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 1-20 were submitted on 05/11/2023. The preliminary amendment filed on 05/11/2023 is acknowledged. Claims 3-9 and 11-20 have been amended.
Claims 1-20 are currently pending and under examination.
Priority
The instant application is a 371 of PCT/IB2021/061976 filed on 12/17/2021 which claims foreign priority to EP application no. 20215789.7 filed on 12/18/2020. The certified copies of the foreign priority applications filed on 05/11/2023 are acknowledged.
Information Disclosure Statement
The information disclosure statements (IDS) submitted on 05/11/2023 are in compliance with the provisions of 37 CFR 1.97. Accordingly, the information disclosure statements are being considered by the examiner.
Specification
The specification is objected to as failing to provide proper antecedent basis for the claimed subject matter. See 37 CFR 1.75(d)(1) and MPEP § 608.01(o). Correction of the following is required: Instant claim 5 recites the contacting of the catalyst with the first selectivity-modifying gaseous composition is at a pressure in the range of 5 barg to 35 barg. The instant specification provides the contacting of the catalyst with the first selectivity-modifying gaseous composition in the pressure range of 15-40 barg and pressures not within those limits are not discussed. Therefore, a lack of antecedent basis exists for the pressure range recited in instant claim 5.
Claim Objections
Claim 2 is objected to because of the following informalities: Instant claim 2 recites “of any of claim 1” in the preamble. Reciting “of any of claim 1” does not allow for clarity in the claim language. Applicant is suggested to remove “any of” to increase claim clarity (see MPEP 2173.02(III)). Appropriate correction is required.
Claim Rejections - 35 USC § 112
The following is a quotation of 35 U.S.C. 112(b):
(b) CONCLUSION.—The specification shall conclude with one or more claims particularly pointing out and distinctly claiming the subject matter which the inventor or a joint inventor regards as the invention.
The following is a quotation of 35 U.S.C. 112 (pre-AIA ), second paragraph:
The specification shall conclude with one or more claims particularly pointing out and distinctly claiming the subject matter which the applicant regards as his invention.
Claims 2-6, 8, 11, and 14 are rejected under 35 U.S.C. 112(b) or 35 U.S.C. 112 (pre-AIA ), second paragraph, as being indefinite for failing to particularly point out and distinctly claim the subject matter which the inventor or a joint inventor (or for applications subject to pre-AIA 35 U.S.C. 112, the applicant), regards as the invention.
Claim 2 recites the limitation "the first selectivity-modifying gaseous composition" in the body of the claim. Claim 2 depends on claim 1 which does not recite a first selectivity-modifying gaseous composition. There is insufficient antecedent basis for this limitation in the claim. In the interest of compact prosecution, “the first selectivity-modifying gaseous composition” recited in instant claims 2-6 and 8 will be interpreted by the examiner to be the “selectivity-modifying gaseous composition” recited in the third paragraph of instant claim 1. In the interest of compact prosecution, any claims that recite limitations in an active step with “the first selectivity-modifying gaseous composition” will be interpreted to be limiting the recited active step in the third paragraph of instant claim 1 with the “selectivity-modifying gaseous composition”.
Similarly, claims 11 and 14 recite the limitation “the third gaseous feed” in the bodies of the respective claims. Claims 11 and 14 both depend on claim 10 which does not recite a third gaseous feed. There is insufficient antecedent basis for these limitations in these claims.
The following is a quotation of 35 U.S.C. 112(d):
(d) REFERENCE IN DEPENDENT FORMS.—Subject to subsection (e), a claim in dependent form shall contain a reference to a claim previously set forth and then specify a further limitation of the subject matter claimed. A claim in dependent form shall be construed to incorporate by reference all the limitations of the claim to which it refers.
The following is a quotation of pre-AIA 35 U.S.C. 112, fourth paragraph:
Subject to the following paragraph [i.e., the fifth paragraph of pre-AIA 35 U.S.C. 112], a claim in dependent form shall contain a reference to a claim previously set forth and then specify a further limitation of the subject matter claimed. A claim in dependent form shall be construed to incorporate by reference all the limitations of the claim to which it refers.
Claims 5 and 7 are rejected under 35 U.S.C. 112(d) or pre-AIA 35 U.S.C. 112, 4th paragraph, as being of improper dependent form for failing to further limit the subject matter of the claim upon which it depends, or for failing to include all the limitations of the claim upon which it depends.
Claim 5 recites a pressure range of 5 to 35 barg for the contacting of the catalyst with the first selectivity-modifying gaseous composition. Claim 5 depends from claim 1 which recites the pressure of the same active step to be 10 barg to 40 barg. The recited range of claim 5 does not further limit the recited range of claim 1. Applicant may cancel the claim(s), amend the claim(s) to place the claim(s) in proper dependent form, rewrite the claim(s) in independent form, or present a sufficient showing that the dependent claim(s) complies with the statutory requirements.
Claim 7 recites “the second selectivity for alcohols is no more than 20% of the first selectivity for alcohols.” Claim 7 depends on claim 1 which recites “a second selectivity for alcohols of no more than 5%.” As disclosed by the specification, the first selectivity of alcohols can be anything greater than 5%. Therefore, claim 7 recites a broader range for the second selectivity of alcohols than what is recited in claim 1 and does not further limit claim 1. Applicant may cancel the claim(s), amend the claim(s) to place the claim(s) in proper dependent form, rewrite the claim(s) in independent form, or present a sufficient showing that the dependent claim(s) complies with the statutory requirements.
Claim Rejections - 35 USC § 103
In the event the determination of the status of the application as subject to AIA 35 U.S.C. 102 and 103 (or as subject to pre-AIA 35 U.S.C. 102 and 103) is incorrect, any correction of the statutory basis (i.e., changing from AIA to pre-AIA ) for the rejection will not be considered a new ground of rejection if the prior art relied upon, and the rationale supporting the rejection, would be the same under either status.
The following is a quotation of 35 U.S.C. 103 which forms the basis for all obviousness rejections set forth in this Office action:
A patent for a claimed invention may not be obtained, notwithstanding that the claimed invention is not identically disclosed as set forth in section 102, if the differences between the claimed invention and the prior art are such that the claimed invention as a whole would have been obvious before the effective filing date of the claimed invention to a person having ordinary skill in the art to which the claimed invention pertains. Patentability shall not be negated by the manner in which the invention was made.
The factual inquiries for establishing a background for determining obviousness under 35 U.S.C. 103 are summarized as follows:
1. Determining the scope and contents of the prior art.
2. Ascertaining the differences between the prior art and the claims at issue.
3. Resolving the level of ordinary skill in the pertinent art.
4. Considering objective evidence present in the application indicating obviousness or nonobviousness.
Claims 1, 7-8, and 10-20 are rejected under 35 U.S.C. 103 as being unpatentable over Jinping et al. (CN1044959248A, published 10/07/2015, found in PTO-892) in view of Paterson et al. (published 11/22/2018, found in IDS dated 05/11/2023).
Jinping et al. teaches a catalyst for preparing mixed alcohols from synthetic gas. The catalyst contains the following ingredients: cobalt and manganese, wherein the mole ratio of cobalt to manganese is 0.1-10. During the operation of synthesis reaction for preparing the mixed alcohols from the synthetic gas, the disclosed catalyst has high activity, high total alcohol selectivity, high C2+ alcohol selectivity and high C6+ alcohol selectivity, can operate at a relatively low temperature, such as temperature of 200-250 °C and has the advantages of high synthetic gas conversion capability, low cost, simplicity and convenience in preparation and easiness in industrial amplification (see Abstract). The catalyst obtained by the invention has high activity, high total alcohol selectivity, high C2+ alcohol selectivity and high C 6+ alcohol selectivity, can be operated at a lower temperature such as 200-250 °C, and has high syngas conversion ability. Low cost, easy preparation and easy industrial amplification. A single pass CO conversion of 36% can be achieved below 250 °C, total oxygenate selectivity can reach 46 wt.%, C2+ alcohol selectivity (C2+ total carbon number of alcohol as a percentage of total oxygenate carbon number) It can reach 97 wt.%, and the C6+ alcohol selectivity can reach 65 wt.% (Note: In this patent, unless otherwise specified, alcohol selectivity refers to oxygenate selectivity) (see last paragraph of Summary of Invention). The catalyst is used in the synthesis gas mixed alcohol reaction, the reaction device is a fixed bed reactor, the catalyst loading is 1.5 g, diluted with 3 g fine quartz sand, the reducing atmosphere is a mixture of H2 and N2, H2/mixing Gas= 10% (molar ratio), the reduction space velocity was 8000 ml·g-1·h-1, the reduction temperature was 300 °C, and the time was 5 h. After the end of the reduction process, the temperature was lowered to 180 °C; then the reactor pressure was back pressured to 2.0 with a mixture of syngas (H2/CO=2) and N2 {syngas/mixture = 10% (molar ratio)). After MPa, the reaction temperature was raised to the target temperature point, and 10% of the syngas in the reactor was gradually replaced with synthesis gas, and vented after about 24 hours. The reaction temperature was 250 °C, the reaction space velocity was 6000 ml·g-1·h-1, the working pressure was 2.0 MPa, and the molar ratio of H2/CO was 2, and the reaction results are shown in Table 1 (see Example 38). The catalytic reaction conditions are: the reaction temperature is 150-300 °C; the working pressure is 0.1-15 Mpa; The reaction space velocity is 100 to 20000 h-1; the synthesis gas is composed of H2 and CO, and the molar ratio of H2/CO is 0.1 to 10: 1; the catalyst is used for activation and activation before the synthesis gas is mixed alcohol. The condition is: in the reducing gas atmosphere, the gradient is heated to 150-600 °C, and the activation is 1- 24 h; the reducing gas atmosphere is H2, CO, syngas or a mixture of the above gas and an inert gas, wherein the atmosphere of the reducing gas is empty. The speed is 1000~20000 h-1. The technician can perform selection optimization according to conventional techniques (see Example 64, paragraph 5).
The teachings of Jinping et al. differ from that of the instantly claimed invention in that Jinping et al. does not teach contacting the catalyst with a second gaseous feed comprising carbon monoxide and hydrogen to provide a second product composition comprising C5+ hydrocarbons, with a second selectivity for alcohols of no more than 5%, and/or a second selectivity for C5+ hydrocarbons of at least 80%. As required by instant claim 10, contacting the catalyst with a second gaseous feed comprising carbon monoxide and hydrogen to provide a third product composition comprising C5+ hydrocarbons and alcohol, with a selectivity of greater than 5% for alcohols, and/or a selectivity of no more than 92% for C5+ hydrocarbons. As required by instant claim 11, the process of claim 10, wherein the contacting of the catalyst with the third gaseous feed is performed with a third selectivity for alcohols of at least 10%. As required by instant claim 15, wherein the catalyst comprises cobalt in an amount of 2-35 wt% on an elemental basis. As required by instant claim 16, wherein the catalyst comprises manganese in an amount of 0.5-20 wt% an elemental basis. As required by instant claim 17, wherein the catalyst comprises a support material that comprises at least one oxide selected from alumina, silica, zirconia, zinc oxide, ceria, and titania. As required by instant claim 18, wherein the catalyst comprises titania, wherein a weight ratio of manganese to cobalt in the catalyst is at least 0.05 on an elemental basis. As required by instant claim 19, wherein the weight ratio of manganese to cobalt in the catalyst is in the range of 0.05 to 3.0 on an elemental basis. As required by instant claim 20, wherein the catalyst comprises up to 15 wt% manganese on an elemental basis.
Paterson et al. teaches manipulation of Fischer-Tropsch synthesis for production of higher alcohols using manganese promoters. See below for Figures 6 and 7 which show the C5+ and alcohol selectivity in percentages. A novel series of cobalt-manganese-on-titania catalysts were prepared via simultaneous impregnation, which are highly active for syngas to long-chain alcohols in both powder and commercial extrudate form. These catalysts were fully characterized by a range of advanced techniques to develop greater understanding of the interaction between cobalt and manganese. These catalysts demonstrated high C5+ selectivity and exceptional long-chain alcohol production at industrially relevant conditions. The three-phase product was analyzed thoroughly by GC and NMR to differentiate between the host of product species formed in Fischer-Tropsch chemistry. These results are particularly significant because long-chain linear alpha olefins and long chain linear alcohols have a high commercial value and synthesis is not always easy. These results provide a novel route to make linear alcohols and olefins by FT. The oxygenate products could in turn be easily dehydrated to make the olefins which maximizes the yield of LAO products or utilized as a source for long chain alcohols following separation. The high long chain oxygenate selectivity under normal low temperature FT conditions highlights the interest of the work, where conventional cobalt FT produces very little alcohol product. Physical mixture experiments that do not indicate the same performance as the co-mixed cobalt and manganese salts
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were also presented (see Conclusion).
It would have been obvious before the effective filing date of the claimed invention to modify the teachings of Jinping et al. with the teachings of Paterson et al. by choosing a catalyst composition as shown in Figure 7 of Paterson et al. used in the method as taught by Jinping et al. that gives a selectivity of alcohols and C5+ hydrocarbons desired by one of ordinary skill in the art. It would have been prima facie obvious for one of ordinary skill in the art to modify the composition of the catalyst used in Fischer-Tropsch synthesis because, as taught by Paterson et al., long-chain linear alpha olefins and long chain linear alcohols have a high commercial value and synthesis is not always easy. One of ordinary skill in the art would have a reasonable expectation of success because Jinping et al. teaches a catalyst that comprises cobalt and manganese.
Claims 2-6 are rejected under 35 U.S.C. 103 as being unpatentable over Jinping et al. (CN1044959248A, published 10/07/2015, found in PTO-892) in view of Paterson et al. (published 11/22/2018, found in IDS dated 05/11/2023) as applied to claim 1 above, and further in view of Mansouri et al. (Int J Ind Chem, published 05/08/2014, found in PTO-892).
The teachings of Jinping et al. and Paterson et al. were discussed above.
The teachings of Jinping et al. and Paterson et al. differ from that of the instantly claimed invention in that Jinping et al. and Paterson et al. do not teach, as required by instant claim 2, the process of claim 1, further comprising, before the contacting with the first gaseous feed and/or the first selectivity-modifying gaseous composition, contacting the catalyst with an activation gaseous composition comprising at least 50 vol% H₂ at a pressure in the range of 2 barg to 30 barg and a temperature in the range of 250 °C to 450 °C. As required by instant claim 3, wherein the first selectivity-modifying gaseous composition comprises at least 50 vol% H₂. As required by instant claim 4, wherein the first selectivity-modifying gaseous composition has a H2:CO molar ratio of at least 3. As required by instant claim 5, wherein the contacting of the catalyst with the first selectivity-modifying gaseous composition is at a pressure in the range of 5 barg to 35 barg. As required by instant claim 6, wherein the contacting of the catalyst with the first selectivity-modifying gaseous composition is at a temperature in the range of 150 °C to 275 °C.
Mansouri et al. teaches very wide product distributions are generally obtained over conventional FT catalysts. Selectivity control remains one of the most important and difficult challenges in the research area of FTS. Generally, the nature of the catalyst, the reactor, and the operating conditions are the main factors affecting the product selectivity and the CO conversion activity for FTS (see Introduction section). An active 25 %Co/75 %Mn/30 wt.% TiO2 catalyst was prepared by co-precipitation method and it showed the highest performance for synthesis of light olefins in FTS. The optimal operating conditions for the production of light olefins were found to be 270 °C under the total pressure of 3 bar at the molar feed ratio of H2/CO = 2/1 (see Conclusion section). The experiments were carried out in a fixed-bed tubular stainless steel micro reactor. A schematic representation of the experimental set up is shown in Fig. 1. All gas lines to the reactor bed were made from 1/400 stainless steel tubing. Three mass flow controllers (Brooks, Model 5850E) were used to adjust automatically flow rate of the inlet gases comprising CO, H2, and N2 (purity of 99.99 %). The mixed gases in the mixing chamber passed into the reactor tube, which was placed inside a tubular furnace (Atbin, Model ATU 150-15) capable of producing temperature up to 1,500 °C and controlled by a digital programmable controller (DPC). The reactor tube was constructed from stainless steel tubing; internal diameter of 20 mm, with the catalyst bed situated in the middle of the reactor. The reaction temperature was controlled by a thermocouple inserted into catalyst bed and visually monitored by a computer equipped with software. Some thermocouples were inserted in the catalyst bed for monitoring the inlet, outlet, and bed temperatures by a DPC. Prior to the catalytic activity measurements, the samples were crushed, sieved (mesh size 0.1–2.5 mm), and then held in middle of the reactor using quartz and asbestos. The catalyst was in situ pre-reduced at atmospheric pressure under H2–N2 flow H2/N2 = 1 (flow rate of each gas = 30 mL/min) at 400 °C for 16 h before synthesis gas exposure. It consists of an electronic back pressure regulator which is able to control the total pressure of the desired process by remote control using TESCOM software package designed. This promotes the yield in the range of 1–100 bar. In each test, 1.0 g catalyst was loaded and the reactor operated about 12 h to ensure steady-state operations were attained. Reactant and product streams were analyzed on-line using a gas chromatograph (Thermo ONIX UNICAM PROGC ?) equipped with sample loop, two thermal conductivity detectors (TCD) and one flame ionization detector (FID) able to perform the analysis of a wide variety of gaseous hydrocarbon mixtures, one TCD used for the analysis of hydrogen and the other one used for all the permanent gases such as N2, O2, and CO. The FID is used for the analysis of hydrocarbons. The system is applicable to the analysis of non-condensable gases, methane through C8 hydrocarbons. The contents of the sample loop were injected automatically into an alumina capillary column (30 m x 0.550 mm). Helium was employed as a carrier gas for optimum sensitivity (flow rate = 30 mL/min). The calibration was carried out using various calibration mixtures and pure compounds obtained from Tarkib Gas Alvand Company (Iran). Experiments were carried out with mixtures of H2, CO, and N2 in a temperature range of 190–270 °C, H2/CO feed ratio of 1/1–3/1 and a pressure range of 1–10 bar. The experimental conditions and obtained data are presented in Table 3 (see Catalytic Test section).
It would have been obvious to combine the teachings of Jinping et al. and Paterson et al. with Mansouri et al. before the effective filing date of the claimed invention by optimizing conditions such as H2/CO ratio, pressure, and temperature to arrive at the claimed invention. It would have been prima facie obvious for one of ordinary skill in the art to combine the method as taught by the combined teachings of Jinping et al. and Paterson et al. with the H2/CO ratio, pressure, and temperature, as taught by Mansouri et al., because, as taught by Mansouri et al., the nature of the catalyst, the reactor, and the operating conditions are the main factors affecting the product selectivity and the CO conversion activity for FTS. One of ordinary skill in the art would have a reasonable expectation of success because all references aim to optimize cobalt-manganese catalyzed Fischer-Tropsch reactions.
Claim 9 is rejected under 35 U.S.C. 103 as being unpatentable over Jinping et al. (CN1044959248A, published 10/07/2015, found in PTO-892) in view of Paterson et al. (published 11/22/2018, found in IDS dated 05/11/2023) as applied to claim 1 above, and further in view of Ojeda et al. (Journal of Catalysis, published 05/21/2010, found in PTO-892).
The combined teachings of Jinping et al. and Paterson et al. were discussed above.
The combined teachings of Jinping et al. and Paterson et al. differ from that of the instantly claimed invention in that the combined teachings of Jinping et al. and Paterson et al. do not teach the process of claim 1 further comprising: monitoring the second selectivity for alcohols and/or the second selectivity for C5+ hydrocarbons; determining whether the second selectivity for alcohols is greater than an alcohols threshold value, and/or whether the second selectivity for C₅+ hydrocarbons is less than a hydrocarbons threshold value; and if the second selectivity for alcohols is greater than the alcohols threshold value, and/or if the second selectivity for C5+ hydrocarbons selectivity is less than the hydrocarbons threshold value, contacting the catalyst with the first selectivity gaseous composition.
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Ojeda et al. teaches a first-order rate dependence of the Fischer-Tropsch reaction rate on the concentration of hydrogen as shown in Figure 3 below. The inlet pressure correlates to concentration of the reactant and the CO conversion rate to HC correlates to hydrocarbons made.
It would have been obvious to combine the teachings of Jinping et al. and Paterson et al. with Ojeda et al. before the effective filing date of the claimed invention by monitoring the reaction products made from the method as taught by the combined teachings of Jinping et al. and Paterson et al. using any monitoring method known to those skilled in the art and increasing the concentration of hydrogen used in the method to increase the output of hydrocarbons as taught by Ojeda et al. to arrive at the instantly claimed invention. It would have been prima facie obvious for one of ordinary skill in the art to combine the combined teachings of Jinping et al. and Paterson et al. with Ojeda et al. because, as taught by Ojeda et al., increasing the concentration increases the conversion rate of Co into CH which increases hydrocarbon production. One of ordinary skill in the art would have a reasonable expectation of success because all references aim to understand the fundamentals of Fischer-Tropsch synthesis.
Double Patenting
The nonstatutory double patenting rejection is based on a judicially created doctrine grounded in public policy (a policy reflected in the statute) so as to prevent the unjustified or improper timewise extension of the “right to exclude” granted by a patent and to prevent possible harassment by multiple assignees. A nonstatutory double patenting rejection is appropriate where the conflicting claims are not identical, but at least one examined application claim is not patentably distinct from the reference claim(s) because the examined application claim is either anticipated by, or would have been obvious over, the reference claim(s). See, e.g., In re Berg, 140 F.3d 1428, 46 USPQ2d 1226 (Fed. Cir. 1998); In re Goodman, 11 F.3d 1046, 29 USPQ2d 2010 (Fed. Cir. 1993); In re Longi, 759 F.2d 887, 225 USPQ 645 (Fed. Cir. 1985); In re Van Ornum, 686 F.2d 937, 214 USPQ 761 (CCPA 1982); In re Vogel, 422 F.2d 438, 164 USPQ 619 (CCPA 1970); In re Thorington, 418 F.2d 528, 163 USPQ 644 (CCPA 1969).
A timely filed terminal disclaimer in compliance with 37 CFR 1.321(c) or 1.321(d) may be used to overcome an actual or provisional rejection based on nonstatutory double patenting provided the reference application or patent either is shown to be commonly owned with the examined application, or claims an invention made as a result of activities undertaken within the scope of a joint research agreement. See MPEP § 717.02 for applications subject to examination under the first inventor to file provisions of the AIA as explained in MPEP § 2159. See MPEP § 2146 et seq. for applications not subject to examination under the first inventor to file provisions of the AIA . A terminal disclaimer must be signed in compliance with 37 CFR 1.321(b).
The filing of a terminal disclaimer by itself is not a complete reply to a nonstatutory double patenting (NSDP) rejection. A complete reply requires that the terminal disclaimer be accompanied by a reply requesting reconsideration of the prior Office action. Even where the NSDP rejection is provisional the reply must be complete. See MPEP § 804, subsection I.B.1. For a reply to a non-final Office action, see 37 CFR 1.111(a). For a reply to final Office action, see 37 CFR 1.113(c). A request for reconsideration while not provided for in 37 CFR 1.113(c) may be filed after final for consideration. See MPEP §§ 706.07(e) and 714.13.
The USPTO Internet website contains terminal disclaimer forms which may be used. Please visit www.uspto.gov/patent/patents-forms. The actual filing date of the application in which the form is filed determines what form (e.g., PTO/SB/25, PTO/SB/26, PTO/AIA /25, or PTO/AIA /26) should be used. A web-based eTerminal Disclaimer may be filled out completely online using web-screens. An eTerminal Disclaimer that meets all requirements is auto-processed and approved immediately upon submission. For more information about eTerminal Disclaimers, refer to www.uspto.gov/patents/apply/applying-online/eterminal-disclaimer.
Claims 1, 7-8, and 10-20 are rejected on the ground of nonstatutory double patenting as being unpatentable over claims 1-6, 9-10,12, 18, and 22 of U.S. Patent No. 11,203,717 B2 (‘717, published 12/24/2020) in view of Jinping et al. (CN1044959248A, published 10/07/2015, found in PTO-892) in further view of Paterson et al. (published 11/22/2018, found in IDS dated 05/11/2023).
‘717 teaches a process for converting a mixture of hydrogen and carbon monoxide gases to a composition comprising alcohols and liquid hydrocarbons by means of a Fischer-Tropsch synthesis reaction, said process comprising contacting a mixture of hydrogen and carbon monoxide gases with a supported Co-Mn Fischer-Tropsch synthesis catalyst, wherein: the support material of the supported Co-Mn Fischer-Tropsch synthesis catalyst comprises a material selected from titania, zinc oxide, zirconia, and ceria; the supported synthesis catalyst comprises cobalt in the range of 5 wt.% to 20 wt.% and comprises manganese in the range of 1.5 wt.% to 15 wt.%, wherein the combined amount of cobalt and manganese in the supported Co-Mn Fischer-Tropsch synthesis catalyst is less than 30 wt.% on an elemental basis, based on the total weight of the supported synthesis catalyst; the weight ratio of manganese to cobalt, on an elemental basis, is 0.2 or greater; the molar ratio of hydrogen to carbon monoxide is at least 1; and the Fischer-Tropsch synthesis reaction is conducted at a pressure in the range of from 1.0 to 10.0 MPa absolute. A process according to claim 1, wherein the support material comprises titania. A process according to claim 2, wherein the support material is titania. A process according to claim 1, wherein the weight ratio of manganese to cobalt present in the supported Co-Mn Fischer-Tropsch synthesis catalyst, on an elemental basis, is in the range of from 0.2 to 3.0. A process according to claim 1, wherein the supported Co-Mn Fischer-Tropsch synthesis catalyst contains from 7.5 wt.% to 20 wt.% of cobalt, on an elemental basis, based on the total weight of the supported synthesis catalyst. A process according to claim 1, wherein the supported Co-Mn Fischer-Tropsch synthesis catalyst contains from 2.5 wt.% to 10 wt.% of manganese, on an elemental basis, based on the total weight of the supported synthesis catalyst. A process according to claim 1, wherein the Fischer-Tropsch synthesis reaction is conducted at a temperature of less than or equal to 300 °C. A process according to claim 1, wherein the Fischer-Tropsch synthesis reaction is conducted at a pressure of less than 7.5 MPa absolute. A process according to claim 1, wherein the weight ratio of manganese to cobalt present, on an elemental basis, is 0.3 or greater, and wherein the supported Co-Mn Fischer-Tropsch synthesis is prepared by impregnation. A process for converting a mixture of hydrogen and carbon monoxide gases to a composition comprising alcohols and liquid hydrocarbons by means of a Fischer-Tropsch synthesis reaction, the process comprising contacting a mixture of hydrogen and carbon monoxide gases with a supported Co-Mn Fischer-Tropsch synthesis catalyst as defined in Claim 12. A process according to claim 1, wherein the process has a selectivity for alcohols of at least 15%.
‘717 differs from that of the instantly claimed invention in that ‘717 does not teach, as required by instant claim 1, contacting the catalyst with a first gaseous feed comprising carbon monoxide and hydrogen for at least 12 hours and a second selectivity for alcohols of no more than 5%, and/or a second selectivity for c5+ hydrocarbons of at least 80%. As required by instant claim 8, wherein the contacting with the first gaseous feed (when performed), the contacting with the first selectivity-modifying gaseous composition, and the contacting with the second gaseous feed are performed in a reactor without removing the catalyst therefrom. As required by instant claim 10, optionally, contacting the catalyst with a first gaseous feed comprising carbon monoxide and hydrogen for at least 12 hours and a selectivity of greater than 5% for alcohols, and/or a selectivity of no more than 92% for C5+ hydrocarbons. As required by instant claim 12, wherein the second selectivity-modifying gaseous composition comprises no more than 75 vol% H₂ and/or a H2:CO molar ratio in the range of 0.25:1 to 0.4:1.
The teachings of Jinping et al. were discussed above.
The teachings of Paterson et al. were discussed above.
It would have been obvious to combine the teachings of ‘717 with Jinping et al. and Paterson et al. before the effective filing date of the claimed invention by allowing the reaction to proceed for at least 12 hours and controlling the selectivity of the reaction as taught by Paterson et al. to arrive at the instantly claimed invention. It would have been prima facie obvious for one of ordinary skill in the art to combine the teachings of ‘717 with Jinping et al. and Paterson et al. because, as taught by Paterson et al., long-chain linear alpha olefins and long chain linear alcohols have a high commercial value and synthesis is not always easy. One of ordinary skill in the art would have a reasonable expectation of success because both references aim to optimize cobalt-manganese catalyzed Fischer-Tropsch reactions.
Claims 2-6 are rejected on the ground of nonstatutory double patenting as being unpatentable over claims 1-6, 9-10,12, 18, and 22 of U.S. Patent No. 11,203,717 B2 (‘717, published 12/24/2020) in view of Jinping et al. (CN1044959248A, published 10/07/2015, found in PTO-892) in further view of Paterson et al. (published 11/22/2018, found in IDS dated 05/11/2023) as applied to claim 1 above, and further in view of Mansouri et al. (Int J Ind Chem, published 05/08/2014, found in PTO-892).
The combined teachings of ‘717, Jinping et al., and Paterson et al. were discussed above.
The combined teachings of ‘717, Jinping et al., and Paterson et al. differ from that of the instantly claimed invention in that ‘717, Jinping et al., and Paterson et al. does not teach, as required by instant claim 2, before the contacting with the first gaseous feed and/or the first selectivity-modifying gaseous composition, contacting the catalyst with an activation gaseous composition comprising at least 50 vol% H₂ at a pressure in the range of 2 barg to 30 barg and a temperature in the range of 250 °C to 450 °C. As required by instant claim 3, wherein the first selectivity-modifying gaseous composition comprises at least 50 vol% H₂. As required by instant claim 4, wherein the first selectivity-modifying gaseous composition has a H2:CO molar ratio of at least 3. As required by instant claim 5, wherein the contacting of the catalyst with the first selectivity-modifying gaseous composition is at a pressure in the range of 5 barg to 35 barg. As required by instant claim 6, wherein the contacting of the catalyst with the first selectivity-modifying gaseous composition is at a temperature in the range of 150 °C to 275 °C.
The teachings of Mansouri et al. were discussed above.
It would have been obvious to combine the teachings of ‘717, Jinping et al., and Paterson et al. with the teachings of Mansouri et al. before the effective filing date of the claimed invention by performing the method as taught by ‘717, Jinping et al., and Paterson et al. and ,as taught by Mansouri et al., modifying the operating conditions to arrive at the instantly claimed invention. It would have been prima facie obvious for one of ordinary skill in the art to modify the operating conditions of the method because, as taught by Mansouri et al., the nature of the catalyst, the reactor, and the operating conditions are the main factors affecting the product selectivity and the CO conversion activity for FTS. One of ordinary skill in the art would have a reasonable expectation of success because all references aim to optimize cobalt-manganese catalyzed Fischer-Tropsch reactions.
Claim 9 is rejected on the ground of nonstatutory double patenting as being unpatentable over claims 1-6, 9-10,12, 18, and 22 of U.S. Patent No. 11,203,717 B2 (‘717, published 12/24/2020) in view of Jinping et al. (CN1044959248A, published 10/07/2015, found in PTO-892) in further view of Paterson et al. (published 11/22/2018, found in IDS dated 05/11/2023) as applied to claim 1 above, and further in view of Ojeda et al. (Journal of Catalysis, published 05/21/2010, found in PTO-892).
The combined teachings of ‘717, Jinping et al., and Paterson et al. were discussed above.
The combined teachings of ‘717, Jinping et al., and Paterson et al. differ from that of the instantly claimed invention in that ‘717, Jinping et al., and Paterson et al. does not teach monitoring the second selectivity for alcohols and/or the second selectivity for C5+ hydrocarbons; determining whether the second selectivity for alcohols is greater than an alcohols threshold value, and/or whether the second selectivity for C₅+ hydrocarbons is less than a hydrocarbons threshold value; and if the second selectivity for alcohols is greater than the alcohols threshold value, and/or if the second selectivity for C5+ hydrocarbons selectivity is less than the hydrocarbons threshold value, contacting the catalyst with the first selectivity gaseous composition.
The teachings of Ojeda et al. were discussed above.
It would have been obvious to combine the teachings of ‘717, Jinping et al., and Paterson et al. with Ojeda et al. before the effective filing date of the claimed invention by monitoring the reaction products made from the method as taught by the combined teachings of ‘717, Jinping et al., and Paterson et al. using any monitoring method known to those skilled in the art and increasing the concentration of hydrogen used in the method to increase the output of hydrocarbons as taught by Ojeda et al. to arrive at the instantly claimed invention. It would have been prima facie obvious for one of ordinary skill in the art to combine the combined teachings of ‘717, Jinping et al., and Paterson et al. with Ojeda et al. because, as taught by Ojeda et al., increasing the concentration increases the conversion rate of carbon monoxide into CH which increases hydrocarbon production. One of ordinary skill in the art would have a reasonable expectation of success because all references aim to understand the fundamentals of Fischer-Tropsch synthesis.
Conclusion
No claim is found allowable.
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/KRISTEN W BRADY/ Examiner, Art Unit 1692
/SCARLETT Y GOON/ Supervisory Patent Examiner, Art Unit 1693