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 .
The After Final Amendment filed 27 January 2026 has been entered. Claims 1 and 10 are amended.
Claims 1-19 are pending for examination below.
Response to Arguments
The After Final Amendment filed 27 January 2026 has been entered for the following reasons:
Claim 1 has been amended to a method comprising a catalyst composition consisting of three components, where each component consists of a finite number of specific options. This filing amends claim 1 to match the scope of previously presented claim 10. Claims 1 and 10 are also amended to delete the language that the catalyst is “free of platinum and chromium”, which is redundant language due to the consisting of language already used, and does not change the scope. Thus, the amendments are minor amendments and are entered as proper.
Upon consideration of the arguments and discussion with Applicant’s representative, the Examiner withdraws the previous Final Rejection of claims 1-19 over Kishimoto in view of Kirshenbaum and Stine. Claim 10 as previously presented includes “consisting of” language for each of the three catalyst components. The cited references do not teach a catalyst that meets the “consisting of” language for each component, thus the cited art was improperly applied to claims 10-19 in the Final Rejection and is withdrawn. With the current amendment to claim 1 to also include the “consisting of” language for each component, the rejection over Kishimoto in view of Kirshenbaum and Stine is additionally withdrawn over claims 1-9. However, upon further consideration, new grounds of rejection of Double Patenting and USC 103 are made below in view of newly presented prior art and a new interpretation of the patents in the double patenting rejection. Thus, the rejection below has been made Non-Final.
The Examiner reached out to Applicant’s representative to discuss an issue that arose with publication US 2022/0080390, which has an effective filing date before the CIP date April 25, 2022. The catalyst in this US 2022/0080390 publication is very similar to the instant application’s claimed catalyst, and to the claimed catalysts of US 11,168,039 and US 11,040,331. However, while US 11,168,039 and US 11,040,331 share the co-assignees Exelus, Inc and Kellogg Brown & Root LLC, the instant application is solely assigned to Kellogg Root & Brown LLC, and US 2022/0080390 is solely assigned to Exelus, Inc. Thus, as currently presented, US 2022/0080390 is valid prior art.
There is no record of a research agreement between Exelus, Inc and Kellogg Brown & Root LLC for the instant application and/or the US 2022/0080390 application at the time of filing. However, the fact that the Patents above include both entities as co-assignees invokes the possibility that a research agreement between the entities was in effect at the time of filing of the instant application and/or the filing of US 2022/0080390. The existence of said research agreement would remove US 2022/0080390 as prior art, but require a further terminal disclaimer over the Patent resulting from US 2022/0080390 (US 11,364,482).
While the Examiner was able to discuss this issue with Applicant’s representative and appreciates the efforts made to obtain the needed information, the information about the possible research agreement was not able to be obtained in the time allotted.
Thus, the Examiner will consider that US 2022/0080390 is valid prior art for purposes of the below rejection. Should it be determined that a research agreement between Exelus, Inc and Kellogg Root & Brown LLC is in effect for the instant application and US 2022/0080390, the 103 rejection including US 2022/0080390 will be withdrawn, but there would be an additional Double Patenting rejection made over the Patent resulting from US 2022/0080390 (US 11,364,482).
Claim Interpretation
The Examiner notes that the instant application is a CIP of 16/823,733, where the CIP was filed on April 25, 2022. The language of a catalyst comprising or consisting of three defined parts being an active catalyst, support, and stabilizer was not present in the parent application as filed. Thus, the catalyst consisting of the three defined parts as claimed only gets the filing date of the CIP application, whereas the method language retains the priority date of March 21, 2019 from the parent. The prior art applied below is valid prior art under these dates.
Claim Suggestions
In order to provide compact prosecution, the following are the amendments the Examiner would propose, again assuming that US 2022/0080390 is valid prior art. If US 2022/0080390 is removed as prior art due to the existence of a research agreement as discussed above, it is not necessary to remove zinc from the list of active metals.
Claim 1 (Currently Amended) A process for recovering catalyst fines from a reactor effluent stream of a catalytic paraffin dehydrogenation reaction, the process comprising:
a. to dehydrogenate the paraffin
the metal oxide catalyst consists
an active catalyst component selected from the group consisting of oxides of
a catalyst support selected from the group consisting of oxides of aluminumand silicon; and
a catalyst stabilizer selected from the group consisting of oxides of zirconium, cerium, dysprosium, erbium, europium, gadolinium, lanthanum, neodymium, praseodymium, samarium, terbium, ytterbium, yttrium, niobium, and tungsten;
b. generating a reactor effluent stream comprising metal oxide catalyst fines after the contacting
c. washing the reactor effluent stream with a wash fluid to transfer the metal oxide catalyst fines from the reactor effluent stream into the wash fluid and form a cooled catalyst effluent stream comprising the metal oxide catalyst fines and a catalyst-free product stream.
Claim 3, line 1, before “group” delete “a” and insert –the—
Cancel claim 4 as not further limiting because one of ordinary skill in the art understands that a dehydrogenation reaction must produce an olefin.
5. (Currently Amended) The process of claim 4, wherein the reactor effluent comprises an olefin the group consisting of propylene, ethylene, and combinations thereof
6. (Currently Amended) The process of claim 1, wherein the contacting occurs at a temperature ranging from about 500°C to about 800°C.
7. (Currently Amended) The process of claim 1, wherein the contacting occurs at a pressure ranging from about 0.01 MPa to about 0.02 MPa.
Cancel claim 9 as not further limiting because the amendment to claim 1 to overcome the art already removes zinc and iron.
10. (Currently Amended) A process for recovering catalyst fines from a reactor effluent stream of a catalytic paraffin dehydrogenation reaction, the process comprising:
a. contacting a metal oxide catalyst with a paraffin having 2-8 carbon atoms in a reactor;
i. wherein the paraffin is selected from the group consisting of propane, n- butane, isobutane, and combinations thereof;
ii. wherein the metal oxide catalyst consists of:
an active catalyst component selected from the group consisting of oxides of
a catalyst support selected from the group consisting of oxides of aluminum, silicon, and combinations thereof; and
a catalyst stabilizer selected from the group consisting of oxides of zirconium, cerium, dysprosium, erbium, europium, gadolinium, lanthanum, neodymium, praseodymium, samarium, terbium, ytterbium, yttrium, niobium, tungsten, and combinations thereof;
b. generating a reactor effluent stream comprising metal oxide catalyst fines after the contacting
c. washing the reactor effluent stream with a wash fluid to transfer the metal oxide catalyst fines from the reactor effluent stream into the wash fluid and form a cooled catalyst effluent stream comprising the metal oxide catalyst fines and a catalyst-free product stream.
12. (Currently Amended) The process of claim 11, further comprising filtering the slurry in one or more filters to yield separated metal oxide catalyst fines.
13. (Currently Amended) The process of claim 12, wherein the slurry is continuously passed through a first filter in a filtration mode to separate the metal oxide catalyst fines from the slurry backflushing mode to remove the separated metal oxide catalyst fines from the second filter.
16. (Currently Amended) The process of claim 10, wherein the reactor effluent stream is washed in a quench tower.
18. (Currently Amended) The process of claim 17, wherein the quench tower has a recirculation loop for continuously recirculating the wash fluid to the contacting elements.
Claim Objections
Claims 1, 3, 5, and 10 are objected to because of the following informalities:
With regard to claim 1, the claim recites in line 10 “consisting of oxides aluminum, or silicon”. This should be “consisting of oxides of aluminum and silicon” for proper grammar and Markush group construction.
Also with regard to claim 1, the claim recites in line “niobium, or tungsten”. This should be “niobium, and tungsten” for proper Markush group construction.
Claims 3, 5, and 10 each recite “selected from a group consisting of…” This should be “selected from the group consisting of” to be proper Markush group language.
Appropriate corrections are required.
Claim Rejections - 35 USC § 112
The following is a quotation of 35 U.S.C. 112(b):
(b) CONCLUSION.—The specification shall conclude with one or more claims particularly pointing out and distinctly claiming the subject matter which the inventor or a joint inventor regards as the invention.
The following is a quotation of 35 U.S.C. 112 (pre-AIA ), second paragraph:
The specification shall conclude with one or more claims particularly pointing out and distinctly claiming the subject matter which the applicant regards as his invention.
Claim 18 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.
With regard to claim 18, the claim recites “The process of claim 16, wherein the quench tower has a recirculation loop for continuously recirculating a wash oil…” However, claim 1 recites a “wash fluid”, not a wash oil. Thus, it is unclear whether the “wash oil” and “wash fluid” are intended to be the same component, or different components, and claim 18 is indefinite.
For purposes of examination, the Examiner will consider that “wash oil” is intended to be a specific version of the “wash fluid”, based on the recitation in claim 19 that the wash fluid can be oil. The Examiner has suggested claim language above which would overcome the 112(b) issue.
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.
Claim 4 is rejected under 35 U.S.C. 112(d) or pre-AIA 35 U.S.C. 112, 4th paragraph, as being of improper dependent form for failing to further limit the subject matter of the claim upon which it depends, or for failing to include all the limitations of the claim upon which it depends.
With regard to claim 4, the claim recites “further comprising generating a reactor effluent stream comprising an olefin.” However, claim 1 already recites generating a reactor effluent stream, and that the reaction in claim 1 is a dehydrogenation reaction of paraffins. One of ordinary skill in the art understands implicitly that dehydrogenation of paraffins must produce at least one olefin. Thus, claim 4 does not further limit claim 1.
Applicant may cancel the claim(s), amend the claim(s) to place the claim(s) in proper dependent form, rewrite the claim(s) in independent form, or present a sufficient showing that the dependent claim(s) complies with the statutory requirements.
Claim Rejections - 35 USC § 103
The following is a quotation of 35 U.S.C. 103 which forms the basis for all obviousness rejections set forth in this Office action:
A patent for a claimed invention may not be obtained, notwithstanding that the claimed invention is not identically disclosed as set forth in section 102, if the differences between the claimed invention and the prior art are such that the claimed invention as a whole would have been obvious before the effective filing date of the claimed invention to a person having ordinary skill in the art to which the claimed invention pertains. Patentability shall not be negated by the manner in which the invention was made.
Claims 10, 18, 18, and 19 are rejected under 35 U.S.C. 103 as being unpatentable over Pretz (US 2020/0197891) in view of Luo et al. (US 2010/0236985) and Mukherjee et al. (US 2022/0080390).
With regard to claims 1-3 and 9, Pretz teaches a method for dehydrogenation of a stream comprising propane (paragraph [0024]) comprising the following steps:
a) reacting the propane (instant claim 3) with a suitable dehydrogenation catalyst (paragraph [0088]) in a fluidized bed reactor (instant claim 2) (paragraph [0026]).
b) producing a reactor effluent stream 380 comprising catalyst fines (paragraph [0043] and Fig. 1).
c) contacting the reactor effluent stream 380 with a quench fluid 510 (wash fluid) in a unit 500 (paragraph [0043] and Fig. 1), where the unit 500 is a quench tower 502 (instant claim 16) (paragraph [0056]), to remove the catalyst fines from the product stream (paragraph [0043]). This step produces a catalyst-free product stream 512 and a quench fluid comprising catalyst fines 514 (cooled catalyst effluent stream) (paragraphs [0045] and [0049], Fig. 1).
Pretz fails to teach i) the reaction time or ii) the specific catalyst composition as claimed.
With regard to i), Luo teaches dehydrogenation of paraffins to olefins (paragraph [0002]) with a metal oxide catalyst (paragraph [0039]) in a fluidized bed reactor (paragraph [0047]). Luo further teaches that the dehydrogenation reaction is conducted under relatively short contact times in order to prevent undesirable side reactions and product degradation where the time is preferable 1 to 8 seconds (paragraph [0042]), which is within the ranges of about 0.05 seconds to 10 minutes of instant claim 1.
Therefore, it would have been obvious to one of ordinary skill in the art before the effective filing date of the invention to use the contact time of Luo in the process of Pretz, because each of Pretz and Luo teach dehydrogenation of paraffins in a fluidized bed reactor comprising a catalyst, Pretz is silent regarding the reaction time, and Luo teaches that contact times of 1 to 8 seconds are suitable for the fluidized bed dehydrogenation of paraffins and provide the benefits of preventing undesirable side reactions and product degradation (paragraph [0042]).
With regard to ii), Pretz teaches the catalyst is a suitable dehydrogenation catalyst (paragraph [0088]), but does not teach the catalyst having the specific composition of claim 10.
Mukherjee teaches a dehydrogenation catalyst composition comprising an active catalyst which is oxides of zinc (instant claim 9), a catalyst support which is oxides of aluminum or silicon, and a stabilizer which is oxides of zirconium, cerium, dysprosium, erbium, europium, gadolinium, lanthanum, neodymium, praseodymium, samarium, terbium, ytterbium, yttrium, tungsten, or mixtures thereof (claim 1, pages 7-8). Mukherjee does not teach any other required components, thus the catalyst of Mukherjee consists of the claimed components having the claimed metals. Mukherjee further teaches that the catalyst is used in dehydrogenation of paragraphs having 2-8 carbon atoms (paragraph [0054]) and that the catalyst provides advantages including improved catalyst activity and selectivity and limited catalyst consumption (paragraph [0077]).
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 Mukherjee in the process of Pretz, because each of Pretz and Mukherjee teach dehydrogenation of C3 paraffins over a catalyst, Pretz teaches any suitable dehydrogenation catalyst can be used, and Mukherjee teaches that the catalyst having the claimed components provides the benefits of improved catalyst activity and selectivity and limited catalyst consumption (paragraph [0077]).
With regard to claims 4 and 5, Pretz teaches that the dehydrogenation produces olefins (paragraph [0023]). Pretz does not specifically teach the olefins include propylene. However, one of ordinary skill in the art is aware that a dehydrogenation reaction converts a paraffin to at least the corresponding olefin having the same carbon number. Thus, because the feed of Pretz comprises propane, the effluent comprises at least propylene, as claimed.
With regard to claim 6, Pretz is silent regarding the temperature.
Luo teaches dehydrogenation of paraffins to olefins (paragraph [0002]) with a metal oxide catalyst (paragraph [0039]) in a fluidized bed reactor (paragraph [0047]) at the short contact time of 1 to 8 seconds. Luo further teaches that when using the short contact times above, the dehydrogenation reaction is conducted at a temperature of 500-800°C (paragraph [0044]), which is the same as the claimed range of about 500 to about 800°C.
Therefore, it would have been obvious to one of ordinary skill in the art at the time of the invention to use the temperature of Luo in the process of Pretz, because each of Pretz and Luo teach dehydrogenation of paraffins in a fluidized bed reactor comprising a catalyst, Pretz is silent regarding the temperature, and Luo teaches that when using the short contact time as claimed, the temperature is 500-800°C (paragraph [0044]).
With regard to claim 7, Pretz is silent regarding the pressure.
Luo teaches dehydrogenation of paraffins to olefins (paragraph [0002]) with a metal oxide catalyst (paragraph [0039]) in a fluidized bed reactor (paragraph [0047]) at the short contact time of 1 to 8 seconds. Luo further teaches that the applicable pressure can be 3.7 psi (0.025 MPa), which is within the range of above 0.01 to about 0.02 MPa of instant claim 7.
Therefore, it would have been obvious to one of ordinary skill in the art at the time of the invention to use the pressure of Luo in the process of Pretz, because each of Pretz and Luo teach dehydrogenation of paraffins in a fluidized bed reactor comprising a catalyst, Pretz is silent regarding the pressure, and Luo teaches that the pressure can be 3.7 psi (0.025 MPa) (paragraph [0045]).
With regard to claim 8, Pretz is silent regarding the presence of a diluent or steam with the paraffin.
Luo teaches dehydrogenation of paraffins to olefins (paragraph [0002]) with a metal oxide catalyst (paragraph [0039]) in a fluidized bed reactor (paragraph [0047]). Luo further teaches that the paraffins are introduced into the reactor with an inert diluent fluid (paragraph [0046]). Thus, Luo teaches that inert diluents are known to be used with the paraffin in the fluidized bed reactor for the dehydrogenation process.
Therefore, it would have been obvious to one of ordinary skill in the art at the time of the invention to add an inert diluent fluid to the paraffin in Pretz, because each of Pretz and Luo teach paraffin dehydrogenation in a fluidized bed reactor, Pretz is silent regarding the presence of an inert diluent, and Luo teaches that inert diluents are known to be used along with the paraffin when introducing the paraffin to the reactor (paragraph [0046]).
Claims 10 and 16-19 are rejected under 35 U.S.C. 103 as being unpatentable over Pretz (US 2020/0197891) in view of Mukherjee et al. (US 2022/0080390).
With regard to claims 10 and 16, Pretz teaches a method for dehydrogenation of a stream comprising propane (paragraph [0024]) comprising the following steps:
a) reacting the propane with a suitable dehydrogenation catalyst (paragraph [0088]).
b) producing a reactor effluent stream 380 comprising catalyst fines (paragraph [0043] and Fig. 1).
c) contacting the reactor effluent stream 380 with a quench fluid 510 (wash fluid) in a unit 500 (paragraph [0043] and Fig. 1), where the unit 500 is a quench tower 502 (instant claim 16) (paragraph [0056]), to remove the catalyst fines from the product stream (paragraph [0043]). This step produces a catalyst-free product stream 512 and a quench fluid comprising catalyst fines 514 (cooled catalyst effluent stream) (paragraphs [0045] and [0049], Fig. 1).
Pretz teaches the catalyst is a suitable dehydrogenation catalyst (paragraph [0088]), but does not teach the catalyst having the specific composition of claim 10.
Mukherjee teaches a dehydrogenation catalyst composition comprising an active catalyst which is oxides of zinc, a catalyst support which is oxides of aluminum or silicon, and a stabilizer which is oxides of zirconium, cerium, dysprosium, erbium, europium, gadolinium, lanthanum, neodymium, praseodymium, samarium, terbium, ytterbium, yttrium, tungsten, or mixtures thereof (claim 1, pages 7-8). Mukherjee does not teach any other required components, thus the catalyst of Mukherjee consists of the claimed components having the claimed metals. Mukherjee further teaches that the catalyst is used in dehydrogenation of paragraphs having 2-8 carbon atoms (paragraph [0054]) and that the catalyst provides advantages including improved catalyst activity and selectivity and limited catalyst consumption (paragraph [0077]).
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 Mukherjee in the process of Pretz, because each of Pretz and Mukherjee teach dehydrogenation of C3 paraffins over a catalyst, Pretz teaches any suitable dehydrogenation catalyst can be used, and Mukherjee teaches that the catalyst having the claimed components provides the benefits of improved catalyst activity and selectivity and limited catalyst consumption (paragraph [0077]).
With regard to claim 17, Pretz teaches the presence of a gas liquid contactor including packing or trays (paragraph [0060]).
With regard to claim 18, Pretz teaches the quench tower 502 comprises a quench fluid recycle inlet 586 and outlet 588 (paragraph [0056, Fig. 2), thus comprising a recirculation loop for continuously recirculating the wash fluid.
With regard to claim 19, Pretz teaches the quench fluid (wash fluid) is water or oil (paragraph [0044])
Claims 11-15 are rejected under 35 U.S.C. 103 as being unpatentable over Pretz (US 2020/0197891) in view of Mukherjee et al. (US 2022/0080390) as applied to claim 10 above, and further in view of Tallman et al. (US 7,011,740).
With regard to claims 11-13, Pretz in view of Mukherjee teaches the method above. Pretz further teaches the separation of the quench fluid comprising the fines 514 includes filtration 504 (paragraph [0054]).
Pretz does not specify that the catalyst stream is converted into a slurry before filtering.
Tallman teaches a method for recovering catalyst from an effluent (column 1, lines 6-7, Abstract). Tallman further teaches:
c) separating the catalyst fines from the effluent by contacting with a quench oil (column 2, line 55).
d) forming a slurry of the fines in the quench oil (instant claim 11) (column 2, line 62).
e) continuously filtering catalyst fines from the slurry (instant claim 12), while a second filter in parallel with a first filter is in backflushing mode to remove the separated metal oxide catalyst fines (instant claim 13) (column 8, lines 4-20). Tallman also teaches that recovering a slurry of the catalyst fines in a quench oil, filtering the fines, and then slurrying the fines again can eliminate catalyst losses in the effluent gas (column 2, lines 18-20, 30-32, 38-40).
Therefore, it would have been obvious to one of ordinary skill in the art before the effective filing date of the invention to form the catalyst fines into a slurry and perform continuous filtration as taught by Tallman for the filtration of Pretz, in order to eliminate catalyst losses in the effluent gas (Tallman column 2, lines 18-20).
With regard to claim 14, Tallman further teaches that the filtration comprises periodically alternating the first and the second filters between filtration and backflushing modes (column 3, lines 8-10).
With regard to claim 15, Tallman further teaches that the catalyst fines are accumulated in a slurry drum (catalyst accumulator) (column 8, lines 7-8).
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, 9, and 10 are rejected on the ground of nonstatutory double patenting as being unpatentable over claims 1 and 2 of U.S. Patent No. 11,168,039 in view of Stine et al. (US 2014/0371504).
Instant claim 1 recites a method comprising:
a) dehydrogenation of paraffins having 2-8 carbon atoms with a metal oxide catalyst composition for a reaction period of about 0.05 seconds to about 10 minutes,
b) producing a reactor effluent comprising catalyst fines, and
c) contacting the reactor effluent stream with a wash fluid to remove the catalyst fines and produce a catalyst-free product stream and a catalyst effluent stream;
wherein the catalyst consists of i) an active catalyst component selected from the group consisting of oxides of zinc, copper, iron, niobium, and combinations thereof, ii) a support selected from the group consisting of oxides of aluminum or silicon, and iii) a stabilizer selected from the group consisting of oxides of zirconium, cerium, dysprosium, erbium, europium, gadolinium, lanthanum, neodymium, praseodymium, samarium, terbium, ytterbium, yttrium, niobium, tungsten, and combinations thereof.
Instant claim 2 recites a fluidized bed reactor or fixed-bed swing reactor, instant claim 3 recites specifically propane, ethane, n-butane, isobutane, or combinations thereof for the paraffin, instant claims 4-5 recite the product includes an olefin which is ethylene, propylene, or combinations thereof, instant claims 6 and 7 recite temperature and pressure conditions, instant claim 9 narrows the active catalyst component to zinc, copper, niobium, or combinations thereof.
Instant claim 10 recites a method comprising:
a) dehydrogenation of propane or butane with a metal oxide catalyst composition,
b) producing a reactor effluent comprising catalyst fines, and
c) contacting the reactor effluent stream with a wash fluid to remove the catalyst fines and produce a catalyst-free product stream and a catalyst effluent stream;
wherein the catalyst consists of i) an active catalyst component selected from the group consisting of oxides of zinc, copper, iron, niobium, and combinations thereof, ii) a support selected from the group consisting of oxides of aluminum or silicon, and iii) a stabilizer selected from the group consisting of oxides of zirconium, cerium, dysprosium, erbium, europium, gadolinium, lanthanum, neodymium, praseodymium, samarium, terbium, ytterbium, yttrium, niobium, tungsten, and combinations thereof.
Claim 1 of the Patent recites a method comprising:
a) dehydrogenation of paraffins having 2-8 carbon atoms with a metal oxide catalyst composition for a reaction period of 0.05 seconds to 10 minutes, a temperature of 500-800°C, and a pressure of 0.01-0.2 MPa,
wherein the catalyst comprises i) an active catalyst component which is zinc oxide, ii) a support selected from the group consisting of oxides of aluminum or silicon, and iii) a stabilizer selected from the group consisting of oxides of zirconium, cerium, dysprosium, erbium, europium, gadolinium, lanthanum, neodymium, praseodymium, samarium, terbium, ytterbium, yttrium, tungsten, and combinations thereof.
Claim 2 of the Patent recites a fluidized bed or fixed-bed swing reactor.
Thus claims 1 and 2 of the Patent encompass claims 1-7, 9, and 10 of the instant application.
The difference is that the Patent does not explicitly recite the steps b) of obtaining catalyst fines and c) of washing the effluent to remove the catalyst fines. However, the Patent recites the same process with the same catalyst as claimed, thus, one of ordinary skill in the art would reasonably expect catalyst fines in the effluent, as claimed. Stine teaches a process for paraffin dehydrogenation in the presence of a metal oxide containing catalyst on an alumina or silica support (paragraphs [0001], [0062], [0068]) and in a fluidized bed reactor (paragraph [0024]). Stine further teaches that the effluent from the reactor is sent to a vapor cooler where water is injected to suppress further reactions, followed by sending the cooled vapor to a water/hydrocarbon separator where water and catalyst fines are collected in the bottom and the hydrocarbon effluent is collected from the top (paragraphs [0032]-[0033]). This is equivalent to the step c) of contacting the rector effluent stream with a wash fluid to transfer the fines to the wash fluid to produce a cooled catalyst stream and a catalyst-free product stream of instant claim 1. Stine further teaches that removing the catalyst fines is useful before sending the olefins to further processes (paragraph [0033]).
Therefore, it would have been obvious to one of ordinary skill in the art at the time of the invention to add the quench step of Stine the process of the Patent because one of ordinary skill in the art would expect the presence of catalyst fines in the effluent of the Patent process, and Stine teaches that it is known and useful to remove the catalyst fines from the hydrocarbon effluent before further use of the olefins (paragraphs [0032]-[0033]).
Claims 1-7, 9, and 10 are rejected on the ground of nonstatutory double patenting as being unpatentable over claims 1, 6, 9, 11, and 16-18 of U.S. Patent No. 11,040,331 in view of Stine et al. (US 2014/0371504).
Instant claim 1 recites a method comprising:
a) dehydrogenation of paraffins having 2-8 carbon atoms with a metal oxide catalyst composition for a reaction period of about 0.05 seconds to about 10 minutes,
b) producing a reactor effluent comprising catalyst fines, and
c) contacting the reactor effluent stream with a wash fluid to remove the catalyst fines and produce a catalyst-free product stream and a catalyst effluent stream;
wherein the catalyst consists of i) an active catalyst component selected from the group consisting of oxides of zinc, copper, iron, niobium, and combinations thereof, ii) a support selected from the group consisting of oxides of aluminum or silicon, and iii) a stabilizer selected from the group consisting of oxides of zirconium, cerium, dysprosium, erbium, europium, gadolinium, lanthanum, neodymium, praseodymium, samarium, terbium, ytterbium, yttrium, niobium, tungsten, and combinations thereof.
Instant claim 2 recites a fluidized bed reactor or fixed-bed swing reactor, instant claim 3 recites specifically propane, ethane, n-butane, isobutane, or combinations thereof for the paraffin, instant claims 4-5 recite the product includes an olefin which is ethylene, propylene, or combinations thereof, instant claims 6 and 7 recite temperature and pressure conditions, instant claim 9 narrows the active catalyst component to zinc, copper, niobium, or combinations thereof.
Instant claim 10 recites a method comprising:
a) dehydrogenation of propane or butane with a metal oxide catalyst composition,
b) producing a reactor effluent comprising catalyst fines, and
c) contacting the reactor effluent stream with a wash fluid to remove the catalyst fines and produce a catalyst-free product stream and a catalyst effluent stream;
wherein the catalyst consists of i) an active catalyst component selected from the group consisting of oxides of zinc, copper, iron, niobium, and combinations thereof, ii) a support selected from the group consisting of oxides of aluminum or silicon, and iii) a stabilizer selected from the group consisting of oxides of zirconium, cerium, dysprosium, erbium, europium, gadolinium, lanthanum, neodymium, praseodymium, samarium, terbium, ytterbium, yttrium, niobium, tungsten, and combinations thereof.
Claims 1, 6, 9, 11, and 16 of the Patent recite a method comprising:
a) dehydrogenation of paraffins having 2-8 carbon atoms with a metal oxide catalyst composition for a reaction period of 0.05 seconds to 10 minutes, a temperature of 500-800°C, and a pressure of 0.01-0.2 MPa,
wherein the catalyst comprises (b) a mixed metal oxide comprising i) an active catalyst component which is selected from oxides of copper, iron, niobium, and zinc, ii) a support selected from the group consisting of oxides of aluminum or silicon, and iii) a stabilizer selected from the group consisting of oxides of zirconium, cerium, dysprosium, erbium, europium, gadolinium, lanthanum, neodymium, praseodymium, samarium, terbium, ytterbium, yttrium, tungsten, and combinations thereof.
Claim 17 of the Patent recites a fluidized bed or fixed-bed swing reactor and claim 18 of the Patent recites the paraffin is propane or isobutane.
Thus claims 1, 6, 9, 11, and 16-18 of the Patent encompass claims 1-7, 9, and 10 of the instant application.
The difference is that the Patent does not explicitly recite the steps b) of obtaining catalyst fines and c) of washing the effluent to remove the catalyst fines. However, the Patent recites the same process with the same catalyst as claimed, thus, one of ordinary skill in the art would reasonably expect catalyst fines in the effluent, as claimed. Stine teaches a process for paraffin dehydrogenation in the presence of a metal oxide containing catalyst on an alumina or silica support (paragraphs [0001], [0062], [0068]) and in a fluidized bed reactor (paragraph [0024]). Stine further teaches that the effluent from the reactor is sent to a vapor cooler where water is injected to suppress further reactions, followed by sending the cooled vapor to a water/hydrocarbon separator where water and catalyst fines are collected in the bottom and the hydrocarbon effluent is collected from the top (paragraphs [0032]-[0033]). This is equivalent to the step c) of contacting the rector effluent stream with a wash fluid to transfer the fines to the wash fluid to produce a cooled catalyst stream and a catalyst-free product stream of instant claim 1. Stine further teaches that removing the catalyst fines is useful before sending the olefins to further processes (paragraph [0033]).
Therefore, it would have been obvious to one of ordinary skill in the art at the time of the invention to add the quench step of Stine the process of the Patent because one of ordinary skill in the art would expect the presence of catalyst fines in the effluent of the Patent process, and Stine teaches that it is known and useful to remove the catalyst fines from the hydrocarbon effluent before further use of the olefins (paragraphs [0032]-[0033]).
Conclusion
The prior art made of record and not relied upon is considered pertinent to applicant's disclosure.
Thakur et al. (US 2020/0199043) teaches a catalyst for dehydrogenation comprising a first component which is a metal of Group VIB, which includes tungsten (stabilizer), a metal of Group VIII, which includes iron (active component), and support material which is alumina or silica (page 5, claims 8 and 9).
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/Alyssa L Cepluch/Examiner, Art Unit 1772
/IN SUK C BULLOCK/Supervisory Patent Examiner, Art Unit 1772