of time”. There is a lack of antecedent basis for the limitation “the second period of time”.
Modified Claim Rejections - 35 USC § 103-Necessitated by Amendment
See rejections of record on p. 3-26 of the OA dated 6/25/2025. The text of those sections of Title 35, U.S. Code not included in this action can be found in a prior Office action. The Applicant canceled claims 1-11, 15, 16, 18, 19, and 21 and incorporated limitations from claims 15 and 16, as well as new limitations from [0055] and Fig. 2 of the specification as filed, into independent claim 12. Therefore, the rejection has been modified to address the amendments.
Claims 12-14 and 17 are rejected under 35 U.S.C. 103 as being unpatentable over Smith, JR. et al.-362 (US 2010/0179362 A1, published on 7/15/2010, of record) in view of Bakshi et al. (US 6,335,473 B1, published 1/1/2002, of record) and further in view of Aittamaa et al. (US 6,613,108 B1, published on 9/2/2003, of record), Smith, JR. et al.-124 (US 5,003,124, 3/26/1991, of record), and Hearn (US 4,447,668 B1, published on 5/8/1984).
Smith, JR. et al.-362 disclose a process for the selective dimerization and etherification of isoolefins comprising feeding a mixed C4 stream comprising isoolefins and a oxygenate to one or more reactors comprising a catalyst (paragraphs 0014-0024). Smith, JR. et al.-362 disclose that any type of reactor may be used to carry out the reactions (paragraph 0021). Examples of reactors suitable for carrying out the reactions involving isoolefin dimerization or oligomerization reactions include distillation column reactors, divided wall column reactors, traditional tubular fixed bed reactors, bubble column reactors, slurry reactors equipped with or without a distillation column, pulsed flow reactors, catalytic distillation columns wherein slurry solid catalysts flow down the column, or any combination of these reactors (paragraph 0021).
In one embodiment of the process an isoolefin is fed to an oligomerization reaction zone along with an oxygen-containing moderator (paragraph 0036). The isoolefin reacts in the presence of a metalized oligomerization catalyst to convert a portion of the isoolefin to oligomers, including dimers and trimers (paragraph 0036). As a side reaction the moderator may react with a portion of at least one of the isoolefin and the oligomerization products in the oligomerization reaction zone to form an oxygenated oligomerization byproduct (paragraph 0036). The reaction effluent may then be fed to a separation system to separate the reaction effluent into the desired fractions (paragraph 0037).
For example, the reaction effluent may be fed to a first distillation column to separate the moderator and unreacted isoolefin from the oligomers and the oxygenated oligomerization byproducts (paragraph 0037). The unreacted isoolefins and moderator may be recovered as overheads and the oligomers and oxygenated oligomerization byproducts may be recovered (paragraph 0037). If desired, the moderator and unreacted isoolefin may be recycled to the oligomerization reaction zone, as required by (paragraph 0037). Examples of moderators that may be utilized include methanol (paragraph 0017). The bottoms fraction may then be fed to a second distillation column where the dimers may be separated from the trimers and oxygenated oligomerization byproducts (paragraph 0038). The dimers may be recovered as an overheads fraction and the trimers and oxygenated oligomerization byproducts may be recovered as a bottoms fraction, (paragraph 0038 and Figure 1). Each may be used in downstream processes, such as the hydrogenation of diisobutene to pure isooctane, (paragraphs 0038, 0004 and 0043). The oligomerization feed may comprise isobutene as the isoolefin, which may further comprise isobutane and the oxygenate can be methanol (paragraphs 0015-0017). The catalysts used in the process are capable of being catalytically active for both dimerization and etherification (paragraphs 0025-0036).
The process of Smith, JR. et al.-362 differs from the instant claims in that although Smith, JR. et al.-362 disclose the use of an oligomerization reaction system and a separation system, Smith, JR. et al.-362 do not expressly disclose that the oligomerization reaction system comprises a first and second fixed bed reactor in conjunction with a catalytic distillation reactor wherein the first reactor effluent is fed to the second reactor and the second reactor effluent is fed to the catalytic distillation reactor.
However, Smith, JR. et al.-362 disclose that any type of reactor may be used to carry out the reactions involving isoolefin dimerization or oligomerization reactions including distillation column reactors, divided wall column reactors, traditional tubular fixed bed reactors or any combination of these reactors. Further, Smith, JR. et al.-362 disclose that examples of the types of reactors that may be used include those disclosed by Bakshi et al., i.e., US 6,335,473 B1, specifically referred to in paragraphs 0021-0022 of Smith, JR. et al.-362, and Aittamaa.
Bakshi et al. disclose a process for reaction of C4 isoolefins with themselves to from oligomers and with C1 to C6 alcohols to form ethers in the presence of acidic catalysts wherein a series of fixed bed boiling point reactors are combined with a catalytic distillation column reactor (column 2, lines 53-57 and column 4, lines 6-55). The use of this reactor system allows for higher conversions of the isoolefins and each of the reactors can be relatively small compared to the use of either bed alone when used to obtain the same level of iso-olefin conversion obtained by the combination (column 4, lines 6-8 and lines 47-55).
Aittamaa et al. disclose that it is known that MTBE and iso-octene (the dimer of isobutene) will be simultaneously produced when the molar ratio of alcohol to isoolefin is below the stoichiometric range (1:1) or in the range of 0.2-0.7:1 (column 1, lines 36-40). A molar ratio of 0.2-0.7 is equivalent to a molar ratio of isoolefin to alcohol of 1.4:1 to 5:1, which encompasses the claimed molar ratio of 2:1 to 5:1 for the dimerization mode and touches the claimed molar ratio of the etherification mode. It is further disclosed that if the ratio is greater than 0.7, only less than 10 wt-% of dimer is formed (column 1, lines 40-41). Further, Aittamaa et al. disclose that when using the process of the invention, iso-olefins can be converted to their dimers or to tertiary ether almost completely (column 3, lines 39-41). Thus, Aittamaa et al. recognized that modifying the molar ratio of isoolefin to alcohol, i.e., C4 to oxygenates, will affect whether the reaction favors the production of dimers or ethers. Further, Aittamaa et al. disclose that one could use a wide range of oxygenate to olefin, which encompasses the claimed molar ratios (column 14, lines 9-12).
Aittamaa also teaches three embodiments, see Fig. 5-7 and discussion thereof in (col. 13-14) which comprise two fixed bed reactors (51, 52, or 61,62 or 71, 72 ) in series, wherein the effluent from the first reactor (51, or 61, or 71) is fed directly to the second reactor (52, or 62, or 72), and the effluent from the second reactor is fed to distillation column (55, 65, or 75). Also see discussion of “reaction zone” in (col. 5, lines 28-43).
Figure 7 of Aittamaa further teaches that column (75), which can optionally be filled with a catalyst (column 11, lines 56-59), produces an overhead stream (D1) comprising unreacted light oxygenates and C4s and a first bottoms stream (B1) comprising dimers, trimers, sand heavy oxygenates are produced. The first bottoms stream (B1) can be fed to a first fractionation column (77) to produce a second overhead stream (D3) comprising oxygenates and a second bottoms stream comprising dimers of the isoolefins and any trimers of the isoolefins. The second overhead stream can be recycled to the first or second reactor, optionally as a “second oxygenate stream”, as line (R2). Though Aittamaa does not explicitly teach subjecting the second bottoms stream to a second fractionation, Aittamaa teaches that the distillation zone can comprise multiple columns. See col. 5, lines 15-28.
The process of Smith, JR. et al.-362 further differs from the instant claims 12-14 in that Smith, JR. et al.-362 do not disclose modifying how the oxygenate is fed to the first and second reactors to be effective as a selectivator for a first and third period of time or as a reactant for a second period of time as disclosed in claims 12 and 13 or transitioning the temperature and/or pressure of the first and second reactors from a dimerization reaction condition used during the first period of time to an etherification reaction condition used during the second period of time as disclosed in claim 14. Nor does Smith, JR. et al.-362 explicitly teach that during the second period of time the first and second fractionation columns are taken out of service via the valve of claim 17.
Smith, JR. et al.-124 disclose a process for the oligomerization of C4 isoolefins or the etherification thereof with C1 to C6 alcohols wherein the reactants may be contacted in one or more reactors including a combination of two fixed bed reactors with a catalytic distillation reactor in the presence of catalysts (column 5, line 37 to column 7, line 35). It is taught that the oligomerizations are run under the same general conditions as the etherifications with the oligomer products being the heavier component of the product stream and it may be desirable in some operations to switch between the oligomerization and etherification reactions by adding or withholding the alcohol as desired.
Hearn is directed toward a process for producing high purity iso-olefins and dimers thereof by dissociation of ethers. See abstract and claims. In Fig. 1, Hearn teaches that a valve (16) can be used to send a crude isobutene stream (22) to produce diisobutene (via line 24) or to recover isobutene (via line 23). See col. 7, lines 25-30. Thus, Hearn describes a system where a valve can be used to take certain parts of the system out of service when the desired product changes.
A person of ordinary skill in the art would have found it prima facie obvious to combine the teachings of Smith, JR et al.-362, Bakshi et al., Aittamaa et al., Smith, JR. et al.-124, and Hearn to arrive at the instantly claimed inventions of independent claims 12 and 17 with a reasonable expectation of success before the effective filing date of the instant application.
Regarding the claimed combination of two fixed bed reactors in series followed by a catalyst distillation reactor system of claims 12 and 17, a person of ordinary skill would have been motivated to arrive at the claimed combination of two fixed bed reactors and a catalytic distillation reactor as taught by Bakshi et al. and Aittamaa et al. for use as the oligomerization reaction system to be used along with the separation system disclosed by Smith, JR et al.-362 in order to carry out the iso-olefin dimerization and oligomerization reactions of Smith, JR. et al.-362, because Smith, JR. et al.-362 disclose that any type of reactor may be used to carry out the reactions including those disclosed by Bakshi et al. and Aittamaa et al. The ordinary skilled artisan would have further been motivated to make the combination, since the use of this reactor system combination allows for higher conversions of the isoolefins and each of the reactors can be relatively small compared to the use of either bed alone when used to obtain the same level of iso-olefin conversion obtained by the combination. Additionally, Aittamaa et al. teaches embodiments (Fig. 5-7) wherein two fixed bed reactors in series are followed by a distillation column which can optionally be packed with a catalyst, such as the catalytic distillation reactor of Bakshi, to produce mixtures of iso-olefin dimers and oxygenates which are concurrently produced and removed in said distillation column. Fig. 5-7 of Aittamaa also teach that the effluent from the first fixed bed reactor is fed directly to the second reactor. Also see MPEP 2143(I)(A).
Regarding the ratio of dimers to oxygenates produced in the reaction of the combined process of Smith-362, Bakshi, and Aittamaa, one having ordinary skill in the art before the effective filing date of the claimed invention would have found it obvious that if desirable one could operate the process of Smith, JR. et al.-362 to selectively react unreacted C4 in a dimerization mode (a first period of time) including a molar ratio of the unreacted C4s to oxygenates from 5:1 to 2:1 or react the unreacted C4 in an etherification mode (a second period of time) including a molar ratio of unreacted C4s to oxygenates from 2:1 to 1:2 based on the teachings of Aittamaa et al. and Smith, JR. et al.-124. Aittamaa et al. discloses that it is known that MTBE and iso-octene (the dimer of isobutene) will be simultaneously produced when the molar ratio of alcohol to iso-olefin is below the stoichiometric range or in the range of 0.2-0.7 and that if the ratio is greater than 0.7, only less than 10 wt-% of dimer is formed. Further, Aittamaa et al. disclose that one could use a wide ratio of oxygenate to olefin, which encompasses the claimed molar ratios (column 14, lines 9-12). Thus, since Aittamaa et al. recognized that modifying the molar ratio of iso-olefin to alcohol, i.e., C4 to oxygenates, will affect whether the reaction favors the production of dimers or ethers one having ordinary skill in the art would have been motivated to modify the molar ratio of C4s to oxygenates to obtain the desired product, including using the claimed molar ratios for either the dimerization mode or the etherification mode.
The teachings of Aittamaa would also lead the skilled artisan to select different molar ratios in each reactor depending on the desired product and conditions in the reaction. Fig. 5-7 of Aittamaa explicitly teach that oxygenate (R2) can be fed to each reactor (see col. 13, line 15-col. 14, line 20).
Smith, JR. et al.-124 also teaches that the selectivity of the products of combined process of Smith-362, Bakshi, and Aittamaa can be predictably controlled through control of the molar ratio between the oxygenate and the C4 feed, which further underscores the predictably of the method. Further, one having ordinary skill in the art before the effective filing date of the claimed invention would have found it obvious that if desirable one could switch between the oligomerization and etherification reactions in the combined process of Smith-362, Bakshi, and Aittamaa, including in the manner as disclosed in claims 12 and 13, since Smith, JR. et al.-124 disclose that if desirable one could switch between the oligomerization and etherification reactions by adding or withholding the alcohol as desired. The ordinary skilled artisan would have further found it obvious to select the appropriate temperature and/or pressure for use in the first and second reactors in order to transition from a dimerization reaction condition used during the first period of time to an etherification reaction condition used during the second period of time as disclosed in claim 14, since the oligomerizations are run under the same general conditions as the etherifications. Also see MPEP 2144.05.
“Generally, differences in concentration or temperature will not support the patentability of subject matter encompassed by the prior art unless there is evidence indicating such concentration or temperature is critical. "Where the general conditions of a claim are disclosed in the prior art, it is not inventive to discover the optimum or workable ranges by routine experimentation." In re Aller , 220 F.2d 454, 105 USPQ 233, 235 (CCPA 1955). Also see MPEP 2144.05.
The process of Smith, JR. et al.-362 further differs from the instant process in that Smith, JR. et al.-362 do not disclose taking the first and second fractionation columns out of service during the second period of time.
However, one having ordinary skill in the art before the effective filing date of the claimed invention would have found it obvious that if desirable one could take the first and second fractionation columns out of service during the second period of time, since Smith, JR. et al.-124 disclose that if desirable one could switch between the oligomerization and etherification reactions by adding or withholding the alcohol as desired. Also see MPEP 2144.04(II).
Additionally, a person of ordinary skill in the art would have found it further obvious to include a valve in the combined process of Smith-362, Bakshi, Aittamaa, and Smith-124 because Hearn teaches that valves can be used to take certain sections of reactions systems out of service when the desired product changes. The combination of Smith-362, Bakshi, Aittamaa, and Smith-124 teach that desired product of the reaction can change between an oligomerization product and an etherification product and how to effect said change such that iso-olefins can be converted to their dimers or to tertiary ether almost completely (column 3, lines 39-41 of Aittamaa). The combined references also teach that the first and second fractionation columns are used to isolate various oligomerization products (for example, see [0037-0038] of Smith-362), but that ethers can be obtained as bottom products in good yields during selective etherification reactions. See (42) in Figs. of Bakshi and discussion thereof in examples 1-2 of col. 7-8. Also see col. 1, line 54-col. 2, line 2 of Smith-124. Thus, if the desired product of the combined process of Smith-362, Bakshi, Aittamaa, and Smith-124 were switched from oligomerization products to etherification products, then the skilled artisan would find it obvious to install a valve, such as that taught by Hearn, between the catalytic distillation reactor system and the first fractionation column and use said valve to take the fractionation columns for oligomer separation out of service. The columns are not needed when the process is run under selective etherification conditions and taking them out of service during this time would predictably lead to a more efficient etherification reaction period.
Further regarding apparatus claim 17, as the combination of Smith, JR et al.-362, Bakshi et al., Aittamaa et al., Smith, JR. et al.-124, and Hearn render the instantly claimed processes prima facie obvious, then the claimed apparatus, which is necessarily used during the claimed process, is also prima facie obvious.
Claims 12-14 and 17 are rejected under 35 U.S.C. 103 as being unpatentable over Aittamaa et al. (US 6,613,108 B1, published on 9/2/2003, of record) in view of Hearn (US 4,447,668 B1, published on 5/8/1984).
Aittamaa et al. disclose that it is known that MTBE and iso-octene (the dimer of isobutene) will be simultaneously produced when the molar ratio of alcohol to isoolefin is below the stoichiometric range or in the range of 0.2-0.7 (column 1, lines 36-40). A molar ratio of 0.2-0.7 is equivalent to a molar ratio of isoolefin to alcohol of 1.4:1 to 5:1, which encompasses the claimed molar ratio of 2:1 to 5:1 for the dimerization mode and touches the claimed molar ratio of the etherification mode of claims 1 and 12. It is further disclosed that if the ratio is greater than 0.7, only less than 10 wt-% of dimer is formed (column 1, lines 40-41). Also see MPEP 2144.05.
Aittamaa et al. disclose a process for dimerizing and etherifying a C4 olefin feed in the presence of an alcohol or another oxygenate in a reaction sequence comprising at least one distillation zone and at least one reaction zone (column 2, lines 25-28). The reaction is carried out at conditions in which at least part of the olefins dimerize (column 2, lines 28-30). The distillation zone is arranged after the reaction zone and a flow comprising oxygenate or the products of reaction are circulated from the distillation zone back to the dimerization (column 2, lines 30-35 and column 6, lines 19-23). The mole ratio of alcohol or other oxygenate is adjusted to be small during the reaction, thus maintaining the rate of dimerization high (column 2, lines 38-40). The product produced by the reaction may be hydrogenated to isooctane, which is useful as a fuel component (the paragraph bridging columns 2 and 3).
When using the process, the isoolefins can be converted to their dimers or to tertiary ether almost completely (ie selectively, column 3, lines 39-41). With the aid of the invention an isobutene processing plant, such as MTBE-unit, can be modified to a dimerization unit without high expenses (column 3, lines 45-47). At the conditions where dimer is formed, the fraction containing ether or alcohol or a mixture thereof, is taken as a side draw from the distillation column and circulated back to the reaction zone (column 3, lines 49-52 and column 6, lines 10-18). The ether or alcohol functions as an oxygen-containing component and decomposes in the reaction zone at least partly to alcohol and olefin. When all the ether is circulated back, then dimers and minor amounts of trimers and heavier hydrocarbons are produced, while if part of the ether is recovered, then alcohol is preferably added in order to maintain the conditions beneficial for dimer selectivity (column 3, lines 52-59).
The conditions in the reaction zone can be optimized to match different production objectives. The switch from one product to another is simple, thus creating perfect flexibility to answer to the demands of the changing market (column 3, lines 60-65). With the aid of recycling flow the temperature in the reactor can be slightly lowered compared to conventional etherification process (the paragraph bridging columns 3 and 4). The rate of reaction can be increased by increasing the temperature in the process (column 4, lines 11-13). The C4 -hydrocarbon feed is a mixed feed (column 6, line 39 to column 7, line 10). The product can be a mixture of iso-octene and MTBE (column 7, lines 20-23). The oxygen-containing compound (an oxygenate) is fed into the process in order to slow down the oligomerization reactions of the olefin, increase dimer selectivity and to decrease the catalyst poisoning (the paragraph bridging columns 7 and 8). The oxygenate can be water, ether or alcohol, such as methanol (column 8, lines 18-23). The formation of dimers can be enhanced by increasing the temperature during the reaction or a lower temperature may be used to favor the formation of ethers (column 9, lines 32-35). The composition of the product flow depends on the process parameters and on the composition of the feed (column 10, lines 15-16). An ether can function as the oxygen-containing compound and decomposes partly to alcohol and olefin in the reactor (column 11, lines 52-54). If all of the ether is circulated back to the reaction zone, the bottoms product of the distillation zone comprises iso-octene (column 11, lines 54-56).
Catalyst can be placed inside some of the distillation columns presented above in order to increase the conversion of olefin, whereby the formation of ether is increased (column 11, lines 56-59). Both dimerized olefin and alkyl ether can be produced in the process (column 11, lines 60-61). In this case, the olefin and alcohol have to react with each other. Thus, for example isobutene and methanol or ethanol are fed to the process. The decreasing of the reaction temperature during the reaction enhances the formation of tertiary ether. A mixture comprising iso-octene and tertiary ethers, the weight fraction of iso-octene of the isobutene reaction products being 20-95 wt%, is recovered as bottoms of the distillation zone. If the tertiary ether is removed from the process, it is necessary to feed more alcohol in order to maintain reaction conditions suitable for the dimerization reaction. Alcohol can be fed either directly to the reaction zone or together with the fresh feed (paragraph bridging columns 11 and 12). The conditions in the reactors can be optimized for the production of only dimers and trimer (80-120°C) or when producing also tertiary ether (50-70°C) (column 12, lines 7-11). Aittamaa et al. further disclose that one could use a wide ratio of oxygenate to olefin, which encompasses the claimed molar ratios for both the claimed dimerization mode and the claimed etherification mode (column 14, lines 9-12).
One having ordinary skill in the art before the effective filing date of the claimed invention would have found it obvious that if desirable one could operate the process of Aittamaa et al. to selectively react unreacted C4 in a dimerization mode (a first period of time) including a molar ratio of the unreacted C4s to oxygenates from 5:1 to 2:1 or react the unreacted C4 in an etherification mode (a second period of time) including a molar ratio of unreacted C4s to oxygenates from 2:1 to 1:2, since Aittamaa et al. disclose that it is known that MTBE and iso-octene (the dimer of isobutene) will be simultaneously produced when the molar ratio of alcohol to isoolefin is below the stoichiometric range or in the range of 0.2-0.7 and that if the ratio is greater than 0.7, only less than 10 wt-% of dimer is formed.
One having ordinary skill in the art would have been motivated to modify the molar ratio of C4s to oxygenates to obtain the desired product, including using the claimed molar ratios for either the dimerization mode or the etherification mode, since Aittamaa et al. recognized that modifying the molar ratio of isoolefin to alcohol, i.e., C4 to oxygenates, will affect whether the reaction favors the production of dimers or ethers. Generally, differences in concentration or temperature will not support the patentability of subject matter encompassed by the prior art unless there is evidence indicating such concentration or temperature is critical. "Where the general conditions of a claim are disclosed in the prior art, it is not inventive to discover the optimum or workable ranges by routine experimentation." In re Aller , 220 F.2d 454, 105 USPQ 233, 235 (CCPA 1955). MPEP 2144.05.
This same argument applies to the concentrations required for “selectivator” activity in claims 12-14. The teachings of Aittamaa would also lead the skilled artisan to select different molar ratios in each reactor depending on the desired product and conditions in the reaction. Aittamaa teaches how and why a person of ordinary skill in the art would modify the disclosed process to select dimer and/or ethers products. Therefore, modifying the known process of Aittamaa according to the explicit suggestions and procedures of Aittamaa to predictably obtain dimers and/or ethers would be prima facie obvious to the skilled artisan and would not require excessive optimization. Also see MPEP 2144.04(II) regarding the omission of elements if not desired as being obvious.
Aittamaa et al. differ from the claimed invention in that Aittamaa et al. do not require the use of two fixed bed reactors in combination with a catalytic distillation reactor and two fractionation columns as required by claims 12 and 17.
However, Aittamaa et al. disclose that for the purposes of their invention the distillation zone designates a distillation system comprising one or more distillation columns, preferably connected in series (column 5, lines 18-21). The distillation column can be any column suitable for distillation (column 5, lines 25-27). The reaction zone comprises at least one, typically two or three reactors and can include tubular reactors, a boiler reactor or a packed bed reactor (column 5, lines 28-43). Catalyst can be placed inside some of the distillation columns presented above in order to increase the conversion of olefin, whereby the formation of ether is increased (column 11, lines 56-59).
Aittamaa also teaches three embodiments, see Fig. 5-7 and discussion thereof in (col. 13-14) which comprise two fixed bed reactors (51, 52, or 61,62 or 71, 72 ) in series, wherein the effluent from the first reactor (51, or 61, or 71) is fed directly to the second reactor (52, or 62, or 72), and the effluent from the second reactor is fed to distillation column (55, 65, or 75). Also see discussion of “reaction zone” in (col. 5, lines 28-43). In Fig. 7, in the column (75), which can optionally be filled with a catalyst (column 11, lines 56-59), an overhead stream (D1) comprising unreacted light oxygenates and C4s and a first bottoms stream (B1) comprising dimers, trimers, sand heavy oxygenates are produced. The first bottoms stream (B1) can be fed to a first fractionation column (77) to produce a second overhead stream (D3) comprising oxygenates and a second bottoms stream comprising dimers of the isoolefins and any trimers of the isoolefins. The second overhead stream can be recycled to the first or second reactor, optionally as a “second oxygenate stream”, as line (R2). Though Aittamaa does not explicitly teach subjecting the second bottoms stream to a second fractionation, Aittamaa teaches that the distillation zone can comprise multiple columns. See col. 5, lines 15-28.
Aittamaa further differs from claims 12 and 17 in that it does not explicitly teach the use of a valve located between the catalytic distillation reactor steam and the first fractionation column configured for taking the first and second fractionation columns out of service during a second period of time.
Hearn is directed toward a process for producing high purity iso-olefins and dimers thereof by dissociation of ethers. See abstract and claims. In Fig. 1, Hearn teaches that a valve (16) can be used to send a crude isobutene stream (22) to produce diisobutene (via line 24) or to recover isobutene (via line 23). See col. 7, lines 25-30. Thus, Hearn describes a system where a valve can be used to take certain parts of the system out of service when the desired product changes.
One having ordinary skill in the art before the effective filing date of the claimed invention would have found it obvious to carry out the process disclosed by Aittamaa et al. in two fixed bed reactors in combination with a catalytic distillation reactor and two fractionation columns, since Aittamaa et al. disclose that for the purposes of their invention the distillation zone designates a distillation system comprising one or more distillation columns, preferably connected in series. The distillation column can be any column suitable for distillation. The reaction zone comprises at least one, typically two or three reactors and can include tubular reactors, a boiler reactor or a packed bed reactor. Catalyst can be placed inside some of the distillation columns presented above in order to increase the conversion of olefin, whereby the formation of ether is increased.
The ordinary skilled artisan would have further been motivated to utilize a catalytic distillation column for at least one of the distillation columns in order to increase the conversion of olefin, for instance when there is a desire to increase the formation of ether. Further regarding claim 12, the skilled artisan would have found it prima facie obvious before the effective filing date of the instant invention to include a second bottoms separation column in order to predictably separate the lighter, more desirable dimer product, from the heavier trimer product.
One having ordinary skill in the art before the effective filing date of the claimed invention would have found it obvious to include a valve in the process disclosed by Aittamaa et because Hearn teaches that valves can be used to take certain sections of reactions systems out of service when the desired product changes. Aittamaa teaches that desired product of the reaction can change between an oligomerization product and an etherification product and how to effect said change such that iso-olefins can be converted to their dimers or to tertiary ether almost completely (column 3, lines 39-41). Aittamaa further teaches that oligomers and ethers are both obtained as bottom products (B1) from the distillation reactor (75) in Fig. 7 and that the bottom product (B1) can be further separated in an additional column to produce an overhead comprising ethers (D3) and a bottoms product comprising oligomers (B3). See col. 13, lines 15-59. As argued above, it would have been obvious to distill the second bottoms fraction (B3) to further separate the dimers from other less desirable oligomerization products. Also see col. 1, line 65-col. 2, line 4 and col. 5, line 65-col. 6, line 9. Thus, if the desired product of the process of Aittamaa were switched from oligomerization products to etherification products, then the skilled artisan would find it obvious to install a valve, such as that taught by Hearn, between the catalytic distillation reactor system and the first fractionation column and use said valve to take the fractionation columns for oligomer separation out of service. The columns are not needed when the process is run under selective etherification conditions and taking them out of service during this time would predictably lead to a more efficient etherification reaction period.
Further regarding claim 17, as the claimed process is rendered prima facie obvious by the teachings of Aittamaa then the claimed apparatus, which is necessarily used during the claimed process, is also prima facie obvious. Also see MPEP 2144.04(II) regarding the omission of elements if not desired as being obvious.
Response to Applicant Arguments on p. 8-13 of the response dated 12/23/2025:
Regarding the rejection over Smith, JR. et al.-362 (US 2010/0179362 A1, published on 7/15/2010, of record) in view of Bakshi et al. (US 6,335,473 B1, published 1/1/2002, of record) and further in view of Aittamaa et al. (US 6,613,108 B1, published on 9/2/2003, of record) and Smith, JR. et al.-124 (US 5,003,124, 3/26/1991, of record), the Applicant argues, regarding independent claims 12 and 17, that the instant invention is distinct from the prior art because it is directed toward a process and system for selectively and changeably, converting a mixed C4 stream into a dimerized product and an etherified product by placing one or more units into service, or taking one or more units out of service. The Applicant argues that these are not alternate system arrangements that may be disposed during commissioning depending on whether the system is desired to produce an oligomer product or an ether product and that it is also not simply accomplished by changing the feedstocks.
Specifically, the Applicant argues that:
“The Examiner asserts that Smith, JR. et al.-362 disclose a process for the selective dimerization and etherification of isoolefins comprising feeding a mixed C4 stream comprising isoolefins and a oxygenate to one or more reactors comprising a catalyst. However, the Examiner admits Smith, JR. et al.-362 fails to disclose selectively reacting unreacted C4 in a dimerization mode (a first period of time) or reacting the unreacted C4 in an etherification mode (a second period of time), and that Smith, JR. et al.-362 fails to disclose "taking the first and second fractionating columns out of service during the second period of time." See Office Action, page 12.
The Examiner asserts, however, that Smith, JR. et al.-124 discloses that it is desirable to switch between oligomerization and etherification reactions by adding or withholding the alcohol as desired. See Office Action, page 12. Applicant respectfully disagrees.
As pointed out by the Examiner, Smith, JR. et al.-124 discloses that, if desirable, one could switch between an oligomerization and etherification reactions by adding or withholding an alcohol as desired. See Smith, JR. et al.-124, col. 8, 11. 27-36. This is a markedly different than the process of "taking the first and second fractionation columns out of service during the second period of time."
However, the Examiner asserts "one having ordinary skill in the art... would have found it obvious that if desirable one could take the first and second fractionation columns out of service during the second period of time, since Smith, JR. et al.-124 disclose that if desirable one could switch between the oligomerization and etherification reactions by adding or withholding the alcohol as desired." This is incorrect. Smith, JR et al. -124 makes no mention of bypassing the fractionation columns, and instead only teaches the addition or removal of alcohol feedstock. The Examiner is making a logical extension that finds no support in the prior art, and this is insufficient to support a finding of obviousness.
Further, the Examiner cites to MPEP 2144.04(II) to support the obviousness of taking fractionation columns out of service. However, as pointed out, that is not what is happening. Starting with Smith, JR et al -124, if one of ordinary skill in the art were to wish to change from oligomerization to etherification, they would only be motivated to adjust the alcohol feedstock and would not be motivated to remove any separation or fractionation columns from service. Conventional knowledge in downstream processing would be to include one or more separation columns to obtain the desired components from a product mixture, and there is no indication in Smith JR et al -124 or Smith, JR. et al. -362 that the separations disclosed therein are inadequate or inappropriate to be used when changing the reaction.
Accordingly, claim 12 as amended is believed to patentable over Smith, JR. et al.-362 in view of Smith, JR. et al.-124. Withdrawal of the rejection and allowance of claim 12, and claims dependent therefrom, is respectfully requested.
Regarding claim 17, claim 17 requires, "a valve located between the catalytic distillation reactor system and the first fractionation column configured for taking the first and second fractionation columns out of service during the second period of time...."
In the Office Action, the Examiner makes the singular statement, "Further regarding apparatus claims 17-19 and 21, as the combination of Smith, JR et al.-362, Bakshi et al., Aittamaa et al., and Smith, JR. et al.-124 render the instantly claimed processes prima facie obvious, then the claimed apparatus, which is necessarily used during the claimed process, is also prima facie obvious."
Applicant reminds the Examiner that to make a proper find of obviousness, the Examiner may not merely point to the presence of all claim elements in the prior art as a complete statement of a rejection for obviousness. The Examiner must provide articulated rationale for why one of ordinary skill in the art would find the claim obvious. See MPEP 2143. Further, in this case, the combination of Smith, JR et al.-362, Bakshi et al., Aittamaa et al., and Smith, JR. et al.-124 fail to disclose or suggest "a valve located between the catalytic distillation reactor system and the first fractionation column" as required by amended claim 17. As argued, Smith, JR et al.-362, Bakshi et al., Aittamaa et al., and Smith, JR. et al.-124 individually fail to disclose removing one or more fractionation columns during a second period of time, via a valve or otherwise. Accordingly, no combination of Smith, JR et al.-362, Bakshi et al., Aittamaa et al., and Smith, JR. et al.-124 would suggest to one of ordinary skill in the art to include a valve located between the catalytic distillation reactor system and the first fractionation column.
Accordingly, claim 17 as amended is believed to patentable over Smith, JR et al.-362, Bakshi et al., Aittamaa et al., and Smith, JR. et al.-124. Withdrawal of the rejection and allowance of claim 17, and claims dependent therefrom, is respectfully requested. ”
These arguments have been fully considered but are not persuasive. In response to applicant's arguments against the references individually, one cannot show nonobviousness by attacking references individually where the rejections are based on combinations of references. See In re Keller, 642 F.2d 413, 208 USPQ 871 (CCPA 1981); In re Merck & Co., 800 F.2d 1091, 231 USPQ 375 (Fed. Cir. 1986). Additionally, Hearns was included as an additional reference to teach the new claim limitation of a valve.
As discussed in the rejection above, a person of ordinary skill in the art would have found it further obvious to include a valve in the combined process of Smith-362, Bakshi, Aittamaa, and Smith-124 because Hearn teaches that valves can be used to take certain sections of reactions systems out of service when the desired product changes. The combination of Smith-362, Bakshi, Aittamaa, and Smith-124 teach that desired product of the reaction can change between an oligomerization product and an etherification product and how to effect said change such that iso-olefins can be converted to their dimers or to tertiary ether almost completely (column 3, lines 39-41 of Aittamaa). The combined references also teach that the first and second fractionation columns are used to isolate various oligomerization products (for example, see [0037-0038] of Smith-362), but that ethers can be obtained as bottom products in good yields during selective etherification reactions. See (42) in Figs. of Bakshi and discussion thereof in examples 1-2 of col. 7-8. Also see col. 1, line 54-col. 2, line 2 of Smith-124. Thus, if the desired product of the combined process of Smith-362, Bakshi, Aittamaa, and Smith-124 were switched from oligomerization products to etherification products, then the skilled artisan would find it obvious to install a valve, such as that taught by Hearn, between the catalytic distillation reactor system and the first fractionation column and use said valve to take the fractionation columns for oligomer separation out of service. The columns are not needed when the process is run under selective etherification conditions and taking them out of service during this time would predictably lead to a more efficient etherification reaction period.
While Hearns specifically provides support for the use of a valve to take the columns out of service, the teachings of the other references show that the first and second fractionation columns are not required if the process is selectively producing etherification products. Smith-362 teaches all of the purification details of the first and second fractionation column as applied to oligomerization products. Therefore, if the selectively of the process were changed according to the predictable and well-known methods of the prior art cited in the rejection, then it would also be obvious to omit any unnecessary purification systems to increase the efficiency of the process. Thus, the Examiner respectfully disagrees with the Applicant regarding the applicability of MPEP 2144.04(II), in particular section (A). The Office maintains that the instantly claimed process and apparatus is obvious in view of the cited prior art.
The Applicant applies the same arguments towards the rejection over Aittamaa, now Aittamaa in view of Hearn. These arguments have been fully considered but are not persuasive. As argued in the rejection: one having ordinary skill in the art before the effective filing date of the claimed invention would have found it obvious to include a valve in the process disclosed by Aittamaa et because Hearn teaches that valves can be used to take certain sections of reactions systems out of service when the desired product changes. Aittamaa teaches that desired product of the reaction can change between an oligomerization product and an etherification product and how to effect said change such that iso-olefins can be converted to their dimers or to tertiary ether almost completely (column 3, lines 39-41). Aittamaa further teaches that oligomers and ethers are both obtained as bottom products (B1) from the distillation reactor (75) in Fig. 7 and that the bottom product (B1) can be further separated in an additional column to produce an overhead comprising ethers (D3) and a bottoms product comprising oligomers (B3). See col. 13, lines 15-59. As argued above, it would have been obvious to distill the second bottoms fraction (B3) to further separate the dimers from other less desirable oligomerization products. Also see col. 1, line 65-col. 2, line 4 and col. 5, line 65-col. 6, line 9. Thus, if the desired product of the process of Aittamaa were switched from oligomerization products to etherification products, then the skilled artisan would find it obvious to install a valve, such as that taught by Hearn, between the catalytic distillation reactor system and the first fractionation column and use said valve to take the fractionation columns for oligomer separation out of service. The columns are not needed when the process is run under selective etherification conditions and taking them out of service during this time would predictably lead to a more efficient etherification reaction period. The Office maintains that the instantly claimed process and apparatus is obvious in view of the cited prior art.
The Office further notes that there are no examples in the specification as filed. Therefore, there is no evidence that the claimed combination of elements provides any unexpected advantages or results over the prior art recited above.
Withdrawn Non-Statutory Double Patenting Rejections
See p. 26-38 of previous OA (6/23/2025) for rejections of record.
The amendments filed 12/23/2025 are persuasive to overcome the rejections of record over US 11939289 and US 11312671. The instant process requires a specific fractionation column sequence and a method for taking the columns out of service that is not taught by the claims of ‘289 and ‘671. Nor do the claims of ‘289 and ‘671 teach the conditions of the first and second periods of time. The claims of ‘289 and ‘371 are directed toward a dimerization process using a divided wall column to obtain high purity dimerization products. It would does appear to be obvious to modify the claimed processes to arrive at the instant inventions based on prior art. Also see p. 13-14 of the response filed 12/23/2025. Therefore, the rejections are withdrawn.
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.
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/AMY C BONAPARTE/ Primary Examiner, Art Unit 1692