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 .
Drawings
The drawings were received on 12/30/2025. These drawings are acceptable.
Claim Rejections - 35 USC § 112
The following is a quotation of the first paragraph of 35 U.S.C. 112(a):
(a) IN GENERAL.—The specification shall contain a written description of the invention, and of the manner and process of making and using it, in such full, clear, concise, and exact terms as to enable any person skilled in the art to which it pertains, or with which it is most nearly connected, to make and use the same, and shall set forth the best mode contemplated by the inventor or joint inventor of carrying out the invention.
The following is a quotation of the first paragraph of pre-AIA 35 U.S.C. 112:
The specification shall contain a written description of the invention, and of the manner and process of making and using it, in such full, clear, concise, and exact terms as to enable any person skilled in the art to which it pertains, or with which it is most nearly connected, to make and use the same, and shall set forth the best mode contemplated by the inventor of carrying out his invention.
Claims 1-9, 18-28 are rejected under 35 U.S.C. 112(a) or 35 U.S.C. 112 (pre-AIA ), first paragraph, as failing to comply with the written description requirement. The claim(s) contains subject matter which was not described in the specification in such a way as to reasonably convey to one skilled in the relevant art that the inventor or a joint inventor, or for applications subject to pre-AIA 35 U.S.C. 112, the inventor(s), at the time the application was filed, had possession of the claimed invention.
Claim 1 recites “the natural gas comprising methane, carbon monoxide, carbon dioxide, and higher hydrocarbons” which lacks support in the specification and as such is considered new matter. The stream that enters the system as supported in the specification is a pipeline gas, and is passed through a series of initial steps including pre-reformer which removes the higher hydrocarbons as well as produced carbon monoxide. The initial stream does not contain carbon monoxide, and the stream entering the autothermal reformer does not appear to actually contain any hydrocarbons beyond any support of “most”, of which most is not clearly defined. As such, it is clear that there is no support for the natural gas stream containing carbon monoxide, only that a later stream formed from the initial natural gas stream upstream of the autothermal reformer has carbon monoxide present in it.
Claim 1 recites “a molecular sieve to remove at least most of the moisture from the syngas stream” which is considered new matter as it does not have support in the specification. While the specification does have support for using a molecular sieve, the location of “from the syngas stream” is broader than the support in the specification for such limitation.
Claim 18 recites “separating at least a portion of the hydrogen from at least a portion of the introduced natural gas” which lacks support in the specification and as such is considered new matter. There is no support for removing hydrogen from a natural gas stream as the separation stages for hydrogen are after the natural gas has been passed through an auto-thermal reformer.
Claim 20 recites “using the gas having the gas temperature from the air separation unit” which lacks support in the specification. As is clear in the drawings, while the gas that is used to cool the stream that is separated into liquid carbon dioxide and hydrogen gas is also used to cool an ammonia stream, they would not be at the same temperature.
Claim 21 recites “wherein the natural gas further comprises hydrogen sulfide and carbon monoxide” which lacks support in the specification and as such is considered new matter. The stream that enters the system as supported in the specification is a pipeline gas, and is passed through a series of initial steps including pre-reformer which removes the higher hydrocarbons as well as produced carbon monoxide. The initial stream does not contain carbon monoxide, and the stream entering the autothermal reformer does not appear to actually contain any hydrocarbons beyond any support of “most”, of which most is not clearly defined. Further, the hydrogen sulfide is removed before the carbon monoxide is added and such there also lacks support for the hydrogen sulfide and carbon monoxide being present in the same stream. As such, it is clear that there is no support for the natural gas stream containing carbon monoxide, only that a later stream formed from the initial natural gas stream upstream of the autothermal reformer has carbon monoxide present in it.
Claim 22 recites “providing a natural gas comprising methane, carbon dioxide, carbon monoxide, hydrogen sulfide and higher hydrocarbons” which lacks support in the specification and as such is considered new matter. The stream that enters the system as supported in the specification is a pipeline gas, and is passed through a series of initial steps including pre-reformer which removes the higher hydrocarbons as well as produced carbon monoxide. The initial stream does not contain carbon monoxide, and the stream entering the autothermal reformer does not appear to actually contain any hydrocarbons beyond any support of “most”, of which most is not clearly defined. Further, the hydrogen sulfide is removed before the carbon monoxide is added and such there also lacks support for the hydrogen sulfide and carbon monoxide being present in the same stream. As such, it is clear that there is no support for the natural gas stream containing carbon monoxide, only that a later stream formed from the initial natural gas stream upstream of the autothermal reformer has carbon monoxide present in it.
Claim 23 recites “wherein the hydrogen is desorbed from the hydrogen-rich adsorption bed by increasing a pressure to a pressure close to a feed pressure of the natural gas” which is considered new matter as it is not supported by the specification. The specification makes it clear that it is the carbon dioxide that is absorbed not the hydrogen (which would be consistent with what one having ordinary skill in the art would expect) and that desorbing happens when the pressure is lowered (see page 18 of the instant specification). There is also no teaching of increasing the pressure of the bed.
Claims 2-9, 19, 24-28 are rejected as being dependent upon a rejected claim.
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 1-9, 18-28 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 1 recites “the natural gas comprising methane, carbon monoxide, carbon dioxide, and higher hydrocarbons” which is considered indefinite. Natural gas is not a stream that contains carbon monoxide, and as claimed it is unclear how or where this stream would be in the system as even in view of the instant specification this limitation is unclear and not supported, as the specification makes it clear the some of the initial methane is converter into carbon monoxide, see rejection above under 35 USC 112(a). Further the specification makes it clear that processes are done on the feed stream prior to entering the autothermal reformer. For the purpose of examination, this limitation is understood that there is an initial natural gas into the overall system, not into the auto-thermal reformer, which stream comprising methane, carbon dioxide, and higher hydrocarbons, and at some point before passing to the auto-thermal reformer, carbon monoxide is added to that stream in some way with higher hydrocarbons only required in the initial feed stream.
Regarding Claim 1, the recitation of “the auto-thermal reformer outputs a syngas stream”
renders indefinite the metes and bounds sought for protection of the claim. In the instant case, the claim recites both an apparatus and process in the same claim. Per MPEP 2173.05(p): “[a] single claim which claims both an apparatus and the method steps of using the apparatus is indefinite under 35 U.S.C. 112(b) or pre-AIA 35 U.S.C. 112, second paragraph.” This limitation and all subsequent limitations rejected for the same reason are understood to only be referring to structural connections or what the component is configured to do.
Claim 1 recites “a molecular sieve to remove at least most of the moisture from the syngas stream” which is indefinite as it is unclear how it relates to the other components in the system, as the syngas stream is effectively removed from the system by other components. For the purpose of examination, as long as the molecular sieve is on a component of the syngas stream the imitation is met.
Regarding Claim 1, the recitation of “a pressure swing adsorption system that receives” renders indefinite the metes and bounds sought for protection of the claim. In the instant case, the claim recites both an apparatus and process in the same claim. Per MPEP 2173.05(p): “[a] single claim which claims both an apparatus and the method steps of using the apparatus is indefinite under 35 U.S.C. 112(b) or pre-AIA 35 U.S.C. 112, second paragraph.”
Regarding Claim 1, the recitation of “the pressure swing adsorption system separates” renders indefinite the metes and bounds sought for protection of the claim. In the instant case, the claim recites both an apparatus and process in the same claim. Per MPEP 2173.05(p): “[a] single claim which claims both an apparatus and the method steps of using the apparatus is indefinite under 35 U.S.C. 112(b) or pre-AIA 35 U.S.C. 112, second paragraph.”
Regarding Claim 1, the recitation of “the pressure swing adsorption system outputs” renders indefinite the metes and bounds sought for protection of the claim. In the instant case, the claim recites both an apparatus and process in the same claim. Per MPEP 2173.05(p): “[a] single claim which claims both an apparatus and the method steps of using the apparatus is indefinite under 35 U.S.C. 112(b) or pre-AIA 35 U.S.C. 112, second paragraph.”
Claim 1 recites “an air separation unit comprising a cold box cooled by a refrigerant to convert the carbon dioxide rich stream into a fluid comprising dense phase carbon dioxide and hydrogen gas” which is considered indefinite as it is unclear how the cold box of the air separation unit would be related to cooling of the carbon dioxide rich stream, as a cold box is generally understood to be referring to a barrier or enclosure. For the purpose of examination, this limitation is understood that the air separation unit produces a stream used as a refrigerant to cool the carbon dioxide rich stream in a heat exchanger.
Claim 1 recites a series of components related to the syngas stream but does not clearly link how those components are related so it is unclear if they are connected or if as long as some aspect of the syngas stream is addressed by these components the limitation is met. This results in it for example being unclear where the molecular sieve is located as the pressure swing adsorption system appear to disassemble the syngas stream. For the purpose of examination, the molecular sieve is understood to be for removing water from the carbon dioxide rich stream from the PSA.
Regarding Claim 4, the recitation of “the one or more membranes output… and output”
in lines 3-4 renders indefinite the metes and bounds sought for protection of the claim. In the instant case, the claim recites both an apparatus and process in the same claim. Per MPEP 2173.05(p): “[a] single claim which claims both an apparatus and the method steps of using the apparatus is indefinite under 35 U.S.C. 112(b) or pre-AIA 35 U.S.C. 112, second paragraph.”
Claim 5 recites “the gas having the gas temperature” which is considered indefinite and lacks antecedent basis in the claim as no previous “has having the gas temperature” is recited. For the purpose of examination, this limitation is understood to refer to the refrigerant in claim 1.
Regarding Claim 7, the recitation of “that aids” in line renders indefinite the metes and bounds sought for protection of the claim. In the instant case, the claim recites both an apparatus and process in the same claim. Per MPEP 2173.05(p): “[a] single claim which claims both an apparatus and the method steps of using the apparatus is indefinite under 35 U.S.C. 112(b) or pre-AIA 35 U.S.C. 112, second paragraph.”
Regarding Claim 8, the recitation of “wherein the hydrogen-rich stream is inputs” renders indefinite the metes and bounds sought for protection of the claim. In the instant case, the claim recites both an apparatus and process in the same claim. Per MPEP 2173.05(p): “[a] single claim which claims both an apparatus and the method steps of using the apparatus is indefinite under 35 U.S.C. 112(b) or pre-AIA 35 U.S.C. 112, second paragraph.”
Regarding Claim 8, the recitation of “wherein the hydrogen-rich stream and nitrogen are input” renders indefinite the metes and bounds sought for protection of the claim. In the instant case, the claim recites both an apparatus and process in the same claim. Per MPEP 2173.05(p): “[a] single claim which claims both an apparatus and the method steps of using the apparatus is indefinite under 35 U.S.C. 112(b) or pre-AIA 35 U.S.C. 112, second paragraph.”
Claim 18 recites “separating at least a portion of hydrogen from at least a portion of the introduced natural gas” which is considered indefinite. The introduced natural gas no longer exists upon entering the catalyst bed as it is converted into hydrogen and carbon dioxide so it unclear how the hydrogen can be removed as such. For the purpose of examination, this limitation is understood to be that the hydrogen is removed from the stream after the catalyst bed.
Claim 19 recites “the introducing” which is considered indefinite as it is unclear if this refers to “introducing the natural gas into a catalyst bed”. For the purpose of examination, this limitation is understood to refer to the limitation of claim 18 above.
Claim 20 recites “the introducing” which is considered indefinite as it is unclear if this refers to “introducing the natural gas into a catalyst bed”. For the purpose of examination, this limitation is understood to refer to the limitation of claim 18 above.
Claim 20 recites “using the gas having the gas temperature from the air separation unit” which is considered indefinite as it is unclear if this means that the gas is still at the same temperature when it is used as a refrigerant for ammonia liquefaction. For the purpose of examination, this limitation is interpreted that it is only the same gas that is required, not the same temperature gas.
A broad range or limitation together with a narrow range or limitation that falls within the broad range or limitation (in the same claim) may be considered indefinite if the resulting claim does not clearly set forth the metes and bounds of the patent protection desired. See MPEP § 2173.05(c). In the present instance, claim 20 recites the broad recitation 0.3-1.5, and the claim also recites or more preferably between about 0.4-1.3, or even more preferably between about 0.6-1.0 which is the narrower statement of the range/limitation. The claim(s) are considered indefinite because there is a question or doubt as to whether the feature introduced by such narrower language is (a) merely exemplary of the remainder of the claim, and therefore not required, or (b) a required feature of the claims. For the purpose of examination, this limitation is interpreted to only required the broadest range.
A broad range or limitation together with a narrow range or limitation that falls within the broad range or limitation (in the same claim) may be considered indefinite if the resulting claim does not clearly set forth the metes and bounds of the patent protection desired. See MPEP § 2173.05(c). In the present instance, claim 20 recites the broad recitation most, and the claim also all which is the narrower statement of the range/limitation. The claim(s) are considered indefinite because there is a question or doubt as to whether the feature introduced by such narrower language is (a) merely exemplary of the remainder of the claim, and therefore not required, or (b) a required feature of the claims. For the purpose of examination, this limitation is interpreted to only require the broadest range.
Claim 20 recites “all or most” which is considered indefinite as claim 18 requires the presence of higher hydrocarbons in the natural gas. For the purpose of examination, this limitation is understood that the higher hydrocarbons are only required to be present at some point in the natural gas, not the entire time it is present.
Claim 21 recites “before the providing” as well as “the introduced natural gas” which are both considered indefinite as it is unclear if they relate to the previous limitation of “providing” and “introducing”. For the purpose of examination, they are considered to relate to those limitations.
Claim 21 recites “converting a first portion of the carbon monoxide in the introduced natural gas” which is considered indefinite. As best understood in view of the specification, and as would be understood in view of one having ordinary skill in the art, shift happens after the natural gas has passed through a reformer so it is unclear how or when natural gas with carbon monoxide would have shift occur. For the purpose of examination, this limitation is interpreted to be after the catalyst bed that the stream produced from the catalyst bed is introduced into the shift, which stream contains carbon monoxide.
The term “most” in claim 21 is a relative term which renders the claim indefinite. The term “most” is not defined by the claim, the specification does not provide a standard for ascertaining the requisite degree, and one of ordinary skill in the art would not be reasonably apprised of the scope of the invention. For the purpose of examination, as long as the step is made with the intention or removing the component or densifying the component recited, the limitation is met.
Claim 21 recites “wherein the hydrogen-rich stream and carbon dioxide rich stream are derived from the carbon monoxide converted gas” which is considered indefinite as the claims previously make it clear the pressure swing adsorption system is what forms the two streams. For the purpose of examination, this limitation is interpreted that the shift reactions happen upstream of the pressure swing adsorption such that the stream for the low temperature shift is passed to the pressure swing adsorption.
Claim 21 recites “removing, by a molecular sieve dryer, most of the water from the carbon dioxide reach stream to form a dried waste gas, wherein the cooling comprises thermally contacting the dried waste gas with a cryogenic liquid to cryogenically convert the most of the carbon dioxide in the dried waste gas to a dense phase to form dense phase carbon dioxide for sequestration and to form a product gas comprising hydrogen;
Claim 21 recites “mixing the product gas with nitrogen to form a make-up gas comprising hydrogen and nitrogen; reacting the nitrogen and hydrogen to form an ammonia-containing gas; chilling the ammonia-containing gas to form liquid ammonia; and separating the liquid ammonia from a purge gas” all of which appears to be limitations already addressed in claim 18 and as such is treated as a repeated limitation.
Claim 22 recites “the natural gas comprising methane, carbon monoxide, carbon dioxide, and higher hydrocarbons” which is considered indefinite. Natural gas is not a stream that contains carbon monoxide, and as claimed it is unclear how or where this stream would be in the system as even in view of the instant specification this limitation is unclear and not supported, as the specification makes it clear the some of the initial methane is converter into carbon monoxide, see rejection above under 35 USC 112(a). Further the specification makes it clear that processes are done on the feed stream prior to entering the catalyst bed. For the purpose of examination, this limitation is understood that there is an initial natural gas into the overall system, not into the auto-thermal reformer, which stream comprising methane, carbon dioxide, and higher hydrocarbons, and at some point before passing to the catalyst bed, carbon monoxide is added to that stream in some way with higher hydrocarbons only required in the initial feed stream.
Claim 23 recites “wherein the hydrogen is desorbed from the hydrogen-rich adsorption bed by increasing a pressure to a pressure close to a feed pressure of the natural gas” which is considered indefinite. One having ordinary skill in the art would recognize that an adsorption bed for carbon dioxide and hydrogen laden stream would adsorb the carbon dioxide not the hydrogen and that depressurization would happen, not pressurization for desorbing as this is consistent with how a pressure swing adsorption system would work, which is also consistent with the instant specification (page 18) which is how the claim is interpreted such that desorbing is depressurization to the pressure as claimed.
A broad range or limitation together with a narrow range or limitation that falls within the broad range or limitation (in the same claim) may be considered indefinite if the resulting claim does not clearly set forth the metes and bounds of the patent protection desired. See MPEP § 2173.05(c). In the present instance, claim 26 recites the broad recitation most, and the claim also all which is the narrower statement of the range/limitation. The claim(s) are considered indefinite because there is a question or doubt as to whether the feature introduced by such narrower language is (a) merely exemplary of the remainder of the claim, and therefore not required, or (b) a required feature of the claims. For the purpose of examination, this limitation is interpreted to only require the broadest range.
While this is meant to be a comprehensive list of all issues in regard to 35 USC 112 in the claims, due to the length and nature of the claims, it may not be possible to indicate every issue in regard to 35 USC 112 and the Applicant is requested to perform a thorough review of the claims for any outstanding issues in regard to 35 USC 112. The applicant is also requested to proof-read any future amendments for any potential issues in regard to 35 USC 112 that can arise from the amendments due to the complexity of the claims.
Claims 2-9, 24-25 are rejected as being dependent upon a rejected claim.
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.
Claim(s) 1-6, 9 is/are rejected under 35 U.S.C. 103 as being unpatentable over LeBlanc et al. (US Patent No. 5736116), hereinafter referred to as LeBlanc and further in view of Olskiv et al. (US Patent No. 6838071), hereinafter referred to as Olskiv and further in view of Terrien et al. (EP 2733115), hereinafter referred to as Terrien and further in view of Hashizume (US PG Pub 20150345859), hereinafter referred to as Hashizume and Tadiello et al. (US PG Pub 20210300757), hereinafter referred to as Tadiello.
With respect to claim 1, LeBlanc teaches (Figure 2) a system, comprising:
an auto-thermal reformer (secondary reformer 112, Column 5, lines 63 which is an autothermal reformer, Column 5, line 11-15) and inlets for steam, molecular oxygen and natural gas (partially reformed effluent 110 is fed to 112, which would include natural gas, Column 5, lines 10-15, 62, as well as oxygen and steam as part of an air/steam which is an oxygen-enriched air stream 120, Column 5, lines 63-66, Table 1), the natural gas comprising methane, carbon monoxide, carbon dioxide, and higher hydrocarbons (initial feed to primary contains methane carbon dioxide, hydrogen sulfide as well as higher hydrocarbons, and after the primary reformer, reformer effluent no longer contains hydrogen sulfide or higher hydrocarbons but does contain carbon monoxide, Table 1, which meets the limitation as understood in view of the rejections under 35 USC 112a/b)
wherein the auto-thermal reformer outputs a syngas stream (autothermal reformer produces an outlet stream 122) comprising at least carbon dioxide, water and hydrogen (Table 1, secondary reformer effluent has hydrogen, carbon monoxide and water)
a separator to separate carbon dioxide fluid from hydrogen (in 140, the stream is separated into a CO2 sub lean stream and a CO2 lean stream Column 6, lines 8-18, 144 which would have hydrogen),
LeBlanc does not teach that the autothermal reformer has a catalyst bed.
Olskiv teaches that in an autothermal reformer the gas stream is brough into contact with a catalyst bed (Column 2, lines 35-36).
Therefore it would have been obvious to a person having ordinary skill in the art at the time the invention was filed to have based on the teaching of Olskiv autothermal reformer of LeBlanc with a catalyst bed since it has been shown that combining prior art elements to yield predictable results is obvious whereby one having common knowledge in the art would recognize that providing a catalyst bed would provide the predictable result of ensuring the necessary reforming process took place.
LeBlanc does not teach a pressure swing adsorption system that receives the syngas stream as an input wherein the pressure swing adsorption system separates the syngas stream into a hydrogen-rich stream and a carbon dioxide-rich stream, and wherein the pressure swing adsorption system outputs the hydrogen-rich stream and the carbon dioxide-rich stream.
Terrien teaches that the syngas stream (15) is first fed to a pressure swing adsorption system (0) which has multiple beds that separates it into a hydrogen stream (23) and a stream that includes carbon dioxide (Paragraphs 23-26).
Therefore it would have been obvious to a person having ordinary skill in the art at the time the invention was filed for the carbon dioxide removal system of LeBlanc (132) to have been a pressure swing adsorption system with multiple beds which produces a carbon dioxide rich stream (it would be rich compared to how it enters as hydrogen is removed) as well as a hydrogen product stream based on the teaching of Terrien since it has been shown that combining prior art elements to yield predictable results is obvious whereby utilizing a pressure swing adsorption system would allow for the recovery of a high purity hydrogen stream (paragraph 24 of Terrien) which would allow active separation of the hydrogen from the effluent stream by what would be common knowledge in the art of maintaining a bed always ready to operate.
LeBlanc does not teach a molecular sieve remove at least most of the moisture is molecular sieve to remove at least most moisture from the syngas stream.
Tadiello teaches that a molecular sieve can be used to free syngas from water which would cause downstream issues such as freezing (paragraph 63).
Therefore, it would have been obvious to a person having ordinary skill in the art at the time the invention was filed to have provided a molecular sieve in LeBlanc to remove water from the syngas stream based on the teaching of Tadiello in order to prevent any downstream issues that might happen such as freezing if further cooling were provided. Freeing the stream from water would be understood as being the same as removing most of the water.
LeBlanc does not unit comprising a cold box cooled by a refrigerant to convert the carbon dioxide-rich stream into a fluid comprising dense phase carbon dioxide and hydrogen gas.
Terrien (Figure 2a) teaches that the tail gas stream (the carbon dioxide rich stream) can be passed via from the adsorption to a carbon dioxide separation unit including a heat exchanger and a separator to provide separation of the carbon dioxide stream into a carbon dioxide liquid (6) and a non-condensable stream which contains hydrogen (5) against a refrigerant (paragraphs 10, 51, 54) and as the hydrogen containing stream is non-condensable has hydrogen gas.
Therefore it would have been obvious to a person having ordinary skill in the art to have for the further separation of hydrogen and carbon dioxide in the stream from the pressure swing adsorption of LeBlanc as modified that contains carbon dioxide to have provide a heat exchanger (which is a cold box) to condense the carbon dioxide so it can be passed to a separator to form a non-condensable stream which contains hydrogen gas and a liquid carbon dioxide stream (which would be a dense phase stream) against a refrigerant in the heat exchanger as part of the carbon dioxide removal system since it has been shown that combining prior art elements to yield predictable results is obvious whereby providing the additional cooling and separation would provide a known way to produce what would be common knowledge in the art of a separation that would can be almost entirety carbon dioxide which has multiple different uses (paragraph 51 of Terrien).
LeBlanc does not teach the cold box is part of an air separation unit.
Hashizume teaches that to liquefy carbon dioxide, cryogenically-separated low temperature gaseous nitrogen from an air separation unit is passed to the carbon dioxide liquefaction unit (paragraph 32).
Therefore it would have been obvious to a person having ordinary skill in the art at the time the invention was filed to have based on the teaching of Hashizume to provide cooling for the liquefaction of the carbon dioxide of LeBlanc to have provided low temperature nitrogen from an air separation unit (which can be considered to be cryogenic) since it has been shown that combining prior art elements to yield predictable results is obvious whereby one having ordinary skill in the art would recognize it common knowledge that nitrogen is a suitable refrigerant for liquefying carbon dioxide that is readily available through air separation. This would result in the nitrogen gas being the claimed refrigerant.
With respect to claim 2, LeBlanc as modified teaches a separator to separate the dense phase carbon dioxide from the hydrogen gas (as modified in claim 1, there is a separator), an input to combine nitrogen with the separated hydrogen gas to form a make-up gas (the separated hydrogen gas would be part of stream 144 which ultimately passes to 152 where it is mixed with nitrogen 198, Column 7, lines 3-4 which forms a make-up gas, Column 6, line 152), a converter to convert the nitrogen and hydrogen in the make-up gas into ammonia (this gas is ultimately passed converter 174 to produce ammonia 176, Column 6, lines 40-41), a chiller to convert the ammonia into liquid ammonia and a residual make-up gas (in heat exchanger 182 which would condense the ammonia, Column 6, lines 45-50 and produce condensed ammonia and ultimately 160 which is a recycle stream, Column 6, line 29, which is a make-up gas as it is mixed with the other make-up gas).
With respect to claim 3, LeBlanc as modified one or more multi-stage compressors, wherein the one or more multi-stage compressors are located subsequent to the pressure swing adsorption system, and wherein the one or more multi-stage compressors are located prior to the molecular sieve dryer, or subsequent to the molecular sieve dryer, or a combination thereof.
Terrien teaches that after a PSA and upstream of drying the produced carbon dioxide stream can be sent to a compressor that includes multiple compression stages (paragraph 27-28).
Therefore it would have been obvious to a person having ordinary skill in the art at the time the invention was filed to have based on the teaching Terrien to have provided upstream of the molecular sieve and downstream of the PSA of LeBlanc as modified to have compressed the syngas stream in a multi-stage compressor since it has been shown that combining prior art elements to yield predictable results is obvious whereby providing compression would provide what would be common knowledge in the art of the ability to bring the stream to the proper pressure for further processing.
With respect to claim 4, LeBlanc teaches high temperature and low temperature water shift reactors (shift converter 128 which can include high and low temperature shift converters in series which react steam and carbon monoxide, Column 6, lines 1-7 which are before the pressure swing adsorption system as modified and in view of the 112b this is the configuration).
LeBlanc does not teach one or more membranes, following high temperature and low temperature water wherein the one or more membranes output a second hydrogen rich-stream that is recycled to the pressure swing adsorption system and output a second carbon dioxide-rich stream.
Terrien teaches that the carbon dioxide rich stream of the system is fed to a membrane separation unit 42 which is downstream form the PSA which produces a hydrogen stream 43 and a hydrogen lean residue stream which has carbon dioxide which is fed back to the processing unit that is the PSA paragraphs 31, 38 and 41, 44 which is upstream of the separation that forms the liquid stream).
Therefore it would have been obvious to a person having ordinary skill in the art at the time the invention was field to have based on the teaching of Terrien to have provided downstream of the PSA and upstream of the carbon dioxide separation to have provided in LeBlanc as modified a membrane separation unit that further separates hydrogen from the carbon dioxide rich stream and recycles some of the hydrogen back to the PSA so that it can recovered be further utilized including as a supplemental feed stream to the PSA unit so as to maximize the use of the available hydrogen to convert in the conversion process (paragraph 41).
With respect to claim 5, LeBlanc as modified teaches the gas having the cryogenic gas temperature comprises nitrogen (as modified the refrigerant is nitrogen).
With respect to claim 6, LeBlanc as modified teaches wherein the auto-thermal reformer is integrated with a high-temperature shift reactor and a low-temperature shift reactor, and wherein an output of the auto-thermal reformer is an input to the high-temperature shift reactor, and an output of the high-temperature shift reactor is an input to the low-temperature shift reactor (shift converter 128 which can include high and low temperature shift converters in series which react stream and carbon monoxide, Column 6, lines 1-7, which means the output from the autothermal reactor is ultimately passed to high and then low temperature shift).
With respect to claim 9, LeBlanc as modified does teaches an ammonia synthesis system loop positioned in a gas flow path between first and second chillers, wherein the hydrogen-rich stream and nitrogen are input to the ammonia synthesis system to synthesize ammonia (hydrogen rich stream is mixed with nitrogen is mixed with nitrogen 198, Column 7, lines 3-4 which forms a make-up gas, Column 6, line 152 and then ultimately used to produce ammonia withdrawn, Column 6, lines 40-41).
Claim(s) 7 is/are rejected under 35 U.S.C. 103 as being unpatentable over LeBlanc/Olksiv/Terrien/Hashizume and further in view of Tomlinson (US Patent No. 10788259), hereinafter referred to as Tomlinson.
With respect to claim 7, LeBlanc as modified does not teach a flooded tube chiller integrated with a propane compression refrigeration cycle that aids in the thermal conversion of the carbon dioxide-rich stream to the dense phase.
Tomlinson teaches that in a liquefaction system a pre-cooling system can be provided which uses a compressor (2-stage compressor) in a closed loop and a flooded-bath and tube exchanger (26) using propane (Figure 9, Column 6, lines 60-67).
Therefore, it would have been obvious to a person having ordinary skill in the art at the time the invention as filed to have based on the teaching of Tomlinson to have provide a pre-cooling system in LeBlanc as part of the liquefaction of the carbon dioxide (thermal conversion) using propane in a closed loop with a compressor and a flooded-bath and tube exchanger since it has been shown that combining prior art elements to yield predictable results is obvious whereby one having ordinary skill in the art would recognize that it is common knowledge in the art that liquefaction can be done using a multi-tiered method which would allow for efficient cooling by matching the cooling levels to specific refrigerants.
Claim(s) 8 is/are rejected under 35 U.S.C. 103 as being unpatentable over LeBlanc/Olksiv/Terrien/Hashizume and further in view of Koh (US PG Pub 20080272340), hereinafter referred to as Koh.
With respect to claim 8, LeBlanc as modified does not teach a cogeneration power plant, wherein the hydrogen-rich stream is input to the cogeneration plant as a fuel source.
Koh teaches that hydrogen generated as part of a syngas production system can be fed as fuel for combustion in a combined heat and power unit (paragraph 26). Combined heat and power may be a plant for cogeneration to generate both power and steam which results in high efficiency compared to conventional production of heat or electricity (paragraph 8).
Therefore it would have been obvious to a person having ordinary skill in the art at the time the invention was field to have based on the teaching of Koh provided the hydrogen from LeBlanc as modified to a cogeneration system instead of to ammonia production since it has been shown that a simple substitution of one known element (one or for another of the hydrogen) to yield predictable results is obvious whereby using the hydrogen in a cogeneration plant as fuel would allow for providing the generation of both power and steam with high efficiency.
Claim(s) 18 is/are rejected under 35 U.S.C. 103 as being unpatentable over LeBlanc and further in view of Olksiv and Terrien.
With respect to claim 18, LeBlanc (Figure 2) teaches providing a natural gas stream comprising methane and carbon dioxide (feed to primary reactor is an initial provide natural gas stream which has higher hydrocarbons and methane, Table 1),
introducing the natural gas into a reformer the presence of steam and molecular oxygen to convert methane into hydrogen and carbon dioxide (partially reformed effluent 110 is fed to secondary reformer 112, which would include some of the natural gas, Column 5, lines 10-15, 62, as well as oxygen and steam as part of an air/steam which is an oxygen-enriched air stream 120, Column 5, lines 63-66, produces and effluent which contains hydrogen and carbon monoxide, Table 1, secondary reformer effluent has hydrogen, carbon monoxide and water),
separating at least a portion of the hydrogen from at least a portion of the introduced natural gas to form a hydrogen-rich stream and a carbon dioxide-rich stream (CO2 142 is separated from the stream to produce a hydrogen richer stream, Column 6, lines 17-20),
mixing product gas with nitrogen to form a make-up gas comprising hydrogen and nitrogen (the separated hydrogen gas would be part of stream 144 which ultimately passes to 152 where it is mixed with nitrogen 198, Column 7, lines 3-4 which forms a make-up gas, Column 6, line 152),
reacting the nitrogen and hydrogen to form an ammonia-containing gas (the mixed gas is ultimately passed to converter 174 which is a reactor to produce ammonia 176, Column 6, lines 34-41, which would be a gas as it is later condensed, column 6, lines 43-44),
chilling the ammonia-containing gas to form liquid ammonia and separating the liquid ammonia from a purge gas (in heat exchanger 182 which would condense the ammonia, Column 6, lines 45-50 and produce condensed ammonia and which is removed as ammonia product stream which as it is form a condensed stream would be a liquid stream and a recycle stream, Column 6, line 42-46, such that 166 could be considered the purge gas or the stream that is not liquefied in 184 can be the purge gas which is separated to form the liquid stream).
LeBlanc does not teach separating at least a portion of the hydrogen from at least a portion of the syngas to form a hydrogen-rich stream is done by using pressure swing adsorption.
Terrien teaches that the syngas stream (15) is first fed to a pressure swing absorption system (0) which has multiple beds that separates it into a hydrogen stream (23) and a stream that includes carbon dioxide (Paragraphs 23-26).
Therefore it would have been obvious to a person having ordinary skill in the art at the time the invention was filed for the carbon dioxide removal system of LeBlanc (132) to have been a pressure swing adsorption system with multiple beds which produces a carbon dioxide rich stream (it would be rich compared to how it enters as hydrogen is removed) as well as a hydrogen product stream based on the teaching of Terrien since it has been shown that combining prior art elements to yield predictable results is obvious whereby utilizing a pressure swing adsorption system would allow for the recovery of a high purity hydrogen stream (paragraph 24 of Terrien) which would allow active separation of the hydrogen from the effluent stream by what would be common knowledge in the art of maintaining a bed always ready to operate.
LeBlanc does not teach cooling the carbon dioxide rich stream to cryogenically convert the carbon dioxide rich stream to a dense phase to form dense phase carbon dioxide and a gas containing hydrogen, separating the dense phase form the gas phase to provide a product gas comprising hydrogen.
Terrien (Figure 2a) teaches that the tail gas stream (the carbon dioxide rich stream) can be passed via from the adsorption to a carbon dioxide separation unit including a heat exchanger and a separator to provide separation of the carbon dioxide stream into a carbon dioxide liquid (6) and a non-condensable stream which contains hydrogen (5) against a refrigerant (paragraphs 10, 51, 54) and as the hydrogen containing stream is non-condensable has hydrogen gas.
Therefore it would have been obvious to a person having ordinary skill in the art to have for the further separation of hydrogen and carbon dioxide in the stream from the pressure swing adsorption of LeBlanc as modified that contains carbon dioxide to have provide a heat exchanger (which is a cold box) to condense the carbon dioxide so it can be passed to a separator to form a non-condensable stream which contains hydrogen gas and a liquid carbon dioxide stream (which would be a dense phase stream) against a refrigerant in the heat exchanger as part of the carbon dioxide removal system since it has been shown that combining prior art elements to yield predictable results is obvious whereby providing the additional cooling and separation would provide a known way to produce what would be common knowledge in the art of a separation that would can be almost entirety carbon dioxide which has multiple different uses (paragraph 51 of Terrien).
LeBlanc does not teach that the autothermal reformer has a catalyst bed.
Olskiv teaches that in an autothermal reformer the gas stream is brough into contact with a catalyst bed (Column 2, lines 35-36).
Therefore, it would have been obvious to a person having ordinary skill in the art at the time the invention was filed to have based on the teaching of Olskiv autothermal reformer of LeBlanc with a catalyst bed since it has been shown that combining prior art elements to yield predictable results is obvious whereby one having common knowledge in the art would recognize that providing a catalyst bed would provide the predictable result of ensuring the necessary reforming process took place.
Claim(s) 19 is/are rejected under 35 U.S.C. 103 as being unpatentable over LeBlanc/Olksiv/Terrien and Hashizume and further in view of Bormann et al. (US PG Pub 20090105356), hereinafter referred to as Bormann and Ahmed (US PG Pub 20180134967), hereinafter referred to as Ahmed.
With respect to claim 19, LeBlanc teaches the introduction is performed to convert methane into hydrogen and carbon dioxide to form a reformed gas (secondary reformer effluent contains carbon dioxide and methane from conversion).
LeBlanc does teach wherein the introducing is performed at a temperature ranging from about 800 to about 1.300°C. LeBlanc does teach the effluent form the primary reactor which is fed into the secondary reformer is at 810 C, but this is not an explicit teaching that is the temperature the stream is at when it enters the autothermal reformer.
Bormann teaches that for economic operation of an autothermal reformer it is required to preheat the feed gas to a temperature as high as possible to reduce the amount of oxygen needed for autothermal cracking reaction (paragraph 7). Thus, the temperature that the introducing is performed at is a result effective variable, known to be set to provide the best economic operation to reduce the amount of oxygen needed. Further, it appears that one of ordinary skill in the art would have had a reasonable expectation of modifying LeBlanc as modified as it involves only adjusting the dimension a component disclosed to require adjustment. Therefore, it would have been obvious to one having ordinary skill in the art at the time of the invention to modify the device of LeBlanc as modified so that the temperature of the introducing was between about 800 to about 1300 C as a matter of routine optimization since it has been held that “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, 456, 105 USPQ 233, 235 (CCPA 1955).
LeBlanc does not teach the steam-to-carbon molar ratio between about 0.2 to about 2.
Olksiv teaches that in an autothermal reformer, the ratio of steam to carbon is 0.6 to 1.4 (Column 4, lines 46-47).
It would have been obvious to a person having ordinary skill in the art at the time the invention was filed to have operated LeBlanc as modified such that the steam-to-carbon molar ratio between about 0.2 to about 2 as applicant appears to have placed no criticality on the claimed range (see page 16 indicating the ratio was about 0.2-2, or more preferably about 0.3-1.8 or even more preferably about 0.5-1.5) and since it has been held that “[i]n the case where the claimed ranges ‘overlap or lie inside ranges disclosed by the prior art’ a prima facie case of obviousness exists.” In re Wertheim, 541 F.2d 257, 191 USPQ 90 (CCPA 1976); In re Woodruff, 919 F.2d 1575, 16 USPQ2d 1934 (Fed. Cir. 1990).
LeBlanc does not teach the oxygen to carbon molar ratio (O/C ratio) between about 0.3-1.5.
Ahmed teaches the molar ratio of the carbon and oxygen feed to an autothermal reformer can be altered to alter the molar ratio of syngas (paragraph 54).
Thus, the carbon to oxygen ratio is a result effective variable, known to be set to provide the best economic operation to be set based on the molar ratio of the syngas. Further, it appears that one of ordinary skill in the art would have had a reasonable expectation of modifying LeBlanc as modified as it involves only adjusting the dimension a component disclosed to require adjustment. Therefore, it would have been obvious to one having ordinary skill in the art at the time of the invention to modify the device of LeBlanc as modified so that the oxygen to carbon molar ratio (O/C ratio) between about 0.3-1.5 as a matter of routine optimization since it has been held that “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, 456, 105 USPQ 233, 235 (CCPA 1955).
LeBlanc does not teach cooling the carbon dioxide-rich stream comprises: thermally contacting a gas having a gas temperature from a cold box of an air separation unit to cool the carbon dioxide stream to the gas temperature and cryogenically convert the carbon dioxide rich stream to dense phase carbon dioxide.
Hashizume teaches that to liquefy carbon dioxide, cryogenically-separated low temperature gaseous nitrogen from an air separation unit is passed to the carbon dioxide liquefaction unit (paragraph 32).
Therefore it would have been obvious to a person having ordinary skill in the art at the time the invention was filed to have based on the teaching of Hashizume to provide cooling for the liquefaction of the carbon dioxide of LeBlanc to have provided low temperature nitrogen from an air separation unit (which can be considered to be cryogenic) since it has been shown that combining prior art elements to yield predictable results is obvious whereby one having ordinary skill in the art would recognize it common knowledge that nitrogen is a suitable refrigerant for liquefying carbon dioxide that is readily available through air separation. This would result in the nitrogen gas being the claimed gas.
Claim(s) 20 is/are rejected under 35 U.S.C. 103 as being unpatentable over LeBlanc/Olksiv/Terrien/Hashizume/Bormann/Ahmed and further in view of Lautenschlager (US PG Pub 20240255220), hereinafter referred to as Lautenschlager.
With respect to claim 20, LeBlanc teaches the O/C ratio is between about 0.3-1.5 (this is the ratio in claim 19 above).
LeBlanc does not teach wherein in the introducing the natural gas has a temperature ranging from about 900 to about 1200°C.
Bormann teaches that for economic operation of an autothermal reformer it is required to preheat the feed gas to a temperature as high as possible to reduce the amount of oxygen needed for autothermal cracking reaction (paragraph 7). Thus, the temperature that the introducing is performed at is a result effective variable, known to be set to provide the best economic operation to reduce the amount of oxygen needed. Further, it appears that one of ordinary skill in the art would have had a reasonable expectation of modifying LeBlanc as modified as it involves only adjusting the dimension a component disclosed to require adjustment. Therefore, it would have been obvious to one having ordinary skill in the art at the time of the invention to modify the device of LeBlanc as modified so that the temperature of the introducing was between about 900 to about 1200 C as a matter of routine optimization since it has been held that “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, 456, 105 USPQ 233, 235 (CCPA 1955).
LeBlanc does not teach the steam-to-carbon molar ratio between about 0.5 to about 1.5.
Olksiv teaches that in an autothermal reformer, the ratio of steam to carbon is 0.6 to 1.4 (Column 4, lines 46-47).
It would have been obvious to a person having ordinary skill in the art at the time the invention was filed to have operated LeBlanc as modified such that the steam-to-carbon molar ratio between about 0.2 to about 2 as applicant appears to have placed no criticality on the claimed range (see page 16 indicating the ratio was about 0.5 to about 1.5, or more preferably about 0.3-1.8 or even more preferably about 0.5-1.5) and since it has been held that “[i]n the case where the claimed ranges ‘overlap or lie inside ranges disclosed by the prior art’ a prima facie case of obviousness exists.” In re Wertheim, 541 F.2d 257, 191 USPQ 90 (CCPA 1976); In re Woodruff, 919 F.2d 1575, 16 USPQ2d 1934 (Fed. Cir. 1990).
LeBlanc as modified does not teach the O/C ratio is between about 0.3-1.5, or more preferably between about 0.4-1.3, or even more preferably between about 0.6-1.0.
Ahmed teaches the molar ratio of the carbon and oxygen feed to an autothermal reformer can be altered to alter the molar ratio of syngas (paragraph 54).
Thus, the carbon to oxygen ratio is a result effective variable, known to be set to provide the best economic operation to be set based on the molar ratio of the syngas. Further, it appears that one of ordinary skill in the art would have had a reasonable expectation of modifying LeBlanc as modified as it involves only adjusting the dimension a component disclosed to require adjustment. Therefore, it would have been obvious to one having ordinary skill in the art at the time of the invention to modify the device of LeBlanc as modified so that the oxygen to carbon molar ratio (O/C ratio) between about 0.3-1.5 as a matter of routine optimization since it has been held that “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, 456, 105 USPQ 233, 235 (CCPA 1955).
LeBlanc as modified does not teach using the gas having the gas temperature from the air separation unit as a refrigerant for ammonia liquefaction in the chilling.
Lautenschlager teaches that a cryogenic fluid provided by air separation can be used to provide cooling for liquefying ammonia (paragraph 33) including nitrogen (paragraph 62).
Therefore it would have been obvious to a person having ordinary skill in the art at the time the invention was filed based on the teaching of Lautenschlager to have utilized the same gas (a part of the stream of nitrogen) that is used to provide cooling to liquefy the carbon dioxide to also liquefy the ammonia of LeBlanc as modified since it has been shown that combining prior art elements to yield predictable results where it would be common knowledge in the art that a refrigerant would be required for ammonia liquefaction and choosing one from the available streams already in the system such as the same nitrogen (which is the gas having the gas temperature) that is sent for the carbon dioxide liquefaction would reduce the need for an additional external refrigerant in the system.
Claim(s) 21 is/are rejected under 35 U.S.C. 103 as being unpatentable over LeBlanc/Olksiv/Terrien and further in view of Ostuni et al. (US PG Pub 20160115017), hereinafter referred to as Ostuni and Zhong (US PG Pub 20180318750), hereinafter referred to as Zhong.
With respect to claim 21, LeBlanc teaches wherein the natural gas further comprises hydrogen sulfide (the initial feed gas has hydrogen sulfide, Column 5, lines 55-57), carbon monoxide (the natural gas that enters 112has carbon monoxide mixed with it, table 1) and further comprising:
absorbing hydrogen sulfide in the natural gas on a zinc oxide catalyst to form a desulfurized natural gas (the natural gas reacts with zinc oxides to remove the hydrogen sulfide, Column 5, lines 55-57, which would be absorbing with the zinc oxide acting as a catalyst), converting a first portion of the carbon monoxide in the introduced natural gas to carbon dioxide in a high temperature; converting a second portion of the carbon monoxide in the high temperature shift gas into carbon dioxide (shift converter 128 which can include high and low temperature shift converters in series which react steam and carbon monoxide to form carbon dioxide, Column 6, lines 1-7, which would have shift gas from high temperature shift reactor then convert in the low temperature shift reactor), wherein the hydrogen-rich stream and carbon dioxide rich stream are derived from the carbon monoxide converted gas (the stream that is from the shift reactions is what is passed to form the carbon monoxide and carbon dioxide streams),
mixing product gas with nitrogen to form a make-up gas comprising hydrogen and nitrogen (the separated hydrogen gas would be part of stream 144 which ultimately passes to 152 where it is mixed with nitrogen 198, Column 7, lines 3-4 which forms a make-up gas, Column 6, line 152),
reacting the nitrogen and hydrogen to form an ammonia-containing gas (the mixed gas is ultimately passed to converter 174 which is a reactor to produce ammonia 176, Column 6, lines 34-41, which would be a gas as it is later condensed, column 6, lines 43-44),
chilling the ammonia-containing gas to form liquid ammonia and separating the liquid ammonia from a purge gas (in heat exchanger 182 which would condense the ammonia, Column 6, lines 45-50 and produce condensed ammonia and which is removed as ammonia product stream which as it is form a condensed stream would be a liquid stream and a recycle stream, Column 6, line 42-46, such that 166 could be considered the purge gas or the stream that is not liquefied in 184 can be the purge gas which is separated to form the liquid stream).
LeBlanc as modified does not teach the zinc oxide catalyst operating in a temperature range from 200 to about 500 C.
Zhong teaches that adsorption reaction rate for zinc oxide is accelerate as the temperature rises (paragraph 99)
Thus, temperature of operation for the zinc oxide catalyst is a result effective variable, known based on the adsorption reaction rate. Further, it appears that one of ordinary skill in the art would have had a reasonable expectation of modifying LeBlanc as modified as it involves only adjusting the dimension a component disclosed to require adjustment. Therefore, it would have been obvious to one having ordinary skill in the art at the time of the invention to modify the device of LeBlanc as modified so that the zinc oxide catalyst operating in a temperature range from 200 to about 500 C as a matter of routine optimization since it has been held that “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, 456, 105 USPQ 233, 235 (CCPA 1955).
LeBlanc does not teach before the providing, converting all or most of higher hydrocarbons in the desulfurized natural gas to methane in a pre-reformed gas. Though LeBlanc does teach a primary reformer which has higher hydrocarbons entering and none leaving (Table 1), which likely means this is what is happening in the primary reactor (108).
Terrien teaches that a pre-reformer can be used upstream of reforming to reform the heavier hydrocarbons in the hydrocarbon containing stream to prevent excessive heat rise in the main reformer (paragraph 17).
Therefore, it would have been obvious to a person having ordinary skill in the art at the time the invention was filed to have based on the teaching of Terrien to have provided a pre-reformer to reform the heavier hydrocarbons in the natural gas of LeBlanc upstream of reforming (a pre-reformer would convert heavy hydrocarbons to methane as would be understood by one having ordinary skill in the art) in order to prevent excessive heat rise during the reforming steps. Further, the actual amount of reformed heavier hydrocarbons would be a result effective variable, where it I desirable to remove them so as to prevent them causing any excessive heat rise. Further, it appears that one of ordinary skill in the art would have had a reasonable expectation of success in modifying LeBlanc as modified as it involves only adjusting a dimension of a component disclose to require adjusting. Therefore, it would have been obvious to one having ordinary skill in the art at the time of the invention to modify the device of Terrien as modified to have had most or all of the heavier hydrocarbons removed as a matter of routine optimization since it has been held that “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, 456, 105 USPQ 233, 235 (CCPA 1955).
LeBlanc does not teach the high temperature shift happens between 400 to 500 C.
Ostuni teaches that high temperature shift happens at 320-500 C (paragraph 4).
It would have been obvious to one having ordinary skill in the art before the effective filing date of the claimed invention to modify LeBlanc based on the teaching of Ostuni so that the high temperature shift temperature is 400 to 500 C degrees as applicant appears to have placed no criticality on the claimed range (the temperatures are indicating as being about the range) and since it has been held that “[i]n the case where the claimed ranges ‘overlap or lie inside ranges disclosed by the prior art’ a prima facie case of obviousness exists.” In re Wertheim, 541 F.2d 257, 191 USPQ 90 (CCPA 1976); In re Woodruff, 919 F.2d 1575, 16 USPQ2d 1934 (Fed. Cir. 1990).
LeBlanc does not explicitly teach the high temperature shift has a catalyst the presence of a high temperature shift catalyst.
Ostuni teaches that high temperature shift happens over a catalyst (paragraph 4).
Therefore it would have been obvious to a person having ordinary skill in the art at the time the invention was filed for the high temperature shift of LeBlanc to have happened over a catalyst since it has been shown that combining prior art elements to yield predictable results is obvious whereby providing a catalyst would provide what would be common knowledge in the art of ensuring the desired shift reaction.
LeBlanc does not teach the low temperature shift happens from 150 to 300 C.
Ostuni teaches that low temperature shift operates at 190 to 250 C (paragraph 4).
It would have been obvious to one having ordinary skill in the art before the effective filing date of the claimed invention to modify LeBlanc based on the teaching of Ostuni so that the low temperature shift temperature is 150 to 300 C degrees as applicant appears to have placed no criticality on the claimed range (the temperatures are indicating as being about the range) and since it has been held that “[i]n the case where the claimed ranges ‘overlap or lie inside ranges disclosed by the prior art’ a prima facie case of obviousness exists.” In re Wertheim, 541 F.2d 257, 191 USPQ 90 (CCPA 1976); In re Woodruff, 919 F.2d 1575, 16 USPQ2d 1934 (Fed. Cir. 1990).
LeBlanc as modified does not teach removing by a dryer, water from the carbon dioxide rich stream to form the dry waste gas.
Terrien teaches that a dryer can be used to remove water from hydrogen lean residue stream (paragraph 47), which would be understood to be a carbon dioxide rich stream.
Therefore it would have been obvious to a person having ordinary skill in the art at the time the invention was filed to have used a drier on the carbon dioxide rich stream of LeBlanc (the tail gas stream from the PSA as modified) since it has been shown that combining prior art elements to yield predictable results is obvious whereby it would be common knowledge in the art to remove water from the stream to prevent any issues that could occur downstream during further processing such as freezing. This would form the dry waste gas stream from the tail gas stream.
Tadiello teaches that a molecular sieve can be used to free syngas from water which would cause downstream issues such as freezing (paragraph 63).
Therefore it would have been obvious to a person having ordinary skill in the art at the time the invention was filed to have provided as the dryer of LeBlanc as modified a molecular sieve to free by water from the stream based on the teaching of Tadiello since it has been shown that combining prior art elements to yield predictable results is obvious, whereby a person having common knowledge in the art would use a known and suitable drier to provide the desired removal of water from the stream when considering what drier to use.
LeBlanc as modified does not teach wherein the cooling comprises thermally contacting the dried waste gas with a cryogenic liquid to cryogenically convert the most of the carbon dioxide in the dried waste gas to a dense phase to form dense phase carbon dioxide for sequestration and to form the product gas comprising hydrogen.
Terrien (Figure 2a) teaches that the tail gas stream (the carbon dioxide rich stream) can be passed via from the adsorption to a carbon dioxide separation unit including a heat exchanger and a separator to provide separation of the carbon dioxide stream into a carbon dioxide liquid (6) and a non-condensable stream which contains hydrogen (5) against a refrigerant (paragraphs 10, 51, 54) and as the hydrogen containing stream is non-condensable has hydrogen gas. Further Terrien teaches that the carbon dioxide rich liquid can be used in the same heat exchanger which provides the cooling of the stream that becomes the carbon dioxide.
Therefore it would have been obvious to a person having ordinary skill in the art to have for the further separation of hydrogen and carbon dioxide in the dried stream from the pressure swing absorption of LeBlanc as modified that contains carbon dioxide to have provide a heat exchanger to condense the dried stream so it can be passed to a separator to form a non-condensable stream which contains hydrogen gas and a liquid carbon dioxide stream (which would be a dense phase stream) against a the liquid carbon dioxide stream (a cryogenic liquid) that is separate refrigerant in the heat exchanger as part of the carbon dioxide removal system since it has been shown that combining prior art elements to yield predictable results is obvious whereby providing the additional cooling and separation would provide a known way to produce what would be common knowledge in the art of a separation that would can be almost entirety carbon dioxide which has multiple different uses (paragraph 51 of Terrien).
Claim(s) 22-24 is/are rejected under 35 U.S.C. 103 as being unpatentable over LeBlanc and further in view of Olksiv, Terrien and Ahmed.
With respect to claim 22, LeBlanc teaches (Figure 2) a method, comprising:
providing a natural gas comprising methane, carbon dioxide, carbon monoxide, hydrogen sulfide, and higher hydrocarbons (initial feed to primary contains methane carbon dioxide, hydrogen sulfide as well as higher hydrocarbons, and after the primary reformer, reformer effluent no longer contains hydrogen sulfide or higher hydrocarbons but does contain carbon monoxide, Table 1, which meets the limitation as understood in view of the rejections under 35 USC 112a/b)
introducing the natural gas in the presence of steam and molecular oxygen into hydrogen and carbon dioxide to form a reformed gas (partially reformed effluent 110 is fed to secondary reformer 112, which would include some of the natural gas, Column 5, lines 10-15, 62, as well as oxygen and steam as part of an air/steam which is an oxygen-enriched air stream 120, Column 5, lines 63-66, produces and effluent which contains hydrogen and carbon monoxide, Table 1, secondary reformer effluent has hydrogen, carbon monoxide, carbon dioxide, and water, which as the shift contains steam would result in some carbon dioxide being produced as well), converting a portion of the carbon monoxide in the reformed gas to carbon dioxide to form a carbon monoxide converted gas (shift converter 128 which can include high and low temperature shift converters in series which react steam and carbon monoxide to form carbon dioxide, Column 6, lines 1-7).
LeBlanc does not teach that the autothermal reformer has a catalyst bed.
Olskiv teaches that in an autothermal reformer the gas stream is brough into contact with a catalyst bed (Column 2, lines 35-36).
Therefore it would have been obvious to a person having ordinary skill in the art at the time the invention was filed to have based on the teaching of Olskiv autothermal reformer of LeBlanc with a catalyst bed since it has been shown that combining prior art elements to yield predictable results is obvious whereby one having common knowledge in the art would recognize that providing a catalyst bed would provide the predictable result of ensuring the necessary reforming process took place.
LeBlanc does teach wherein the introducing is performed at a temperature ranging from about 800 to about 1.300°C. LeBlanc does teach the effluent form the primary reactor which is fed into the secondary reformer is at 810 C, but this is not an explicit teaching that is the temperature the stream is at when it enters the autothermal reformer.
Bormann teaches that for economic operation of an autothermal reformer it is required to preheat the feed gas to a temperature as high as possible to reduce the amount of oxygen needed for autothermal cracking reaction (paragraph 7). Thus, the temperature that the introducing is performed at is a result effective variable, known to be set to provide the best economic operation to reduce the amount of oxygen needed. Further, it appears that one of ordinary skill in the art would have had a reasonable expectation of modifying LeBlanc as modified as it involves only adjusting the dimension a component disclosed to require adjustment. Therefore, it would have been obvious to one having ordinary skill in the art at the time of the invention to modify the device of LeBlanc as modified so that the temperature of the introducing was between about 800 to about 1300 C as a matter of routine optimization since it has been held that “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, 456, 105 USPQ 233, 235 (CCPA 1955).
LeBlanc does not teach the steam-to-carbon molar ratio between about 0.2 to about 2.
Olksiv teaches that in an autothermal reformer, the ratio of steam to carbon is 0.6 to 1.4 (Column 4, lines 46-47).
It would have been obvious to a person having ordinary skill in the art at the time the invention was filed to have operated LeBlanc as modified such that the steam-to-carbon molar ratio between about 0.2 to about 2 as applicant appears to have placed no criticality on the claimed range (see page 16 indicating the ratio was about 0.2-2, or more preferably about 0.3-1.8 or even more preferably about 0.5-1.5) and since it has been held that “[i]n the case where the claimed ranges ‘overlap or lie inside ranges disclosed by the prior art’ a prima facie case of obviousness exists.” In re Wertheim, 541 F.2d 257, 191 USPQ 90 (CCPA 1976); In re Woodruff, 919 F.2d 1575, 16 USPQ2d 1934 (Fed. Cir. 1990).
LeBlanc does not teach the oxygen to carbon molar ratio (O/C ratio) between about 0.3-1.5.
Ahmed teaches the molar ratio of the carbon and oxygen feed to an autothermal reformer can be altered to alter the molar ratio of syngas (paragraph 54).
Thus, the carbon to oxygen ratio is a result effective variable, known to be set to provide the best economic operation to be set based on the molar ratio of the syngas. Further, it appears that one of ordinary skill in the art would have had a reasonable expectation of modifying LeBlanc as modified as it involves only adjusting the dimension a component disclosed to require adjustment. Therefore, it would have been obvious to one having ordinary skill in the art at the time of the invention to modify the device of LeBlanc as modified so that the oxygen to carbon molar ratio (O/C ratio) between about 0.3-1.5 as a matter of routine optimization since it has been held that “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, 456, 105 USPQ 233, 235 (CCPA 1955).
LeBlanc does not teach separating a portion of the carbon dioxide from a portion of the hydrogen gas to form a hydrogen-rich adsorption bed and a carbon dioxide-rich tail gas.
Terrien teaches that the syngas stream (15) is first fed to a pressure swing absorption system (0) which has multiple beds that separates it into a hydrogen stream (23) and a stream that includes carbon dioxide (Paragraphs 23-26). The hydrogen is removed from the feed stream by the PSA and the tail gas is the carbon dioxide stream (paragraph 24). The carbon dioxide stream is the removed stream after depressurization (paragraph 24).
Therefore it would have been obvious to a person having ordinary skill in the art at the time the invention was filed for the carbon dioxide removal system of LeBlanc (132) to have been a pressure swing adsorption system with multiple beds which produces a carbon dioxide rich stream after depressurization (it would be rich compared to how it enters as hydrogen is removed) as well as a hydrogen product stream based on the teaching of Terrien since it has been shown that combining prior art elements to yield predictable results is obvious whereby utilizing a pressure swing adsorption system would allow for the recovery of a high purity hydrogen stream (paragraph 24 of Terrien) which would allow active separation of the hydrogen from the effluent stream by what would be common knowledge in the art of maintaining a bed always ready to operate. The carbon dioxide is the adsorbed stream as it is removed during depressurization, which meets the limitation as best understood in view of 112a/112b.
LeBlanc does not teach cryogenically separating the carbon dioxide from the hydrogen in the carbon dioxide-rich tail gas to form a dense phase fluid comprising most of the carbon dioxide in the carbon dioxide-rich tail gas and a product gas comprising most of the hydrogen in the carbon dioxide-rich tail gas.
Terrien (Figure 2a) teaches that the tail gas stream (the carbon dioxide rich stream) can be passed via from the adsorption to a carbon dioxide separation unit including a heat exchanger and a separator to provide separation of the carbon dioxide stream into a carbon dioxide liquid (6) and a non-condensable stream which contains hydrogen (5) against a refrigerant (paragraphs 10, 51, 54) and as the hydrogen containing stream is non-condensable has hydrogen gas.
Therefore it would have been obvious to a person having ordinary skill in the art to have for the further separation of hydrogen and carbon dioxide in the stream from the pressure swing absorption of LeBlanc as modified that contains carbon dioxide to have provide a heat exchanger (which is a cold box) to condense the carbon dioxide so it can be passed to a separator to form a non-condensable stream which contains hydrogen gas and a liquid carbon dioxide stream (which would be a dense phase stream and as it is a liquid carbon dioxide stream would be understood to have most of the hydrogen removed) against a refrigerant in the heat exchanger as part of the carbon dioxide removal system since it has been shown that combining prior art elements to yield predictable results is obvious whereby providing the additional cooling and separation would provide a known way to produce what would be common knowledge in the art of a separation that would can be almost entirety carbon dioxide which has multiple different uses (paragraph 51 of Terrien).
With respect to claim 23, Terrien does not teach wherein the hydrogen is desorbed from the hydrogen-rich adsorption bed by increasing a pressure to a pressure close to a feed pressure of the natural gas. There would be desorption by pressure change as that is how a PSA operates.
Terrien teaches that depressurization can operate at different pressures including higher pressure to decrease both the size and energy consumption required for downstream compression (paragraph 25).
Thus, the pressure of the desorbing is a result effective variable set based on further operations of the stream. Further, it appears that one of ordinary skill in the art would have had a reasonable expectation of modifying LeBlanc as modified as it involves only adjusting the dimension a component disclosed to require adjustment. Therefore, it would have been obvious to one having ordinary skill in the art at the time of the invention to modify the device of LeBlanc as modified the pressure of the PSA is brought to close to a feed pressure of the natural gas as a matter of routine optimization since it has been held that “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, 456, 105 USPQ 233, 235 (CCPA 1955).
With respect to claim 24, LeBlanc as modified teaches mixing product gas with nitrogen to form a make-up gas comprising hydrogen and nitrogen (the separated hydrogen gas from the cryogenic step would be part of stream 144 which ultimately passes to 152 where it is mixed with nitrogen 198, Column 7, lines 3-4 which forms a make-up gas, Column 6, line 152),
reacting the nitrogen and hydrogen to form an ammonia-containing gas (the mixed gas is ultimately passed to converter 174 which is a reactor to produce ammonia 176, Column 6, lines 34-41, which would be a gas as it is later condensed, column 6, lines 43-44),
chilling the ammonia-containing gas to form liquid ammonia and separating the liquid ammonia from a purge gas (in heat exchanger 182 which would condense the ammonia, Column 6, lines 45-50 and produce condensed ammonia and which is removed as ammonia product stream which as it is form a condensed stream would be a liquid stream and a recycle stream, Column 6, line 42-46, such that 166 could be considered the purge gas or the stream that is not liquefied in 184 can be the purge gas which is separated to form the liquid stream).
Claim(s) 25 is/are rejected under 35 U.S.C. 103 as being unpatentable over LeBlanc/Olksiv/Terrien/Ahmed and further in view of Tadiello.
With respect to claim 25, LeBlanc as modified does teach the converted gas comprises water and further comprising, before cryogenically separating, removing, by a molecular sieve dryer, most of the water from one of the tail gas and carbon monoxide converted gas.
Terrien teaches that a dryer can be used to remove water from hydrogen lean residue stream (paragraph 47), which would be understood to be a carbon dioxide rich stream.
Therefore it would have been obvious to a person having ordinary skill in the art at the time the invention was filed to have used a drier on the carbon dioxide rich stream of LeBlanc (the tail gas stream from the PSA as modified) since it has been shown that combining prior art elements to yield predictable results is obvious whereby it would be common knowledge in the art to remove water from the stream to prevent any issues that could occur downstream during further processing such as freezing. This would form the dry waste gas stream from the tail gas stream.
Tadiello teaches that a molecular sieve can be used to free syngas from water which would cause downstream issues such as freezing (paragraph 63).
Therefore it would have been obvious to a person having ordinary skill in the art at the time the invention was filed to have provided as the dryer of LeBlanc as modified a molecular sieve to free by water from the stream based on the teaching of Tadiello since it has been shown that combining prior art elements to yield predictable results is obvious, whereby a person having common knowledge in the art would use a known and suitable drier to provide the desired removal of water from the stream when considering what drier to use.
Claim(s) 26 is/are rejected under 35 U.S.C. 103 as being unpatentable over LeBlanc/Olskiv/Terrien/Ahmed and further in view of Zhong, Ostuni and Roesch et al. (US PG Pub 20180038642), hereinafter referred to as Roesch.
With respect to claim 26, LeBlanc as modified teaches absorbing hydrogen sulfide in the natural gas on a zinc oxide catalyst (the natural gas reacts with zinc oxides to remove the hydrogen sulfide, Column 5, lines 55-57, which would be absorbing with the zinc oxide acting as a catalyst).
LeBlanc as modified does not teach before the introducing: converting all or most of higher hydrocarbons in natural gas to methane.
Terrien teaches that a pre-reformer can be used upstream of reforming to reform the heavier hydrocarbons in the hydrocarbon containing stream to prevent excessive heat rise in the main reformer (paragraph 17).
Therefore it would have been obvious to a person having ordinary skill in the art at the time the invention was filed to have based on the teaching of Terrien to have provided a pre-reformer to reform the heavier hydrocarbons in the natural gas of LeBlanc upstream of reforming (a pre-reformer would convert heavy hydrocarbons to methane as would be understood by one having ordinary skill in the art) in order to prevent excessive heat rise during the reforming steps. Further, the actual amount of reformed heavier hydrocarbons would be a result effective variable, where it I desirable to remove them so as to prevent them causing any excessive heat rise. Further, it appears that one of ordinary skill in the art would have had a reasonable expectation of success in modifying LeBlanc as modified as it involves only adjusting a dimension of a component disclose to require adjusting. Therefore, it would have been obvious to one having ordinary skill in the art at the time of the invention to modify the device of Terrien as modified to have had most or all of the heavier hydrocarbons removed as a matter of routine optimization since it has been held that “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, 456, 105 USPQ 233, 235 (CCPA 1955).
LeBlanc as modified does not teach wherein the converting or absorbing is on pipeline natural gas, and that the natural gas is derived from the pipeline gas.
Roesch teaches that a source of natural gas for a reformer can be a natural gas from a pipeline (paragraph 171).
Therefore it would have been obvious to a person having ordinary skill in the art at the time the invention was filed to have based on the teaching of Roesch to have had the natural gas source of LeBlanc as modified to have been pipeline gas since it has been shown that combining prior art elements to yield predictable results is obvious where one having ordinary skill in the art would recognize that it would be common knowledge in the art that choosing pipeline gas as the source of the natural gas for the system would provide a known and reliable source for the natural gas. Thus the feed natural gas, and ultimately the natural gas passing through each system is pipeline gas.
LeBlanc does not teach the zinc oxide catalyst is at a temperature ranging from about 200 to about 600 C.
Zhong teaches that adsorption reaction rate for zinc oxide is accelerate as the temperature rises (paragraph 99)
Thus, temperature of operation for the zinc oxide catalyst is a result effective variable, known based on the adsorption reaction rate. Further, it appears that one of ordinary skill in the art would have had a reasonable expectation of modifying LeBlanc as modified as it involves only adjusting the dimension a component disclosed to require adjustment. Therefore, it would have been obvious to one having ordinary skill in the art at the time of the invention to modify the device of LeBlanc as modified so that the zinc oxide catalyst operating in a temperature range from 200 to about 600 C as a matter of routine optimization since it has been held that “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, 456, 105 USPQ 233, 235 (CCPA 1955).
Claim(s) 27 is/are rejected under 35 U.S.C. 103 as being unpatentable over LeBlanc/Olskiv/Terrien/Ahmed and further in view of Ostuni.
With respect to claim 27 converting a first portion of the carbon monoxide in the introduced natural gas to carbon dioxide in a high temperature; converting a second portion of the carbon monoxide in the high temperature shift gas into carbon dioxide (shift converter 128 which can include high and low temperature shift converters in series which react steam and carbon monoxide to form carbon dioxide, Column 6, lines 1-7, which would have shift gas from high temperature shift reactor then convert in the low temperature shift reactor), wherein the hydrogen-rich stream and carbon dioxide rich stream are derived from the carbon monoxide converted gas (the stream that is from the shift reactions is what is passed to form the carbon monoxide and carbon dioxide streams).
Ostuni teaches that high temperature shift happens at 320-500 C (paragraph 4).
It would have been obvious to one having ordinary skill in the art before the effective filing date of the claimed invention to modify LeBlanc based on the teaching of Ostuni so that the high temperature shift temperature is 400 to 500 C degrees as applicant appears to have placed no criticality on the claimed range (the temperatures are indicating as being about the range) and since it has been held that “[i]n the case where the claimed ranges ‘overlap or lie inside ranges disclosed by the prior art’ a prima facie case of obviousness exists.” In re Wertheim, 541 F.2d 257, 191 USPQ 90 (CCPA 1976); In re Woodruff, 919 F.2d 1575, 16 USPQ2d 1934 (Fed. Cir. 1990).
LeBlanc does not explicitly teach the high temperature shift has a catalyst the presence of a high temperature shift catalyst.
Ostuni teaches that high temperature shift happens over a catalyst (paragraph 4).
Therefore it would have been obvious to a person having ordinary skill in the art at the time the invention was filed for the high temperature shift of LeBlanc to have happened over a catalyst since it has been shown that combining prior art elements to yield predictable results is obvious whereby providing a catalyst would provide what would be common knowledge in the art of ensuring the desired shift reaction.
LeBlanc does not teach the low temperature shift happens from 150 to 300 C.
Ostuni teaches that low temperature shift operates at 190 to 250 C (paragraph 4).
It would have been obvious to one having ordinary skill in the art before the effective filing date of the claimed invention to modify LeBlanc based on the teaching of Ostuni so that the low temperature shift temperature is 150 to 300 C degrees as applicant appears to have placed no criticality on the claimed range (the temperatures are indicating as being about the range) and since it has been held that “[i]n the case where the claimed ranges ‘overlap or lie inside ranges disclosed by the prior art’ a prima facie case of obviousness exists.” In re Wertheim, 541 F.2d 257, 191 USPQ 90 (CCPA 1976); In re Woodruff, 919 F.2d 1575, 16 USPQ2d 1934 (Fed. Cir. 1990).
Claim(s) 28 is/are rejected under 35 U.S.C. 103 as being unpatentable over LeBlanc/Olskiv/Terrien/Ahmed and further in view of Bormann
With respect to claim 28, LeBlanc does not teach wherein in the introducing the natural gas has a temperature ranging from about 900 to about 1200°C.
Bormann teaches that for economic operation of an autothermal reformer it is required to preheat the feed gas to a temperature as high as possible to reduce the amount of oxygen needed for autothermal cracking reaction (paragraph 7). Thus, the temperature that the introducing is performed at is a result effective variable, known to be set to provide the best economic operation to reduce the amount of oxygen needed. Further, it appears that one of ordinary skill in the art would have had a reasonable expectation of modifying LeBlanc as modified as it involves only adjusting the dimension a component disclosed to require adjustment. Therefore, it would have been obvious to one having ordinary skill in the art at the time of the invention to modify the device of LeBlanc as modified so that the temperature of the introducing was between about 900 to about 1200 C as a matter of routine optimization since it has been held that “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, 456, 105 USPQ 233, 235 (CCPA 1955).
LeBlanc does not teach the steam-to-carbon molar ratio between about 0.5 to about 1.5.
Olksiv teaches that in an autothermal reformer, the ratio of steam to carbon is 0.6 to 1.4 (Column 4, lines 46-47).
It would have been obvious to a person having ordinary skill in the art at the time the invention was filed to have operated LeBlanc as modified such that the steam-to-carbon molar ratio between about 0.2 to about 2 as applicant appears to have placed no criticality on the claimed range (see page 16 indicating the ratio was about 0.5 to about 1.5, or more preferably about 0.3-1.8 or even more preferably about 0.5-1.5) and since it has been held that “[i]n the case where the claimed ranges ‘overlap or lie inside ranges disclosed by the prior art’ a prima facie case of obviousness exists.” In re Wertheim, 541 F.2d 257, 191 USPQ 90 (CCPA 1976); In re Woodruff, 919 F.2d 1575, 16 USPQ2d 1934 (Fed. Cir. 1990).
LeBlanc as modified does not teach the O/C ratio is between about 0.3-1.5, or more preferably between about 0.4-1.3, or even more preferably between about 0.6-1.0.
Ahmed teaches the molar ratio of the carbon and oxygen feed to an autothermal reformer can be altered to alter the molar ratio of syngas (paragraph 54).
Thus, the carbon to oxygen ratio is a result effective variable, known to be set to provide the best economic operation to be set based on the molar ratio of the syngas. Further, it appears that one of ordinary skill in the art would have had a reasonable expectation of modifying LeBlanc as modified as it involves only adjusting the dimension a component disclosed to require adjustment. Therefore, it would have been obvious to one having ordinary skill in the art at the time of the invention to modify the device of LeBlanc as modified so that the oxygen to carbon molar ratio (O/C ratio) between about 0.3-1.5 as a matter of routine optimization since it has been held that “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, 456, 105 USPQ 233, 235 (CCPA 1955).
Response to Arguments
Applicant’s arguments, see pages 16-20, filed 12/30/2025, with respect to the rejection(s) of claim(s) 1 under 35 USC 103 have been fully considered and are persuasive. Therefore, the rejection has been withdrawn. However, upon further consideration, a new ground(s) of rejection is made in view of LeBlanc. While Terrien is still used in the rejection, it is not provided as the primary reference and only used for showing specific limitations to be obvious.
Conclusion
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/BRIAN M KING/Primary Examiner, Art Unit 3763
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