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 .
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.
Specification
The title of the invention is not descriptive. A new title is required that is clearly indicative of the invention to which the claims are directed.
The following title is suggested: Methods for Treating Aqueous Feed Streams and Converting a Carbon Constituent into Carbonates.
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 1-20 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 limitation “and an impurity of no more than 50,000 ppm in total of a metal, a hard mineral, and combinations thereof;” claim 10 recites the limitation “and no more than 50,000 ppm of an impurity comprising a metal, a hard mineral, or combinations thereof;” claim 19 recites the limitation “no more than 30,000 ppm of an impurity comprising: a metal, a hard mineral, or combinations thereof”. In each of these independent claims it is unclear what components of the feed stream, i.e. what metals and what minerals exactly, constitute an impurity versus being constituents that can be considered a proper part of the feed itself. For example, it is unclear if the potassium, calcium, and sodium ions that eventually make up the hydroxides recited in claim 3 are to be considered integral components of the brine or are counted among the “impurities.”
Claims 2-9, 11-18, and 20 each depend upon claims 1, 10 or 19 without resolving the indefiniteness, while claims 6, 16, 17 and 20 each additionally recite further limitations on the impurity level without clarifying what would constitute an impurity. All of these claims are likewise rejected.
For the purposes of further examination “impurity” will be interpreted as meaning transition and post-transition series metal ions as well as any suspended inorganic solids (hard minerals).
Claims 1, 10, and 19 recite the limitation “at least one percent to no more than thirty percent (by volume) of a hydroxide constituent.” Calculating a percent composition of a soluble solid salt by volume percent is non-standard in the art, and it is not described in the specification how this calculation is to be carried out. It is therefore unclear what compositions are covered by the claim.
For the purposes of further examination “percent (by volume)” may be interpreted as requiring a weight per volume percentage calculated based upon the weight of the hydroxide (in grams) and either one hundred volumes of the solution or one hundred volumes the solvent (in milliliters); alternatively, it may be interpreted as a volume of the solid hydroxide (as determined by a density of the pure substance) per one hundred volumes of solvent or one hundred volumes of solution.
Claim 9 recites the limitation “wherein the skimming dish is disposed above a normal operation level of the clarifier.” It is indefinite what is required by this limitation. The specification ([0044], [0070], and [0087]) provides some discussion of skimming devices, but does not clarify what constitutes a “normal operation level of the clarifier.” In particular, it is not clear if the skimmer must be positioned above a position at which a skimmer is normally positioned in a clarifier, or if the skimmer must rather be positioned above the surface level of the clarifier under normal operating conditions. For the purposes of further examination, any of these interpretations may be used.
Claim 10 is drawn to a method of converting a carbon constituent to a carbonate constituent, but the method steps recited in the claim do not mention any carbon constituent or a carbonate constituent, or any step which can be interpreted as accomplishing this transformation. It is therefore indefinite if the method of claim 10 requires the conversion of a carbon constituent into a carbonate constituent or not.
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, 6-14 and 16-18 are rejected under 35 U.S.C. 103 as being unpatentable over Saini (US 2019/0160395 A1) in view of Igunnu et al. (International Journal of Low-Carbon Technologies 2014, 9, 157–177), and as evidenced by Yaws (Yaws’ Handbook of Physical Properties for Hydrocarbons and Chemicals, 2008, Table of Inorganic Compounds. Retrieved from https://app.knovel.com/hotlink/itble/rcid:kpYHPPHC0B/id:kt0059W4X3/yaws-handbook-physical/inorganic-compounds; hereinafter “Yaws 2008”) and Yaws (Yaws' Critical Property Data for Chemical Engineers and Chemists, 2012, Table 125: Density of Aqueous Solutions - sodium hydroxide. Knovel. Retrieved from https://app.knovel.com/hotlink/epgrph/rcid:kpYCPDCECD/id:kt00AAKGVX/yaws-critical-property/yaws-criti-table-125-density?curve_ids=kr07CY2AJ1; hereinafter Yaws 2012), and with respect to claims 4 and 14 as further evidenced by NOAA (“Carbon dioxide now more than 50% higher than pre-industrial levels,” 3 June 2022, Retrieved from the Internet: <URL: https://www.noaa.gov/news-release/carbon-dioxide-now-more-than-50-higher-than-pre-industrial-levels>).
Regarding claim 1, Saini teaches a process for treating a feed stream ( a mixture of brine/waste water and oil and/or gas) in a manner that results in converting a carbon constituent (CO2) into a carbonate constituent (sodium carbonate; Fig. 2), the process comprising:
providing the feed stream to a first treatment step, the feed stream being aqueous and comprising a hydrocarbonaceous component (a mixture comprising brine (e.g., oil field waste water), oil and/or other liquid-phase hydrocarbon(s), and gas from a well stream; [0029]);
using the first treatment step to remove the hydrocarbonaceous component from the feed stream to form a first treated stream (to separate a mixture comprising brine (e.g., oil field waste water), oil and/or other liquid-phase hydrocarbon(s), and gas from a well stream into a first stream comprising the brine (waste water), a second stream comprising liquid-phase, water-insoluble materials (e.g., the oil and/or liquid-phase hydrocarbons), and a third stream comprising the gas-phase materials; [0029]);
using electrolysis to react the first treated stream to produce a treated aqueous stream comprising a hydroxide constituent (electrochemical membrane separation cell is configured to separate sodium and chloride ions in the waste water into sodium hydroxide (NaOH); [0030]); and,
providing the treated aqueous stream and an air stream comprising the carbon constituent to a neutralization reactor, wherein the carbon constituent and the hydroxide constituent are reactive to a point whereby at least some of the carbon constituent is converted to the carbonate constituent (a gas containing CO2 (e.g., air…) is compressed… one of the purified NaOH streams is combined with the (heated) compressed gas to react the NaOH in the purified stream with CO2 in the gas and form sodium carbonate; [0047]-[0048]). Such a reaction takes place in a vessel that can be considered a neutralization reactor.
Saini further teaches that the hydroxide component may comprise a 30 wt% solution of NaOH (… first NaOH solution leaving the cell may have a concentration in excess of 25% (e.g., about 30%) by weight; [0032]). A 30% by weight solution of NaOH in water will comprise 30 g of NaOH per 100 g of solution. The density of pure NaOH is 2.13 g/mL and the density of a 30% NaOH solution is 1.3 g/ml, as evidenced by Yaws 2008 (Inorganic Compounds, entry 2897) and Yaws 2012 (Table 125: density of Aqueous Solutions, calculated from formula). Therefore, calculated as volumes, such a solution will have 14 mL of NaOH dissolved in 77 mL of solution, or will have a percent hydroxide by volume of 18%, meeting the limitation of at least one percent and no more than 30 percent (by volume) required by the instant claim.
Saini does not explicitly teach that the feed stream comprises at least one ppm to no more than ten percent (by volume) of a hydrocarbonaceous component. However, Saini does teaches that the feed stream may, or may not, contain oil ([0029]) and therefore teaches general conditions that would include at least one ppm to no more than ten percent (by volume) of a hydrocarbonaceous component.
The courts have found 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). See MPEP 2144.05 II. Therefore, the claimed ranges merely represent an obvious variant and/or routine optimization of the values of the cited prior art.
Saini is also silent on the level of impurities in the feed material and on what fraction of the hydrocarbonaceous component has been removed in the first treatment step.
Regarding the impurity level, while what metals and minerals constitute an impurity is indefinite (see Claim Rejections – 35 USC § 112), for the purposes of further examination “impurity” will be interpreted as meaning transition and post-transition series metal ions as well as any suspended inorganic solids (hard minerals).
Igunnu teaches methods of treating produced water where the composition of produced water from oilfields typically contains less than 1000 ppm total suspended solids, and less than 2500 ppm heavy metal ions (those in Table 1 excluding sodium, potassium, calcium, and magnesium, where mg/L is equivalent to ppm).
Therefore, it would have been obvious to one of ordinary skill in the art before the effective filing date of the claimed invention to use in the method of Saini a feed stream such as that described by Igunnu with less than 3,500 pm total impurities. One of ordinary skill in the art would have been motivated to do so because using a typical produced water feed stream from an oilfield, as taught by Saini, would have these characteristics, as taught by Igunnu.
Regarding the fraction of the hydrocarbonaceous component removed in the first treatment, while Saini is silent on the precise fraction of hydrocarbons removed, they do teach separating the oil from the brine ([0029]). One of ordinary skill in the art would be motivated to remove as much as the hydrocarbon as possible, including at least 99% (by volume) of the hydrocarbonaceous component, in order to minimize downstream environmental effects, as taught by Igunnu (Dissolved and dispersed oil content in produced water is dangerous to the environment; Section 2.1).
It is again noted the courts have found 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). See MPEP 2144.05 II. Therefore, the claimed ranges merely represent an obvious variant and/or routine optimization of the values of the cited prior art.
Regarding claim 2, modified Saini teaches the process of claim 1, where Saini teaches the feed stream comprising oilfield water, which comprises waste water, brine, and produced water (The extraction of hydrocarbons, such as oil and/or gas, from oil fields often uses brine, and produces waste water as a byproduct; [0003]).
Regarding claim 3, modified Saini teaches the process of claim 1, where Saini teaches the hydroxide component comprising sodium hydroxide (electrochemical membrane separation cell is configured to separate sodium and chloride ions in the waste water into sodium hydroxide (NaOH); [0030]).
Regarding claim 4, modified Saini teaches the process of claim 1, where Saini teaches using air from the atmosphere ([0036]), but is silent on the carbon dioxide of the air. However, atmospheric air contains carbon dioxide at approximately 420 ppm, as evidenced by NOAA (¶ 2). Therefore Saini teaches using an air stream that meets the limitations of the instant claim, with at least 200 ppm and no more than 500 ppm carbon dioxide.
Regarding claim 6, modified Saini teaches the process of claim 1, where Igunnu teaches that typical oilfield waste water has impurity metal content of 320 to 2430 ppm and a suspended solids content (TSS) of 1 to 1000 ppm (Table 1). This is interpreted as an impurity content of 320 to 3430 ppm, of which up to 75% is suspended solids.
It is noted that the courts have stated where the claimed ranges “overlap or lie inside the ranges disclosed by the prior art” a prima facie case of obviousness exists (see 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); Titanium Metals Corp. of America v. Banner, 778 F2d 775. 227 USPQ 773 (Fed. Cir. 1985) (see MPEP 2144.05.01). Therefore, the claimed ranges merely represent an obvious variant and/or routine optimization of the impurity content of the cited prior art.
Regarding claim 7, modified Saini teaches the process of claim 1, but does not teach the feed stream being injected with microbubbles prior to the first treatment step.
However, Igunnu teaches that injecting microbubbles (fine gas bubbles) is a method to remove suspended solids and oil from produced water (gas is injected into produced water, suspended particulates and oil droplets are attached to the air bubbles as it rises. This results into the formation of foam on the surface of the water which is skimmed off as froth; Section 4.5).
Therefore, it would have been obvious to one of ordinary skill in the art before the effective filing date of the claimed invention subject the oilfield water of Saini to a pre-treatment by injecting microbubbles, as taught by Igunnu. One of ordinary skill in the art would have been motivated to do so in order to remove suspended solids from the feed stream, as taught by Igunnu.
Regarding claim 8, modified Saini teaches the method of claim 1, but does not teach mixing the first treated stream with an additive that comprises one of an oxidizer, an agglomerate, a caustic, a polymer, and combinations thereof.
However, Igunnu teaches that chemical oxidation treatment of produced water is an established and reliable technology for the removal of color, odor, COD, BOD, organics and some inorganic compounds (Section 4.10).
Therefore, it would have been obvious to one of ordinary skill in the art before the effective filing date of the claimed invention to mix the first treated stream with an additive that comprises an oxidant. One of ordinary skill in the art would have been motivated to do so in order to remove color, odor, and undesirable components from the treated stream, as taught by Igunnu.
Regarding claim 10, Saini teaches a process for treating a feed stream in a manner that results in converting a carbon constituent into a carbonate constituent (Fig. 2), the process comprising:
providing the feed stream to a first treatment step (phase separator … is configured to separate a mixture; [0029]), the feed stream being aqueous and comprising a hydrocarbonaceous component (a mixture comprising brine (e.g., oil field waste water), oil and/or other liquid-phase hydrocarbon(s), and gas from a well stream; [0029]);
providing a first treated stream from the first treatment step to a secondary processing step (electrochemical membrane separation cell may receive the first stream comprising the waste water; [0030]);
using electrolysis in the secondary processing step to produce a treated aqueous stream comprising a hydroxide constituent (separate sodium and chloride ions in the waste water into sodium hydroxide (NaOH) …by electrolysis…to form a fourth stream comprising a first NaOH solution; [0030])).
Saini further teaches that the hydroxide component may comprise a 30 wt% solution of NaOH (… first NaOH solution leaving the cell may have a concentration in excess of 25% (e.g., about 30%) by weight; [0032]). A 30% by weight solution of NaOH in water will comprise 30 g of NaOH per 100 g of solution. The density of pure NaOH is 2.13 g/mL and the density of a 30% NaOH solution is 1.3 g/ml, as evidenced by Yaws 2008 (Inorganic Compounds, entry 2897) and Yaws 2012 (Table 125: density of Aqueous Solutions, calculated from formula). Therefore, calculated as volumes, such a solution will have 14 mL of NaOH dissolved in 77 mL of solution, or will have a percent hydroxide by volume of 18%, meeting the limitation of at least one percent and no more than 30 percent (by volume) required by the instant claim.
Saini does not explicitly teach that the feed stream comprises at least one ppm to no more than ten percent (by volume) of a hydrocarbonaceous component and is silent on the level of impurities in the feed material.
However, Saini does teaches that the feed stream may, or may not, contain oil or gas ([0029]) and therefore teaches general conditions that would include at least one ppm to no more than ten percent (by volume) of a hydrocarbonaceous component.
The courts have found 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). See MPEP 2144.05 II. Therefore, the claimed ranges merely represent an obvious variant and/or routine optimization of the values of the cited prior art.
Regarding the impurity level, while what metals and minerals constitute an impurity is indefinite (see Claim Rejections – 35 USC § 112), for the purposes of further examination “impurity” will be interpreted as meaning transition and post-transition series metal ions as well as any suspended inorganic solids (hard minerals).
Igunnu teaches the composition of produced water from oilfields as typically containing less than 1000 ppm total suspended solids, and less than 2500 ppm heavy metal ions (those in Table 1 excluding sodium, potassium, calcium, and magnesium, where mg/L is equivalent to ppm).
Therefore, it would have been obvious to one of ordinary skill in the art before the effective filing date of the claimed invention to use in the method of Saini a feed stream such as that described by Igunnu with less than 3,500 pm total impurities. One of ordinary skill in the art would have been motivated to do so because using a typical produced water feed stream from an oilfield, as taught by Saini, would have these characteristics, as taught by Igunnu.
Regarding claim 11, modified Saini teaches the process of claim 10, and Saini further teaches providing the treated aqueous stream and an air stream comprising the carbon constituent to a neutralization reactor, wherein the carbon constituent and the hydroxide constituent are converted to a carbonate constituent (a gas containing CO2 (e.g., air…) is compressed… one of the purified NaOH streams is combined with the (heated) compressed gas to react the NaOH in the purified stream with CO2 in the gas and form sodium carbonate; [0047]-[0048]), where the carbon constituent and the hydroxide constituent are reactive to a point whereby at least 90% (by weight) of the carbon constituent is converted to the carbonate constituent (CO2 in the heated gas undergoes a reactive absorption reaction with the NaOH to form sodium carbonate … 90% or more… of the carbon dioxide is removed from the heated gas; [0038]). Such a reaction takes place in a vessel that can be considered a neutralization reactor.
Regarding claim 12, modified Saini teaches the process of claim 11, where Saini teaches the feed stream comprising oilfield water, which comprises waste water, brine, and produced water (The extraction of hydrocarbons, such as oil and/or gas, from oil fields often uses brine, and produces waste water as a byproduct; [0003]).
Regarding claim 13, modified Saini teaches the process of claim 12, where Saini teaches the hydroxide component comprising sodium hydroxide (electrochemical membrane separation cell is configured to separate sodium and chloride ions in the waste water into sodium hydroxide (NaOH); [0030]).
Regarding claim 14, modified Saini teaches the process of claim 12, where Saini teaches using atmospheric air ([0036]) and where the hydroxide component comprises sodium hydroxide (electrochemical membrane separation cell is configured to separate sodium and chloride ions in the waste water into sodium hydroxide (NaOH); [0030]), but is silent on the carbon dioxide level of the air.
However, atmospheric air contains carbon dioxide at approximately 420 ppm, as evidenced by NOAA (¶ 2). Therefore Saini teaches using an air stream that meets the limitations of the instant claim, with at least 200 ppm and no more than 500 ppm carbon dioxide.
Regarding claim 16, modified Saini teaches the process of claim 13, where Igunnu teaches that typical oilfield waste water has impurity metal content of 320 to 2430 ppm and a suspended solids content (TSS) of 1 to 1000 ppm (Table 1). This is interpreted as an impurity content of 320 to 3430 ppm, which overlaps with the instantly claimed range of less than 3,000 ppm. Igunnu also teaches that solids in the feed can cause serious problems such as clogged lines (Section 2.4).
Therefore, it would have been obvious to one of ordinary skill in the art before the effective filing date of the claimed invention to pre-treat the aqueous feed stream in order to remove suspended solids (TSS), which would reduce the impurity content of a typical feed to a range of 320 to 2430 ppm, which falls within the instantly claimed range of less than 3000. One of ordinary skill in the art would have been motivated to do so in order to remove the solids which could lead to clogged lines, as taught by Igunnu. Even if not all suspended solids were removed in the pretreatment, the original impurity range taught by Igunnu overlaps with the instantly claimed range.
It is noted that the courts have stated where the claimed ranges “overlap or lie inside the ranges disclosed by the prior art” a prima facie case of obviousness exists (see 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); Titanium Metals Corp. of America v. Banner, 778 F2d 775. 227 USPQ 773 (Fed. Cir. 1985) (see MPEP 2144.05.01). Therefore, the claimed ranges merely represent an obvious variant and/or routine optimization of the impurity content of the cited prior art.
Regarding claim 17, modified Saini teaches the process of claim 10, where Igunnu teaches that typical oilfield waste water has impurity metal content of 320 to 2430 ppm and a suspended solids content (TSS) of 1 to 1000 ppm (Table 1). This is interpreted as an impurity content of 320 to 3430 ppm, which overlaps with the instantly claimed range of less than 3,000 ppm.
It is noted that the courts have stated where the claimed ranges “overlap or lie inside the ranges disclosed by the prior art” a prima facie case of obviousness exists (see 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); Titanium Metals Corp. of America v. Banner, 778 F2d 775. 227 USPQ 773 (Fed. Cir. 1985) (see MPEP 2144.05.01). Therefore, the claimed ranges merely represent an obvious variant and/or routine optimization of the impurity content of the cited prior art.
Regarding claim 18, modified Saini teaches the process of claim 17, but Saini does not teach the first treatment step comprising dissolved air floatation.
However, Igunnu teaches that dissolved air floatation is one method that can be used to treat oilfield produced water in order to remove suspended particles, including hydrocarbons and suspended solids such as grease and oil, natural
organic matter, volatile organics and small particles (Section 4.5).
Therefore, it would have been obvious to one of ordinary skill in the art before the effective filing date of the claimed invention to use a first treatment in the method of Saini that includes a dissolved air floatation, a taught by Igunnu. One of ordinary skill in the art would have been motivated to do so in order to remove solids and oil that can interfere with downstream processes by clogging flow lines (Section 2.4) and which have a negative effect on the environment (Section 2.1), as taught by Igunnu.
Claims 5 and 15 are rejected under 35 U.S.C. 103 as being unpatentable over Saini (US 2019/0160395 A1) in view of Igunnu et al. (International Journal of Low-Carbon Technologies 2014, 9, 157–177), as applied to claim 1, and further in view of Shim et al. (Environ. Eng. Res. 2016, 21(3), 297-303).
Regarding claim 5, modified Saini teaches the process of claim 1, where Saini teaches the carbonate component comprising sodium carbonate (react the NaOH in the purified stream with CO2 in the gas and form sodium carbonate; [0048]). Saini does not teach the carbonate component comprising any of the bicarbonates recited in the instant claim.
However, Shim teaches that captured carbon dioxide can produce sodium bicarbonate from sodium hydroxide (carbon dioxide, reacting with an aqueous solution of sodium hydroxide, could be converted to sodium bicarbonate (NaHCO3); abstract), that sodium bicarbonate has a wide range of uses (¶. 297, col. 2, ¶ 2), and that production of sodium bicarbonate captures two equivalents of carbon dioxide per two NaOH (p. 598, Eq. 7) while production of sodium carbonate captures only 1 equivalent of carbon dioxide (p. 298, Eq. 5).
Therefore, it would have been obvious to one of ordinary skill in the art before the effective filing date of the claimed invention to further modify the method of Saini to generate a sodium bicarbonate product, as taught by Shim, instead of sodium carbonate. One of ordinary skill in the art would have been motivated to do so because sodium bicarbonate has many potential uses and because generation of sodium bicarbonate captures more carbon dioxide, as taught by Shim.
Regarding claim 15, modified Saini teaches the process of claim 14, where Saini teaches the carbonate component comprising sodium carbonate (react the NaOH in the purified stream with CO2 in the gas and form sodium carbonate; [0048]). Saini does not teach the carbonate component comprising any of the bicarbonates recited in the instant claim.
However, Shim teaches that captured carbon dioxide can produce sodium bicarbonate from sodium hydroxide (carbon dioxide, reacting with an aqueous solution of sodium hydroxide, could be converted to sodium bicarbonate (NaHCO3); abstract), that sodium bicarbonate has a wide range of uses (¶. 297, col. 2, ¶ 2), and that production of sodium bicarbonate captures two equivalents of carbon dioxide per two NaOH (p. 598, Eq. 7) while production of sodium carbonate captures only 1 equivalent of carbon dioxide (p. 298, Eq. 5).
Therefore, it would have been obvious to one of ordinary skill in the art before the effective filing date of the claimed invention to further modify the method of Saini to generate a sodium bicarbonate product, as taught by Shim, instead of sodium carbonate. One of ordinary skill in the art would have been motivated to do so because sodium bicarbonate has many potential uses and because generation of sodium bicarbonate captures more carbon dioxide, as taught by Shim.
Claim 9 is rejected under 35 U.S.C. 103 as being unpatentable over Saini (US 2019/0160395 A1) in view Igunnu et al. (International Journal of Low-Carbon Technologies 2014, 9, 157–177), as applied to claim 1, and further in view of Baeuerle (US 2016/0297692 A1), Wang (US 2003/0024866 A1), and Kemco (“Dissolved Air Floatation”, Retrieved from the Internet: <URL: /https://www.kemcosystems.com/technology/wastewater-recovery/dissolved-air-flotation/>; archived 2 December 2021).
Regarding claim 9, modified Saini teaches the method of claim 1 but Saini does not teach providing the first treated stream to a secondary processing step that comprises operating a clarifier with a layer of tubular packing, where the clarifier is configured with a skimming dish, wherein the skimming dish is disposed above a normal operation level of the clarifier.
However, Baeuerle teaches a method for purifying an oil/water mixture (abstract) very similar to the feed stream used in the method of Saini. Baeuerle further teaches that their method may include oblique tube clarifiers to assist in clarifying the feed stream ([0039]). Baeuerle also teaches the use of pressure/release flotation (or Dissolved Air Floatation, DAF) to form a separated oil phase on the surface where it can be skimmed off ([0048]). It is unclear from Baeuerle whether the tube clarifiers and the skimming device are together in a single clarifier unit.
However, Wang teaches an integrated apparatus that contains both a gravity settling mechanism and a dissolved air-floatation mechanism (abstract). Wang further teaches that tube settlers may be used in the gravity settling chamber to improve solids removal ([0029]) and that a skimming device (skimming dish) is installed on top of the DAF unit for removing sludge ([0026] and claim 4). It is unclear from Wang if the skimming dish is disposed above the normal operation level of the clarifier.
However, Kemco teaches the specifics of a DAF processing tank where the skimming dish (skimmer) is positioned above the normal operation level of the clarifier (p. 2), where the normal operation level is interpreted as the surface of the water level in the clarifier.
Therefore, it would have been obvious to one of ordinary skill in the art before the effective filing date of the claimed invention to provide the first treated stream of modified Saini to a secondary processing step that comprises operating a clarifier with a layer of tubular packing, where the clarifier is configured with a skimming dish, and where the skimming dish is disposed above a normal operation level of the clarifier, as taught by Baeuerle, and Kemco.
One of ordinary skill in the art would have been motivated to do so because Baeuerle teaches that tube clarifiers (tube settlers) and DAF are effective at treating produced water to reduce residual oil ([0039]), Wang teaches that an integrated clarifier can achieve better effluent quality in shorter times than traditional apparatuses ([0023]), and Kemco teaches the positioning of the skimming dish (skimmer) where Baeuerle and Wang are silent.
Claims 19 and 20 are rejected under 35 U.S.C. 103 as being unpatentable over Saini (US 2019/0160395 A1 in view of Igunnu et al. (International Journal of Low-Carbon Technologies 2014, 9, 157–177) and Shim et al. (Environ. Eng. Res. 2016; 21(3), 297-303), and as evidenced by Yaws (Yaws’ Handbook of Physical Properties for Hydrocarbons and Chemicals, 2008, Table of Inorganic Compounds. Retrieved from https://app.knovel.com/hotlink/itble/rcid:kpYHPPHC0B/id:kt0059W4X3/yaws-handbook-physical/inorganic-compounds; hereinafter “Yaws 2008”), Yaws (Yaws' Critical Property Data for Chemical Engineers and Chemists, 2012, Table 125: Density of Aqueous Solutions - sodium hydroxide. Knovel. Retrieved from https://app.knovel.com/hotlink/epgrph/rcid:kpYCPDCECD/id:kt00AAKGVX/yaws-critical-property/yaws-criti-table-125-density; hereinafter Yaws 2012), and NOAA (“Carbon dioxide now more than 50% higher than pre-industrial levels,” 3 June 2022, Retrieved from the Internet: <URL: https://www.noaa.gov/news-release/carbon-dioxide-now-more-than-50-higher-than-pre-industrial-levels>).
Regarding claim 19, Saini teaches a process for treating a feed stream in a manner that results in converting a carbon constituent into a carbonate constituent (Fig. 2), the process comprising:
providing the feed stream to a treatment step (phase separator … is configured to separate a mixture; [0029]), the feed stream being aqueous and comprising a hydrocarbonaceous component (a mixture comprising brine (e.g., oil field waste water), oil and/or other liquid-phase hydrocarbon(s), and gas from a well stream; [0029]);
using electrolysis to react the feed stream via the treatment step to produce a treated aqueous stream consisting of a hydroxide constituent (separate sodium and chloride ions in the waste water into sodium hydroxide (NaOH) …by electrolysis…to form a fourth stream comprising a first NaOH solution; [0030]);
providing the treated aqueous stream and an air stream comprising the carbon constituent to a neutralization reactor, wherein the carbon constituent and the hydroxide constituent are reactive to a point whereby at least some of the carbon constituent is converted to the carbonate constituent,
wherein the feed stream comprises produced water, waste water, brine, and combinations thereof,
wherein the hydroxide component comprises one of potassium hydroxide, calcium hydroxide, sodium hydroxide, and combinations thereof,
wherein the air stream comprises atmospheric air, which comprises approximately 420 ppm carbon dioxide, as evidenced by NOAA (¶ 2).
Saini further teaches that the hydroxide component may comprise a 30 wt% solution of NaOH (… first NaOH solution leaving the cell may have a concentration in excess of 25% (e.g., about 30%) by weight; [0032]). A 30% by weight solution of NaOH in water will comprise 30 g of NaOH per 100 g of solution. The density of pure NaOH is 2.13 g/mL and the density of a 30% NaOH solution is 1.3 g/ml, as evidenced by Yaws 2008 (Inorganic Compounds, entry 2897) and Yaws 2012 (Table 125: density of Aqueous Solutions, calculated from formula). Therefore, calculated as volumes, such a solution will have 14 mL of NaOH dissolved in 77 mL of solution, or will have a percent hydroxide by volume of 18%, meeting the limitation of at least one percent and no more than 30 percent (by volume) required by the instant claim.
Saini does not explicitly teach that the feed stream comprises at least one ppm to no more than ten percent (by volume) of a hydrocarbonaceous component, is silent on the level of impurities in the feed stream, and does not teach the carbonate component comprising any of the bicarbonates recited in the instant claim.
However, Saini does teaches that the feed stream may, or may not, contain oil or gas ([0029]) and therefore teaches general conditions that would include at least one ppm to no more than ten percent (by volume) of a hydrocarbonaceous component.
The courts have found 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). See MPEP 2144.05 II. Therefore, the claimed ranges merely represent an obvious variant and/or routine optimization of the values of the cited prior art.
Regarding the impurity level, while what metals and minerals constitute an impurity is indefinite (see Claim Rejections – 35 USC § 112), for the purposes of further examination “impurity” will be interpreted as meaning transition and post-transition series metal ions as well as any suspended inorganic solids (hard minerals).
Igunnu teaches the composition of produced water from oilfields as typically containing less than 1000 ppm total suspended solids, and less than 2500 ppm heavy metal ions (those in Table 1 excluding sodium, potassium, calcium, and magnesium, where mg/L is equivalent to ppm).
Therefore, it would have been obvious to one of ordinary skill in the art before the effective filing date of the claimed invention to use in the method of Saini a feed stream such as that described by Igunnu with less than 3,500 pm total impurities. One of ordinary skill in the art would have been motivated to do so because using a typical produced water feed stream from an oilfield, as taught by Saini, would have these characteristics, as taught by Igunnu.
Regarding the carbonate component, while Saini teaches that the carbonate component is sodium carbonate, Shim teaches that captured carbon dioxide can also produce sodium bicarbonate from sodium hydroxide (carbon dioxide, reacting with an aqueous solution of sodium hydroxide, could be converted to sodium bicarbonate (NaHCO3); abstract), that sodium bicarbonate has a wide range of uses (¶. 297, col. 2, ¶ 2), and that production of sodium bicarbonate captures two equivalents of carbon dioxide per two NaOH (p. 598, Eq. 7) while production of sodium carbonate captures only 1 equivalent of carbon dioxide (p. 298, Eq. 5).
Therefore, it would have been obvious to one of ordinary skill in the art before the effective filing date of the claimed invention to further modify the method of Saini to generate a sodium bicarbonate product, as taught by Shim, instead of sodium carbonate. One of ordinary skill in the art would have been motivated to do so because sodium bicarbonate has many potential uses and because generation of sodium bicarbonate captures more carbon dioxide, as taught by Shim.
Regarding claim 20, modified Saini teaches the process of claim 19, where Igunnu teaches that typical oilfield waste water has impurity metal content of 320 to 2430 ppm and a suspended solids content (TSS) of 1 to 1000 ppm (Table 1). This is interpreted as an impurity content of 320 to 3430 ppm, which overlaps with the instantly claimed range of less than 3,000 ppm.
It is noted that the courts have stated where the claimed ranges “overlap or lie inside the ranges disclosed by the prior art” a prima facie case of obviousness exists (see 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); Titanium Metals Corp. of America v. Banner, 778 F2d 775. 227 USPQ 773 (Fed. Cir. 1985) (see MPEP 2144.05.01). Therefore, the claimed ranges merely represent an obvious variant and/or routine optimization of the impurity content of the cited prior art.
Conclusion
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/NICHOLAS A. PIRO/Assistant Examiner, Art Unit 1738
/PAUL A WARTALOWICZ/Primary Examiner, Art Unit 1735