DETAILED ACTION
Notice of Pre-AIA or AIA Status
The present application, filed on or after March 16, 2013, is being examined under the first inventor to file provisions of the AIA .
Priority
Receipt is acknowledged of certified copies of papers required by 37 CFR 1.55.
Information Disclosure Statement
The information disclosure statement (IDS) submitted on 10/09/2023 has been considered by the examiner.
Claim Rejections - 35 USC § 112
The following is a quotation of 35 U.S.C. 112(b):
(b) CONCLUSION.—The specification shall conclude with one or more claims particularly pointing out and distinctly claiming the subject matter which the inventor or a joint inventor regards as the invention.
The following is a quotation of 35 U.S.C. 112 (pre-AIA ), second paragraph:
The specification shall conclude with one or more claims particularly pointing out and distinctly claiming the subject matter which the applicant regards as his invention.
Claims 8 and 15 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 8 recites the limitation "the pre-reforming stage" in line 2. There is insufficient antecedent basis for this limitation in the claim.
Claim 15 recites the limitation "the " in line 2. There is insufficient antecedent basis for this limitation in the claim.
Claim Rejections - 35 USC § 103
The following is a quotation of 35 U.S.C. 103 which forms the basis for all obviousness rejections set forth in this Office action:
A patent for a claimed invention may not be obtained, notwithstanding that the claimed invention is not identically disclosed as set forth in section 102, if the differences between the claimed invention and the prior art are such that the claimed invention as a whole would have been obvious before the effective filing date of the claimed invention to a person having ordinary skill in the art to which the claimed invention pertains. Patentability shall not be negated by the manner in which the invention was made.
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.
This application currently names joint inventors. In considering patentability of the claims the examiner presumes that the subject matter of the various claims was commonly owned as of the effective filing date of the claimed invention(s) absent any evidence to the contrary. Applicant is advised of the obligation under 37 CFR 1.56 to point out the inventor and effective filing dates of each claim that was not commonly owned as of the effective filing date of the later invention in order for the examiner to consider the applicability of 35 U.S.C. 102(b)(2)(C) for any potential 35 U.S.C. 102(a)(2) prior art against the later invention.
Claims 1-4, 7-13 are rejected under 35 U.S.C. 103 as being unpatentable over Barnett et al (WO 2022155425 A1 as cited in IDS 10/09/2023 in view of Rhinesmith et al (US 20090255181 A1) and Ruhl et al (US 5567398).
Regarding claim 1, Barnett discloses ways to reduce CO2 emissions in a methanol production process and apparatus by removing CO2 from the syngas and processing a purge stream from the methanol synthesis loop to recover hydrogen as a source of a low-carbon fuel to fire the steam methane reformer ([0009] meeting limitation "A process for producing a carbon dioxide depleted synthesis gas product by steam reforming of a hydrocarbon-containing feed gas").
In one aspect, the invention is embodied in a low-CO2 emission methanol process, comprising the steps of: (a) mixing a hydrocarbon feed stock with water to form a mixed feed stream ([0013] meeting limitation "providing a feed gas stream containing … hydrocarbons"). As used herein, "hydrocarbon" refers to any compound comprising carbon and hydrogen ([0047] meeting limitation "gaseous or vaporized hydrocarbons").
Barnett further discloses (b) reforming the mixed feed stream in a reforming furnace comprising a radiant section and a convection section to form a syngas stream ([0013] meeting limitation "(b) introducing the feed gas stream …into a main reforming stage, reacting the feed gas stream in the main reforming stage under steam reforming conditions "). The reforming step (b) preferably comprises a crossover temperature of 566 °C (1050 °F) or less ([0059]). The crossover temperature (XOT) refers to the temperature of the mixed feed stream (natural gas and steam) crossing from the convection preheat to the reformer catalyst tube ([0035] meeting limitation "heated to a steam reforming inlet temperature"). Steam methane reformer 108 generally includes catalyst filled tubes that are heated in a radiant section of a furnace in a manner well known to those skilled in the art ([0091] meeting limitation "in a plurality of reformer tubes filled with a solid particulate reforming catalyst"). The feedstock passes internally through the tubes which are externally heated to supply the energy needed for the endothermic conversion to syngas in stream 130 ([0091] meeting limitation "to produce a crude synthesis gas stream"). For purposes herein, “synthesis gas” or “syngas” refers to a mixture of primarily hydrogen and carbon monoxide, e.g., from a reformer, but which may also comprise water and carbon dioxide ([0054] meeting limitation "containing hydrogen, carbon monoxide, carbon dioxide and unreacted hydrocarbons"). As used herein, “fired heater” refers to a furnace unit in which a fluid stream is heated by one or more fuel burners in a firebox ([0040]). The heating may be effected by passing the fluid through tubes disposed in the firebox, which is dominated by radiant heat transfer and referred to herein as the “radiant section" ([0040]) Steam-methane reformers are used in the following discussion as one non-limiting example of a fired heater ([0040] meeting limitation "said reformer tubes being arranged in a reformer furnace, the interior of which is heated by means of a plurality of burners"). (c) supplying air (or oxy gen-enriched air) and a carbon-lean fuel stream comprising hydrogen to fire the radiant section ([0013] meeting limitation "by burning at least one fuel gas with a … air stream as oxidant"). (d) passing flue gas from the radiant section to the convection section; (e) cooling the flue gas in the convection section and optionally removing particulates from the flue gas; (I) discharging the cooled flue gas ([0013] meeting limitation "to form a flue gas stream, discharging said flue gas stream from said reformer furnace").
Barnett further discloses (g) cooling the syngas stream ([0013]). In the foregoing embodiment or any other embodiment, step (g) can comprise generating steam, preheating boiler feed water, heat exchange with air or cooling water, or a combination thereof ([0067]). Syngas stream 130 from SMR 108 comprises a mixture of primarily hydrogen, carbon monoxide, and carbon dioxide, with lesser amounts of inerts such as nitrogen and argon and unreacted hydrocarbons such as methane ([0093] meeting limitation “crude syngas stream”). The stream 130 is cooled in exchangers 132, 134, 136 to generate steam ([0093] meeting limitation "(c) discharging the crude synthesis gas stream from the main reforming stage and introducing the crude synthesis gas stream into a first cooling device, cooling the crude synthesis gas stream in the first cooling device")….by air cooling or cooling water exchange via line 142 at 40 °C (104 °F) for example ([0093] Meeting limitation "in indirect heat exchange with a first coolant stream"). (h) passing the cooled syngas directly to …an absorber-stripper unit ([0013] meeting limitation "discharging the cooled crude synthesis gas stream from the first cooling device").
Barnett further discloses the dried synthesis gas in stream 146 is then passed through a CO2 removal system 150 to recover CO2 product stream 152 ([0094] meeting limitation "(d) introducing the cooled crude synthesis gas stream and/or the flue gas stream into a carbon dioxide absorption column"). The CO2 can be removed, for example, by adsorption, absorption, cryogenically, using membranes and the like ([0094] meeting limitation " operating by means of a physical or chemical carbon dioxide absorption process"). The CO2 removal system preferably comprises an absorber-stripper using a solvent ([0094]). In absorption column 154, the synthesis gas is contacted with the solvent from stream 158 and CO2 is absorbed ([0094] meeting limitation "bringing the cooled crude synthesis gas stream in the carbon dioxide absorption column into contact with a liquid carbon dioxide selective absorbent stream fed to the carbon dioxide absorption column"). CO2-lean synthesis gas stream 160 is obtained overhead ([0094] meeting limitation "discharging a carbon dioxide depleted synthesis gas product stream as the overhead product of the carbon dioxide absorption column") C02-rich absorbent is collected as a bottoms stream 162 ([0094] meeting limitation "and discharging a carbon dioxide loaded absorbent stream as the bottom product of the carbon dioxide absorption column") and supplied to stripper 156 ([0094] meeting limitation "(e) introducing the carbon dioxide loaded absorbent stream into an absorbent regeneration column") where it is heated by means of reboiler 164 to obtain CO2 product stream 152 overhead, and CO2-lean solvent stream 158 as a bottoms product ([0094 meeting limitation "discharging a carbon dioxide enriched hot vapor stream or gas stream as the overhead product of the absorbent regeneration column and a carbon dioxide depleted hot absorbent stream as the bottoms product of the absorbent regeneration column").
Regarding limitation "contacting the carbon dioxide loaded absorbent stream in the absorbent regeneration column with a hot vapor or gas stripping stream", Barnett discloses stripper 156 where it is heated by means of reboiler 164 ([0094]). The instant specification discloses in the amine regenerator, the solution is almost completely freed from the absorbed carbon dioxide by stripping steam generated in an amine reboiler (Pg. 2 lines 27-29). Therefore, Barnett meets this limitation.
Barnett does not disclose the air is preheated in step b or steps (f)-(h).
Rhinesmith discloses a method of generating hydrogen-enriched fuel gas and carbon dioxide… for storage or sequestration (abstract). The carbon dioxide recovery system is designed to separate the carbon dioxide from the hydrogen rich water-gas stream ([0128]). This is accomplished by absorbing the carbon dioxide in a carbon dioxide recovery solvent ([0128]). The carbon dioxide recovery solvent section (shown in FIGS. 6 and 7) removes the carbon dioxide from the carbon dioxide recovery solvent and recycles the carbon dioxide recovery solvent back to the gas absorption section of the carbon dioxide recovery system ([0132]).
Referring to FIG.7, the overhead gas exiting the top of the solvent stripper 46, i.e. carbon dioxide enriched hot vapor or gas stream, then flows to the solvent stripper reflux condenser 49, i.e. second cooling device, where it is cooled to 15° F. by external refrigeration (shown in FIG. 8), condensing most of the vaporized carbon dioxide recovery solvent from the carbon dioxide, resulting in a carbon dioxide recovery stream (reflux) containing little carbon dioxide, i.e. liquid condensate stream, and a gas stream (carbon dioxide product gas), i.e. carbon dioxide enriched cooled vapor stream or gas stream, containing little carbon dioxide recovery solvent ([0144] meeting limitation “(f) introducing the carbon dioxide enriched hot vapor stream or gas stream into a second cooling device, cooling the carbon dioxide enriched hot vapor stream or gas stream in the second cooling device in indirect heat exchange with a second coolant stream, discharging the carbon dioxide enriched cooled vapor stream or gas stream and a liquid condensate stream from the second cooling device” where refrigerant is interpreted as second coolant stream).
The carbon dioxide recovery solvent is separated from the carbon dioxide product gas in the solvent stripper reflux accumulator 50 ([0144] meeting limitation “(g) introducing the carbon dioxide enriched cooled vapor stream or gas stream and the liquid condensate stream into a phase separation device”) and returned to the solvent stripper 46 by the solvent stripper reflux pump 47 ([0144] meeting limitation “discharging the liquid condensate stream from the phase separation device, and at least partially recycling the liquid condensate stream to the absorbent regeneration column”). The carbon dioxide product gas flows to the refrigerant subcooler 51 ([0144] meeting limitation “discharging a gaseous carbon dioxide rich gas stream from the phase separation device”).
The lean carbon dioxide recovery solvent, i.e. carbon dioxide depleted hot absorbent stream, leaves the solvent stripper 46 at 271°F. and 415 psia and is cooled in the Solvent cross exchanger 44, i.e. third cooling device, to 34°F. by incoming rich carbon dioxide recovery solvent, i.e. third coolant stream ([0144] meeting limitation “(h) introducing the carbon dioxide depleted hot absorbent stream into a third cooling device, cooling the carbon dioxide depleted hot absorbent stream in the third cooling device in indirect heat exchange with a third coolant stream”).
Thus, prior to the effective filing date of the claimed invention it would have been obvious to one of ordinary skill in the art to modify the process of Barnett to include steps f-h in order to remove the carbon dioxide from the carbon dioxide recovery solvent and recycle the carbon dioxide recovery solvent back to the gas absorption section of the carbon dioxide recovery system as taught by Rhinesmith.
Ruhl discloses the operation of the endothermic reaction apparatus 10 will now be described in relation to the reforming of a reformable feed stock (Col. 11 lines 65-67). An endothermic reactant, i.e. feed gas stream, is flowed through the reaction tube 52, i.e. reforming stage, counter-currently (Col. 18 lines 59-60). As the endothermic reactant moves through the reaction catalyst, it will absorb heat and react to produce an endothermic product, i.e. crude synthesis gas (Col. 18 lines 63-65). The endothermic reactant will absorb heat from the combustion products flowing counter-currently through the exothermic reaction chamber, i.e. reformer furnace (Col. 18 lines 65-68). In the region of the air and fuel supply tubes 156 and 157, heat will be transferred from the hot endothermic product, i.e. crude synthesis gas, to the air and fuel, i.e. first coolant stream, being supplied through the air and fuel supply tubes, thereby to preheat the air and fuel while also cooling the hot endothermic product (Col. 19 lines 3-7). The air and fuel are preferably preheated to a sufficiently high temperature such that when the fuel exiting from the nozzle tubes 90 contacts the air in the exothermic reaction chamber 81, the fuel will auto-ignite (Col. 10 lines 44-48).
Thus, prior to the effective filing date of the claimed invention it would have been obvious to one of ordinary skill in the art for at least one coolant stream selected from the group consisting of: the first coolant stream, the second coolant stream, and the third coolant stream, to be formed by at least one air stream which is preheated when passing through the cooler or coolers and to be fed as a preheated air stream as oxidant to step (b) in the method of Barnett in order to preheat the air and fuel such that the fuel will auto-ignite as taught by Ruhl.
Regarding claim 2, Barnett in view of Rhinesmith and Ruhl discloses all the limitations in the claims as set forth above and Rhinesmith further discloses the lean carbon dioxide recovery solvent, i.e. carbon dioxide depleted hot absorbent stream, leaves the solvent stripper 46 at 271°F. and 415 psia and is cooled in the Solvent cross exchanger 44, i.e. third cooling device, to 34°F. by incoming rich carbon dioxide recovery solvent, i.e. carbon dioxide loaded absorbent stream ([0144] meeting limitation “wherein, between step (d) and (e), the carbon dioxide loaded absorbent stream is heated in indirect heat exchange against the carbon dioxide depleted hot absorbent stream before being introduced into the absorbent regeneration column, the carbon dioxide-depleted hot absorbent stream being cooled and passed on to step (h)”).
Regarding claim 3, Barnett in view of Rhinesmith and Ruhl discloses all the limitations in the claims as set forth above and Barnett further discloses air from intake line 210 can be conveyed by forced draft fan 212 through cold air preheater 214… and then to a burner 216 via line 218 for combustion ([0099] meeting limitation “wherein the at least one preheated air stream is further heated by indirect heat exchange before it is passed as oxidant to step (b)”).
Regarding claim 4, Barnett in view of Rhinesmith and Ruhl discloses all the limitations in the claims as set forth above including Barnett discloses C02-rich absorbent is collected as a bottoms stream 162 and supplied to stripper 156 where it is heated by means of reboiler 164 to obtain CO2 product stream 152 overhead, and CO2-lean solvent stream 158 as a bottoms product ([0094] meeting limitation “wherein the contacting of the carbon dioxide loaded absorbent stream in the absorbent regeneration column in step (e) is carried out with a hot vaporous stripping agent stream generated as inherent vapor in the bottom of the absorbent regeneration column by means of a reboiler”).
Regarding claim 7, Barnett in view of Rhinesmith and Ruhl discloses all the limitations in the claims as set forth above and Barnett further discloses the reformer can comprise: … one or more pre-reformers disposed externally of the convection section and further comprising a preheat exchange coil disposed in the convection section to pre-heat the partially reformed stream from the one or more pre-reformers for supply to the primary reformer ([0074] meeting limitation “wherein between steps (a) and (b), the hydrocarbon containing feed gas is first introduced into a pre-reformer, in which the hydrocarbon containing feed gas is converted under pre-reforming conditions to a pre- reformed hydrocarbon containing feed gas, and the pre-reformed hydrocarbon- containing feed gas is then fed to step (b)”).
Regarding claim 8, Barnett in view of Rhinesmith and Ruhl discloses all the limitations in the claims as set forth above and Barnett further discloses the feed stream 114 is … passed through desulfurizer 204… and thence passed through pre-reformer 108B ([0098] meeting limitation “wherein the feed gas containing hydrocarbons is subjected to a desulfurization step prior to reaction in the pre- reforming stage and/or in the main reforming stage”).
Regarding claim 9, Barnett in view of Rhinesmith and Ruhl discloses all the limitations in the claims as set forth above including Barnett discloses amine scrubbing of CO2 is particularly effective at the higher pressure of the synthesis gas 146 relative to the lower pressure of flue gas ([0094] meeting limitation “wherein an absorbent is used according to the following alternatives:(a) a chemical absorbent, preferably an amine containing chemical absorbent; or (b) a physical absorbent”).
Regarding claim 10, Barnett discloses ways to reduce CO2 emissions in a methanol production process and apparatus by removing CO2 from the syngas and processing a purge stream from the methanol synthesis loop to recover hydrogen as a source of a low-carbon fuel to fire the steam methane reformer ([0009] meeting limitation “a plant for producing a carbon dioxide depleted synthesis gas product by steam reforming of a hydrocarbon-containing feed gas”). The apparatus comprises: a mixing station to mix a hydrocarbon feed stock with water and form a mixed feed stream ([0072] meeting limitation “(a) a means for providing a feed gas stream containing gaseous or vaporized hydrocarbons”); a reformer in a reforming furnace… to reform the mixed feed stream and form a syngas stream ([0072] meeting limitation “(b) a main reforming stage”). Steam methane reformer 108 generally includes catalyst filled tubes that are heated in a radiant section of a furnace in a manner well known to those skilled in the art ([0091] meeting limitation “comprising a plurality of reformer tubes filled with a solid particulate reforming catalyst and arranged in a reformer furnace”). An air intake and a carbon-lean fuel stream to fire one or more burners in the radiant section ([0072] meeting limitation “the interior of which is heatable by means of a plurality of burners by burning at least one fuel gas with … air stream as an oxidant to form a flue gas stream”).
Barnett discloses (b) reforming the mixed feed stream in a reforming furnace comprising a radiant section and a convection section to form a syngas stream ([0013] meeting limitation “a means for introducing the feed gas stream … into the main reforming stage,").
The reforming step (b) preferably comprises a crossover temperature of 566 °C (1050 °F) or less ([0059]). The crossover temperature (XOT) refers to the temperature of the mixed feed stream (natural gas and steam) crossing from the convection preheat to the reformer catalyst tube ([0035] meeting limitation "heated to a steam reforming inlet temperature"). One or more process heat exchangers to cool the syngas stream ([0072] meeting limitation “a means for discharging a crude synthesis gas stream from the main reforming stage”). A flue to pass flue gas from the radiant section and through the convection section ([0072] meeting limitation “a means for discharging the flue gas stream from said reformer furnace”).
Barnett discloses One or more process heat exchangers to cool the syngas stream ([0072] meeting limitation “(c) a first cooling device suitable for cooling the crude synthesis gas stream”). The stream 130 is cooled in exchangers 132, 134, 136 to generate steam in line 138 for example, to preheat boiler feed water for example in line 140, and by air cooling or cooling water exchange via line 142 for example ([0093] meeting limitation “in indirect heat exchange with a first coolant stream, a means for introducing the crude synthesis gas stream into the first cooling device, a means for discharging the cooled crude synthesis gas stream from the first cooling device”). The dried synthesis gas in stream 146 is then passed through a CO2 removal system 150 to recover CO2 product stream 152 ([0094] meeting limitation “(d) a carbon dioxide absorption column configured to perform a physical or chemical carbon dioxide absorption process”). The CO2 can be removed, for example, by adsorption, absorption, cryogenically, using membranes and the like ([0094]). In absorption column 154, the synthesis gas is contacted with the solvent from stream 158 and CO2 is absorbed ([0094] meeting limitation “a means for introducing the cooled crude synthesis gas stream and/or the flue gas stream into the carbon dioxide absorption column, a means for introducing a liquid, cooled, carbon dioxide selective absorbent stream into the carbon dioxide absorption column”). CO2-lean synthesis gas stream 160 is obtained overhead ([0094] meeting limitation “a means for discharging a carbon dioxide depleted syngas product stream as the overhead product of the carbon dioxide absorption column”). C02-rich absorbent is collected as a bottoms stream 162 ([0094] meeting limitation “and a means for discharging a carbon dioxide loaded absorbent stream as the bottom product of the carbon dioxide absorption column”) and supplied to stripper 156 ([0094] meeting limitation “(e) an absorbent regeneration column, a means for introducing the carbon dioxide loaded absorbent stream into the absorbent regeneration column”) where it is heated by means of reboiler 164 to obtain CO2 product stream 152 overhead, and CO2-lean solvent stream 158 as a bottoms product ([0094] meeting limitation “a means for discharging a carbon dioxide enriched hot vapor stream or gas stream as the overhead product of the absorbent regeneration column and a means for discharging a carbon dioxide-depleted hot absorbent stream as the bottoms product of the absorbent regeneration column” and “a means for generating a vapor or gas stripping stream in the absorbent regeneration column”).
Barnett does not disclose (f)-(i).
Rhinesmith discloses a system for generating hydrogen-enriched fuel gas and carbon dioxide (abstract).
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As illustrated above in Figure 7, Rhinesmith discloses (f)-(h).
Thus, prior to the effective filing date of the claimed invention it would have been obvious to one of ordinary skill in the art to modify the apparatus of Barnett to include (f)-(h) in order to remove the carbon dioxide from the carbon dioxide recovery solvent and recycle the carbon dioxide recovery solvent back to the gas absorption section of the carbon dioxide recovery system as taught by Rhinesmith.
Ruhl discloses the operation of the endothermic reaction apparatus 10 will now be described in relation to the reforming of a reformable feed stock (Col. 11 lines 65-67). An endothermic reactant, i.e. feed gas stream, is flowed through the reaction tube 52, i.e. reforming stage, counter-currently (Col. 18 lines 59-60). As the endothermic reactant moves through the reaction catalyst, it will absorb heat and react to produce an endothermic product, i.e. crude synthesis gas (Col. 18 lines 63-65). The endothermic reactant will absorb heat from the combustion products flowing counter-currently through the exothermic reaction chamber, i.e. reformer furnace (Col. 18 lines 65-68). In the region of the air and fuel supply tubes 156 and 157, heat will be transferred from the hot endothermic product, i.e. crude synthesis gas, to the air and fuel, i.e. first coolant stream, being supplied through the air and fuel supply tubes, thereby to preheat the air and fuel while also cooling the hot endothermic product (Col. 19 lines 3-7 meeting limitation “a means for introducing at least one air stream into at least one cooling device selected from the group consisting of: the first cooling device”). The air and fuel are preferably preheated to a sufficiently high temperature such that when the fuel exiting from the nozzle tubes 90 contacts the air in the exothermic reaction chamber 81, the fuel will auto-ignite (Col. 10 lines 44-48 meeting limitation “a means for discharging at least one preheated air stream from the at least one cooling device, and a means for supplying the at least one preheated air stream as oxidant to the main reforming stage”).
Thus, prior to the effective filing date of the claimed invention it would have been obvious to one of ordinary skill in the art to modify the apparatus of Barnett by including a means for introducing at least one air stream into at least one cooling device selected from the group consisting of: the first cooling device, the second cooling device, and the third cooling device, a means for discharging at least one preheated air stream from the at least one cooling device, and a means for supplying the at least one preheated air stream as oxidant to the main reforming stage in order to preheat the air and fuel such that the fuel will auto-ignite as taught by Ruhl.
Regarding claim 11, Barnett in view of Rhinesmith and Ruhl discloses all the limitations in the claims as set forth above and Rhinesmith further discloses the lean carbon dioxide recovery solvent, i.e. carbon dioxide depleted hot absorbent stream, leaves the solvent stripper 46 at 271°F. and 415 psia and is cooled in the Solvent cross exchanger 44, i.e. third cooling device, to 34°F. by incoming rich carbon dioxide recovery solvent, i.e. carbon dioxide loaded absorbent stream ([0144] meeting limitation “further comprising a means for allowing the carbon dioxide loaded absorbent stream to be heated in indirect heat exchange against the carbon dioxide depleted hot absorbent stream prior to its introduction into the absorbent regeneration column, wherein the carbon dioxide depleted hot absorbent stream is cooled and fed to the third cooling device”).
Regarding claim 12, Barnett in view of Rhinesmith and Ruhl discloses all the limitations in the claims as set forth above and Barnett further discloses air from intake line 210 can be conveyed by forced draft fan 212 through cold air preheater 214… and then to a burner 216 via line 218 for combustion ([0099] meeting limitation “further comprising a means allowing the at least one preheated air stream to be further heated by indirect heat exchange”).
Regarding claim 13, Barnett in view of Rhinesmith and Ruhl discloses all the limitations in the claims as set forth above including Barnett discloses C02-rich absorbent is collected as a bottoms stream 162 and supplied to stripper 156 where it is heated by means of reboiler 164 to obtain CO2 product stream 152 overhead, and CO2-lean solvent stream 158 as a bottoms product ([0094] meeting limitation “wherein the absorbent regeneration column comprises a reboiler configured to generate a vapor stream or gas stream in the bottom of the column as a stripping agent stream”).
Claims 5-6, 14-15 are rejected under 35 U.S.C. 103 as being unpatentable over Barnett et al (WO 2022155425 A1 as cited in IDS 10/09/2023 in view of Rhinesmith et al (US 20090255181 A1) and Ruhl et al (US 5567398) and in further view of Rafati et al (US 20190135626 A1).
Regarding claim 5, Barnett in view of Rhinesmith and Ruhl discloses all the limitations in the claims as set forth above and Barnett further discloses if desired, SMR reformer 108 can optionally include shift converters… which react CO and H2O to make more hydrogen and CO2 ([0092]).
Barnett in view of Rhinesmith and Ruhl does not disclose wherein between step (c) and (d) the cooled crude synthesis gas stream is introduced into a carbon monoxide shift conversion stage and is converted with a stream of steam under carbon monoxide shift conversion conditions into a shift converted synthesis gas stream enriched in hydrogen and carbon dioxide and depleted in carbon monoxide, wherein the shift converted synthesis gas stream is introduced into a fourth cooling device and is cooled therein in indirect heat exchange with a fourth coolant stream, wherein the cooled converted synthesis gas stream is discharged from the fourth cooling device and is introduced into the carbon dioxide absorption column instead of the cooled crude synthesis gas stream in step (d).
Rafati discloses systems and methods can be configured for separation of carbon dioxide from a process stream, such as a process stream in a hydrogen production system (abstract). The system can comprise: a CO+H2 syngas reactor … with feed streams of hydrocarbon fuel, steam, and optionally waste fuel gas plus CO2, (preferably wherein the reactor system can comprise one or more of an SMR, a PDX, an ATR, a PDX+GHR, or an ATR+GHR), i.e. reforming stage; a waste heat boiler, i.e. first cooling device, configured to cool syngas produced in the reactor system and produce saturated high pressure steam; … one or more catalytic CO shift reactors, which convert CO by reaction with contained steam to produce H2+CO2 ([0026] meeting limitation “wherein between step (c) and (d) the cooled crude synthesis gas stream is introduced into a carbon monoxide shift conversion stage and is converted with a stream of steam under carbon monoxide shift conversion conditions into a shift converted synthesis gas stream enriched in hydrogen and carbon dioxide and depleted in carbon monoxide”); a heat exchanger system, i.e. fourth cooling device, configured to cool the syngas and condense excess steam, which provides heat required for preheating boiler feed water ([0026] meeting limitation “wherein the shift converted synthesis gas stream is introduced into a fourth cooling device and is cooled therein in indirect heat exchange with a fourth coolant stream”); optionally a chemical or physical absorbent CO2 removal system placed upstream of the first PSA unit ([0026] meeting limitation “wherein the cooled converted synthesis gas stream is discharged from the fourth cooling device and is introduced into the carbon dioxide absorption column instead of the cooled crude synthesis gas stream in step (d)”).
Rafati further discloses the present disclosure provides a simple and economic process to capture and purify CO2 as a by-product from waste streams generated from various processes such as oxy-fuel combustion and power generation, natural gas processing and hydrogen generation ([0028]).
Thus, prior to the effective filing date of the claimed invention it would have been obvious to one of ordinary skill in the art to add a step between step (c) and (d) wherein the cooled crude synthesis gas stream is introduced into a carbon monoxide shift conversion stage and is converted with a stream of steam under carbon monoxide shift conversion conditions into a shift converted synthesis gas stream enriched in hydrogen and carbon dioxide and depleted in carbon monoxide, wherein the shift converted synthesis gas stream is introduced into a fourth cooling device and is cooled therein in indirect heat exchange with a fourth coolant stream, wherein the cooled converted synthesis gas stream is discharged from the fourth cooling device and is introduced into the carbon dioxide absorption column instead of the cooled crude synthesis gas stream in step (d) in the method of Barnett in view of Rhinesmith and Ruhl in order to capture and purify CO2 as a by-product from waste streams generated from various processes such as oxy-fuel combustion and power generation, natural gas processing and hydrogen generation as taught by Rafati.
Regarding claim 6, Barnett in view of Rhinesmith, Ruhl, and Rafati discloses all the limitations in the claims as set forth above including Ruhl discloses in the region of the air and fuel supply tubes 156 and 157, heat will be transferred from the hot endothermic product, i.e. shift converted synthesis gas stream, to the air and fuel, i.e. fourth coolant stream, being supplied through the air and fuel supply tubes, thereby to preheat the air and fuel while also cooling the hot endothermic product (Col. 19 lines 3-7 meeting limitation “wherein the fourth coolant stream is formed by at least one air stream which is preheated in the process”). The air and fuel are preferably preheated to a sufficiently high temperature such that when the fuel exiting from the nozzle tubes 90 contacts the air in the exothermic reaction chamber 81, the fuel will auto-ignite (Col. 10 lines 44-48 meeting limitation “and is fed as a preheated air stream as oxidant to step (b)”).
Regarding claim 14, Barnett in view of Rhinesmith and Ruhl discloses all the limitations in the claims as set forth above and Barnett further discloses if desired, SMR reformer 108 can optionally include shift converters… which react CO and H2O to make more hydrogen and CO2 ([0092]).
However, Barnett in view of Rhinesmith and Ruhl does not disclose further comprising a carbon monoxide shift conversion stage arranged downstream of the main reforming stage and upstream of the carbon dioxide absorption column.
Rafati discloses systems and methods can be configured for separation of carbon dioxide from a process stream, such as a process stream in a hydrogen production system (abstract). The system can comprise: a CO+H2 syngas reactor … with feed streams of hydrocarbon fuel, steam, and optionally waste fuel gas plus CO2, (preferably wherein the reactor system can comprise one or more of an SMR, a PDX, an ATR, a PDX+GHR, or an ATR+GHR), i.e. main reforming stage; … one or more catalytic CO shift reactors, which convert CO by reaction with contained steam to produce H2+CO2 ; … optionally a chemical or physical absorbent CO2 removal system placed upstream of the first PSA unit ([0026] meeting limitation “further comprising a carbon monoxide shift conversion stage arranged downstream of the main reforming stage and upstream of the carbon dioxide absorption column”).
Rafati further discloses the present disclosure provides a simple and economic process to capture and purify CO2 as a by-product from waste streams generated from various processes such as oxy-fuel combustion and power generation, natural gas processing and hydrogen generation ([0028]).
Thus, prior to the effective filing date of the claimed invention it would have been obvious to one of ordinary skill in the art to further comprise a carbon monoxide shift conversion stage arranged downstream of the main reforming stage and upstream of the carbon dioxide absorption column in the system of Barnett in view of Rhinesmith and Ruhl in order to capture and purify CO2 as a by-product from waste streams generated from various processes such as oxy-fuel combustion and power generation, natural gas processing and hydrogen generation as taught by Rafati.
Regarding claim 15, Barnett in view of Rhinesmith and Ruhl discloses all the limitations in the claims as set forth above.
However, Barnett in view of Rhinesmith and Ruhl does not disclose further comprising a fourth cooling device arranged downstream of the carbon monoxide shift conversion stage and upstream of the carbon dioxide absorption column, configured to supply at least one air stream as a fourth cooling stream to the fourth cooling device.
Rafati discloses systems and methods can be configured for separation of carbon dioxide from a process stream, such as a process stream in a hydrogen production system (abstract). The system can comprise: a CO+H2 syngas reactor … with feed streams of hydrocarbon fuel, steam, and optionally waste fuel gas plus CO2, (preferably wherein the reactor system can comprise one or more of an SMR, a PDX, an ATR, a PDX+GHR, or an ATR+GHR), i.e. main reforming stage; a waste heat boiler, i.e. first cooling device, configured to cool syngas produced in the reactor system and produce saturated high pressure steam; … one or more catalytic CO shift reactors, which convert CO by reaction with contained steam to produce H2+CO2; a heat exchanger system, i.e. fourth cooling device, configured to cool the syngas and condense excess steam, which provides heat required for preheating boiler feed water ([0026] meeting limitation “further comprising a fourth cooling device arranged downstream of the carbon monoxide shift conversion stage and upstream of the carbon dioxide absorption column”); optionally a chemical or physical absorbent CO2 removal system placed upstream of the first PSA unit ([0026]).
Thus, prior to the effective filing date of the claimed invention it would have been obvious to one of ordinary skill in the art further comprising a fourth cooling device arranged downstream of the carbon monoxide shift conversion stage and upstream of the carbon dioxide absorption column in the system of Barnett in view of Rhinesmith and Ruhl in order to capture and purify CO2 as a by-product from waste streams generated from various processes such as oxy-fuel combustion and power generation, natural gas processing and hydrogen generation as taught by Rafati.
Regarding the limitation “configured to supply at least one air stream as a fourth cooling stream to the fourth cooling device”, Rafati does not specifically disclose the fourth cooling stream is air.
However, as discussed above, Ruhl discloses in the region of the air and fuel supply tubes 156 and 157, heat will be transferred from the hot endothermic product, i.e. crude synthesis gas, to the air and fuel, i.e. coolant stream, being supplied through the air and fuel supply tubes, thereby to preheat the air and fuel while also cooling the hot endothermic product (Col. 19 lines 3-7). The air and fuel are preferably preheated to a sufficiently high temperature such that when the fuel exiting from the nozzle tubes 90 contacts the air in the exothermic reaction chamber 81, the fuel will auto-ignite (Col. 10 lines 44-48). Therefore, Ruhl teaches using air as a coolant stream.
Thus, prior to the effective filing date of the claimed invention it would have been obvious to one of ordinary skill in the art to configure the supply of at least one air stream as a fourth cooling stream to the fourth cooling device in the apparatus of Barnett in view of Rhinesmith and Ruhl in order to preheat the air and fuel such that the fuel will auto-ignite as taught by Ruhl.
Conclusion
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/N.L.Q./Examiner, Art Unit 1738
/PAUL A WARTALOWICZ/Primary Examiner, Art Unit 1735
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