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 .
Claim Interpretation
The term “water of sufficient purity” is interpreted as defined in Para [0023] of the instant Specification.
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 1-5 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. The terms in parenthesis make the claims indefinite. The steps recited in parenthesis are out of order or repeat. It is unclear if there are required or not. Additionally it is unclear if these are required to be performed in numerical order or in the order they are listed.
Furthermore in claims 1 and 2, the phrase “…a granular concentrate of one or more lithium-containing aluminosilicate minerals, including a-spodumene…” is indefinite. It is unclear if the a-spodumene is required to be present or is part of the selection of “one or more” minerals or not and thus can be selected but is not required.
Claim 3 recites the limitation "the ambient gas pressure" in line 1. There is insufficient antecedent basis for this limitation in the claim. Additionally the term “ambient” is indefinite since it is generally interpreted as the surrounding pressure. This makes it unclear if this term refers to the gas pressure outside of the reactor or simply the gas pressure in the second reactor.
Claims 2-4 are rejected due to the virtue of their dependence on claim 1.
Allowable Subject Matter
Claims 1 and 5 would be allowable if rewritten or amended to overcome the rejection(s) under 35 U.S.C. 112(b) or 35 U.S.C. 112 (pre-AIA ), 2nd paragraph, set forth in this Office action.
Claims 2-4 would be allowable if rewritten to overcome the rejection(s) under 35 U.S.C. 112(b) or 35 U.S.C. 112 (pre-AIA ), 2nd paragraph, set forth in this Office action and to include all of the limitations of the base claim and any intervening claims.
The following is a statement of reasons for the indication of allowable subject matter: Claim 1 requires “A process for co-producing Li, Al, and Si-O materials from a hard rock source in the form of a granular concentrate of one or more lithium-containing aluminosilicate minerals, including spodumene, comprising:
providing a hard rock source in the form of a granular concentrate of one or more lithium-containing aluminosilicate minerals, including α-spodumene (Step 1);
calcining the granular concentrate at an elevated temperature to obtain a granular concentrate that includes β-spodumene (Step 2);
mixing the granular concentrate that includes β-spodumene with an aqueous solution of nitric acid and then agitating or stirring the resulting acidic mixture in a first reactor at a temperature greater than or equal to (≥) about 120 ºC and at a pressure greater than or equal to (≥) about 1 atm to effect leaching of Li and Al (Step 3);
conveying the acidic mixture to a second reactor to extract N-O-H gas at a temperature greater than or equal to (≥) about 120 ºC to form a slurry from which N-O-H gas has been removed (Step 4);
conveying the slurry from the second reactor through a cooling unit to a separator where it is divided into two fractions, one fraction rich in leached granular β-spodumene, and the other fraction comprising an aqueous liquid that contains dissolved lithium nitrate (LiNO3) and dissolved aluminum nitrate (Al(NO3)3), wherein the fraction rich in leached granular β-spodumene contains some residual LiNO3- and Al(NO3)3-containing aqueous liquid formed during Li-Al leaching (Steps 5 and 6);
transferring the fraction comprising an aqueous liquid that contains dissolved LiNO3 and Al(NO3)3 to a first liquid mixer (Steps 5, 6, and 8);
mixing the leached granular β-spodumene-rich fraction with water of sufficient purity, either prior to or after the leached granular β-spodumene-rich fraction enters a mixer-washer, to form a water-slurried leached granular β-spodumene-rich fraction, leading to mixing of the water of sufficient purity with the residual LiNO3- and Al(NO3)3-containing aqueous liquid formed during Li-Al leaching, to form a wash water containing LiNO3 and Al(NO3)3 (Steps 5–7);
conveying the water-slurried leached granular β-spodumene-rich fraction to a separator where the solids and liquid are divided into two fractions, one fraction comprising leached granular β-spodumene, and the other fraction comprising the wash water containing LiNO3 and Al(NO3)3 (Step 7);
transferring the wash water to the first liquid mixer where it coalesces with the previously separated LiNO3- and Al(NO3)3-containing liquid that enters said first liquid mixer to form a LiNO3- and Al(NO3)3-containing aqueous liquid (Step 8);
optionally, sending the water-washed leached granular solids to an optional reactor where said water-washed leached granular solids are mixed with aqueous/crystalline sodium hydroxide (NaOH) and/or aqueous/crystalline potassium hydroxide (KOH) to produce a (Na and/or K,Li,Al,Si-O)-H2O liquid (Step 39);
transferring the liquid in the first liquid mixer to a third reactor (Step 9a); and
subjecting the LiNO3- and Al(NO3)3-containing aqueous liquid in the third reactor to treatment that results in formation of a H2O-containing aluminous precipitate (“Al(OH)3”) that contains either amorphous Al-O-H solid material or amorphous Al-O-H solid material mixed with quasi-crystalline Al-O-H phases, that treatment comprising one or more of: (i) a heat treatment at a temperature sufficient to decompose the Al(NO3)3 dissolved in the liquid (Step 9a); (ii) reaction with an aqueous liquid that contains dissolved NH4OH (Step 9b); (iii) contact with aqueous (NH4)2CO3 (Step 9c); and (iv) contact with solid (NH4)2CO3 (Step 9c).”
Regarding claim 1, Hunwick US 2017/0175228 teaches a process for extracting lithium, aluminum, and silicon materials (Hunwick, [0150], Eqn. 1) from lithium-containing aluminosilicate minerals, including spodumene (Hunwick, [0150-[0151]), LiAlSi2O6, comprising at least the steps of:
providing a hard-rock source in the form of a granular concentrate of one or more lithium-containing aluminosilicate minerals, including spodumene (Hunwick, [0144], α-spodumene as a filter cake) (Step 1);
calcining the concentrate at an elevated temperature sufficient to convert substantially all of the spodumene therein from its natural alpha (α) polymorphic crystal structure to a synthetic beta (β) crystal structure (Hunwick, [0144]) (Step 2);
providing an aqueous solution of nitric acid (HNO3) (Hunwick, [0148]-[0149]) (Step 3);
mixing the calcined concentrate with the aqueous solution of nitric acid (Hunwick, [0148]-[0149]), and then subjecting the resulting mixture to conditions sufficient to effect leaching of lithium (Li) and aluminum (Al) from the calcined concentrate in a first primary reactor (Hunwick, [0032], “This solution can contain essentially all of the lithium values leached from the calcined spodumene ore concentrates, along with some aluminum, iron and other metal values leached from the spodumene, as soluble nitrates.”) (Step 4);
optionally, further reacting the concentrate with nitric acid in one or more secondary reactor(s), to form a slurry (optional Step 5) (this step is optional and need not be met for the method of Hunwick to read on the claim);
separating the slurry into two fractions (Hunwick, [0031], “solids-liquids separation stage (e.g. a filtration stage)”), where one fraction contains leached granular β-spodumene (Hunwick, [0032], filter cake), and the other fraction is a LiNO3(aq)- and Al(NO3)3(aq)-containing liquid containing a small amount of entrained or suspended solid material (Hunwick, [0032], “This solution can contain essentially all of the lithium values leached from the calcined spodumene ore concentrates, along with some aluminum, iron and other metal values leached from the spodumene, as soluble nitrates.”), the leached granular β-spodumene-containing fraction being washed with high-purity water, separated from that washwater (Hunwick, [0032]), and then, [optionally, contacted with an aqueous solution of Na and/or K hydroxide under conditions sufficient to dissolve Li, Al, and SiO2, and then subjected to recovery of: (i) Li as one or more of Li2CO3, LiOH(aq), LiOH·xH2O (where x = 1, 2, 3, or 6), and/or Li2O·ySiO2 (where y = 1 or 2); (ii) Al as one or more of Al(OH)3, Al2O3 H2O, and/or Al2O3; and (iii) SiO2 as either retained in (Na,K)2SiO3(aq) and/or as precipitated silica and/or silica gel] (the preceding portion in brackets is interpreted to be optional, so Hunwick need not teach this portion to meet the claim limitations) (Step 8); and
combining the LiNO3(aq)- and Al(NO3)3(aq)-containing washwater from the mixer with the LiNO3(aq)- and Al(NO3)3(aq)-containing liquid fraction containing a small amount of entrained or suspended solid material in a third primary reactor (Hunwick, [0032], it is implicit that a third reactor receives the filtrate from the filtration stage and that the washings from the filter cake would be part of the received solution) (Step 9).
However, there is no teaching or suggestion regarding “…conveying the acidic mixture to a second reactor to extract N-O-H gas at a temperature greater than or equal to (≥) about 120 ºC to form a slurry from which N-O-H gas has been removed (Step 4);
conveying the slurry from the second reactor through a cooling unit to a separator where it is divided into two fractions, one fraction rich in leached granular β-spodumene, and the other fraction comprising an aqueous liquid that contains dissolved lithium nitrate (LiNO3) and dissolved aluminum nitrate (Al(NO3)3), wherein the fraction rich in leached granular β-spodumene contains some residual LiNO3- and Al(NO3)3-containing aqueous liquid formed during Li-Al leaching (Steps 5 and 6);
transferring the fraction comprising an aqueous liquid that contains dissolved LiNO3 and Al(NO3)3 to a first liquid mixer (Steps 5, 6, and 8);
mixing the leached granular β-spodumene-rich fraction with water of sufficient purity, either prior to or after the leached granular β-spodumene-rich fraction enters a mixer-washer, to form a water-slurried leached granular β-spodumene-rich fraction, leading to mixing of the water of sufficient purity with the residual LiNO3- and Al(NO3)3-containing aqueous liquid formed during Li-Al leaching, to form a wash water containing LiNO3 and Al(NO3)3 (Steps 5–7);
conveying the water-slurried leached granular β-spodumene-rich fraction to a separator where the solids and liquid are divided into two fractions, one fraction comprising leached granular β-spodumene, and the other fraction comprising the wash water containing LiNO3 and Al(NO3)3 (Step 7);
transferring the wash water to the first liquid mixer where it coalesces with the previously separated LiNO3- and Al(NO3)3-containing liquid that enters said first liquid mixer to form a LiNO3- and Al(NO3)3-containing aqueous liquid (Step 8);
optionally, sending the water-washed leached granular solids to an optional reactor where said water-washed leached granular solids are mixed with aqueous/crystalline sodium hydroxide (NaOH) and/or aqueous/crystalline potassium hydroxide (KOH) to produce a (Na and/or K,Li,Al,Si-O)-H2O liquid (Step 39);
transferring the liquid in the first liquid mixer to a third reactor (Step 9a); and
subjecting the LiNO3- and Al(NO3)3-containing aqueous liquid in the third reactor to treatment that results in formation of a H2O-containing aluminous precipitate (“Al(OH)3”) that contains either amorphous Al-O-H solid material or amorphous Al-O-H solid material mixed with quasi-crystalline Al-O-H phases, that treatment comprising one or more of: (i) a heat treatment at a temperature sufficient to decompose the Al(NO3)3 dissolved in the liquid (Step 9a); (ii) reaction with an aqueous liquid that contains dissolved NH4OH (Step 9b); (iii) contact with aqueous (NH4)2CO3 (Step 9c); and (iv) contact with solid (NH4)2CO3 (Step 9c).”
Claims 2-4 are indicated as containing allowable subject matter due to the virtue of their dependence on claim 1.
Claim 5 requires “5. A process of co-producing Li, Al, and Si-O materials from a granular concentrate including spodumene in its alpha (α) crystallographic form, comprising:
providing a granular concentrate including spodumene in its alpha (α) crystallographic form (Step 1);
calcining the concentrate at an elevated temperature to convert substantially all of the α-spodumene to the beta (β) crystallographic form (Step 2); mixing the resulting β-spodumene concentrate with an aqueous solution of nitric acid (HNO3) and/or a N-O-H gas plus water (H2O), at a temperature ≥ about 120 °C, and at a pressure between about one atmosphere (1 atm) and about 10 atm, prior to, or after, entry into a first reactor to form an acidic mixture (Step 3);
in the first reactor, stirring or agitating the contained acidic mixture for a period of time sufficient to effect leaching of Li and Al from the β-spodumene at ≥ about 120 °C, and at a pressure ≥ about 1 atm (Step 3);
conveying the resulting acidic mixture to a second reactor to extract N-O-H gas, wherein, if necessary, ambient gas pressure is reduced to about 1 atm to form a substantially gas-depleted slurry (Steps 3 and 4);
conveying the substantially gas-depleted slurry from the second reactor through a cooling unit to a separator, where it is divided into two fractions, one fraction being rich in leached granular β-spodumene and the other fraction comprising an aqueous liquid that contains dissolved lithium nitrate (LiNO3) and dissolved aluminum nitrate (Al(NO3)3) (Steps 4 and 5);
transferring the LiNO3- and Al(NO3)3-containing aqueous liquid to a first liquid mixer (Step 6);
mixing the leached granular β-spodumene-rich fraction with water of sufficient purity, either prior to or after the leached granular β-spodumene-rich fraction enters a mixer-washer, to form a water-slurried leached granular β-spodumene-rich fraction, leading to mixing of the water of sufficient purity with the residual LiNO3- and Al(NO3)3-containing aqueous liquid formed during Li-Al leaching, to form a wash water containing dissolved LiNO3 and Al(NO3)3; (Steps 5–7);
conveying the water-slurried leached granular β-spodumene-rich fraction to a separator where the solids and liquid are divided into two fractions, one fraction comprising leached granular β-spodumene and the other fraction comprising the wash water containing LiNO3 and Al(NO3)3 (Step 7);
transferring the wash water to the first liquid mixer where it coalesces with the previously separated LiNO3- and Al(NO3)3-containing liquid that enters said first liquid mixer to form a LiNO3- and Al(NO3)3-containing aqueous liquid (Steps 7 and 8);
optionally, sending the water-washed leached granular solids to a ninth reactor, where they are mixed with (i) aqueous and/or crystalline sodium hydroxide (NaOH) and/or (ii) aqueous and/or crystalline potassium hydroxide (KOH) to produce a (Na and/or K,Li,Al,Si-O)-H2O liquid (Step 39);
transferring the liquid in the first liquid mixer to a third reactor (Step 8);
subjecting the LiNO3- and Al(NO3)3-containing aqueous liquid in the third reactor to treatment that results in formation of a H2O-containing aluminous precipitate (“Al(OH)3”) that contains amorphous Al-O-H solid material or amorphous Al-O-H solid material mixed with quasi-crystalline Al-O-H phases, that treatment comprising one or more of: (i) a heat treatment at a temperature sufficient to decompose the Al(NO3)3 dissolved in the liquid (Step 9a); (ii) reaction with an aqueous liquid that contains dissolved ammonium hydroxide, NH4OH (Step 9b); (iii) contact with aqueous ammonium carbonate, (NH4)2CO3 (Step 9c); and (iv) contact with solid (NH4)2CO3 (Step 9c), with the proviso that when only treatment (i) is used, the process steps further include cooling the slurry flowing out of the third reactor (Step 10);
transferring the slurry to a mixer-separator where it is sufficiently stirred and/or agitated and thereafter divided into two fractions, one fraction comprising the aluminous precipitate formed in the third reactor and the other fraction comprising an aqueous liquid that contains dissolved LiNO3 (Step 11);
transferring the fraction comprising an aqueous liquid that contains dissolved LiNO3- from the separator to a second liquid mixer (Step 11);
mixing the slurry containing Al(OH)3 with water of sufficient purity and conveying the resulting slurry to a mixer-washer where it is stirred and/or agitated prior to being divided into two fractions, one fraction being rich in Al(OH)3, and the other fraction comprising a wash water that contains dissolved LiNO3 (Steps 11 and 12);
conveying the separated fraction comprising the wash water to the second liquid mixer where it coalesces with the previously separated LiNO3-containing aqueous liquid transferred to that liquid mixer (Step 12);
converting the separated Al(OH)3 to one or more Al-O-H solids (Step 13 and optional Step 14);
transferring the coalesced LiNO3-containing aqueous liquid from the second liquid mixer to a fourth reactor (Step 15);
combining the coalesced LiNO3-containing aqueous liquid in the fourth reactor with NH3-CO2 gas and/or aqueous (NH4)2CO3 and/or solid (NH4)2CO3, thereby inducing precipitation of solid Li2CO3 with simultaneous formation of aqueous NH4NO3 to form a Li2CO3-, NH4NO3-, and (NH4)2CO3-containing aqueous slurry (Step 16);
transferring the Li2CO3-, NH4NO3-, and (NH4)2CO3-containing aqueous slurry from the fourth reactor to a fifth reactor where heating to a temperature of about 100 °C, and at a pressure of about 1 atm, results in the decomposition of substantially all remaining dissolved (NH4)2CO3, as evidenced by production of a NH3-CO2 off gas, to form a Li2CO3- and NH4NO3-containing slurry (Steps 16 and 17);
cooling the Li2CO3- and NH4NO3-containing slurry flowing out of the fifth reactor, and then transferring it to a mixer-separator where it is stirred and/or agitated, and thereafter divided into two fractions, one fraction comprising the solid Li2CO3 formed in the fourth reactor and the other fraction comprising a NH4NO3-containing aqueous liquid (Steps 18 and 19);
transferring the NH4NO3-containing aqueous liquid to a third liquid mixer, and mixing the fraction comprising the solid Li2CO3 with water of sufficient purity prior to sending it to a mixer-washer where it is stirred and/or agitated, the result being formation and separation, in a separator connected to the mixer-washer, of a wash water that contains dissolved NH4NO3 (Steps 19 and 20);
transferring the NH4NO3-containing wash water to the third liquid mixer where it coalesces with the previously-separated NH4NO3-containing aqueous liquid that enters that liquid mixer (Step 20);
optionally, conveying the moist Li2CO3 from the separator to a dryer, and optionally thereafter transferring the dried Li2CO3 to a chemical conversion system, or optionally transferring the moist Li2CO3 from the separator directly to the chemical conversion system where the chemical conversion system is used to convert or react Li2CO3 to produce aqueous LiOH and/or solid LiOH∙xH2O (x = 1, 2, 3, or 6) (Steps 20–22);
upon its exit from the third liquid mixer, optionally heating the NH4NO3-containing aqueous liquid to a temperature of about 120 °C as it flows toward an additional mixer where it is combined with an excess amount of solid magnesium oxide (MgO), the MgO optionally being preheated prior to its mixing with the NH4NO3-containing aqueous liquid, to form a multiphase material (Steps 23 and 24);
conveying the multiphase material from the additional mixer to a sixth reactor where its temperature is maintained at about 120 °C, which results in the formation of an aqueous slurry of magnesium nitrate (Mg(NO3)2) and magnesium hydroxide (Mg(OH)2), and NH3 gas (Steps 24 and 25);
conveying the NH3 to a gas mixer where it is combined with both provided CO2 and the NH3-CO2 gas produced in the fifth reactor (Steps 25 and 26);
conveying the mixed NH3-CO2 gas through a cooling unit, and thereafter recycling it back to precipitate additional Li2CO3 (Step 16), or optionally sending it to a seventh reactor where it is mixed with H2O to form aqueous (NH4)2CO3, the resulting (NH4)2CO3-containing aqueous liquid then being recycled back to precipitate additional Li2CO3 (Steps 26 and 27);
transferring the aqueous slurry co-produced in the sixth reactor—it comprising Mg(NO3)2, Mg(OH)2, and H2O—to a mixer where it is stirred and/or agitated and thereafter separated into two fractions, one fraction containing Mg(OH)2-rich solids and the other fraction being an aqueous liquid that contains dissolved Mg(NO3)2 (Steps 25 and 28);
conveying the Mg(NO3)2-containing aqueous liquid to a fourth liquid mixer (Step 28);
mixing the Mg(OH)2-rich solids with water, and then sending the resulting slurry to a mixer-washer where it is stirred and/or agitated, the result being formation of a wash water that contains dissolved Mg(NO3)2 (Steps 28 and 29);
transferring the Mg(OH)2- and Mg(NO3)2-containing aqueous slurry to a separator where it is divided into two fractions, one fraction comprising moist Mg(OH)2 plus any residual MgO, and the other fraction being the Mg(NO3)2-containing wash water formed in the mixer-washer (Step 29); transferring the Mg(NO3)2-containing wash water to the fourth liquid mixer where it coalesces with the previously-separated Mg(NO3)2-containing aqueous liquid which enters that liquid mixer (Step 29);
transferring a portion of the moist Mg(OH)2 ± MgO to a first furnace where it is heated to a maximum temperature of about 600 °C, the result being production of MgO and water vapor, the MgO being recycled back to Step 24 (Steps 29 and 33);
transferring the Mg(NO3)2-containing aqueous liquid from the fourth liquid mixer to an evaporator where it is heated to a temperature of about 150 °C, which initiates production of molten Mg(NO3)2·xH2O (x ≤ 6), water vapor, and any generated N-O-H gas (Steps 30 and 31);
after exiting the evaporator, conveying the H2O-depleted Mg(NO3)2·xH2O liquid to a mixer where it is blended with a portion of the moist Mg(OH)2 ± MgO produced previously (Step 29) (Steps 31 and 32);
transferring the Mg(NO3)2·xH2O-Mg(OH)2 ± MgO slurry from the mixer to a second furnace where it is heated up to a maximum temperature of about 600 °C, the purpose being to form MgO plus solid impurities, along with a NO2- and O2-containing N-O-H gas (Steps 32 and 34);
conveying the MgO + solid impurities to a mixer-washer where the solids are slurried with a liquid in which MgO is substantially insoluble, but also in which the solid impurities are substantially soluble (Steps 34 and 35);
stirring or agitating the MgO-containing slurry prior to sending it to a separator where it is divided into two fractions, one fraction comprising MgO, which is recycled back to Step 24, and the other fraction being the liquid that is enriched in impurities (Step 35);
optionally treating the liquid in a way that divides it into two fractions, one fraction being a purified liquid and the other fraction comprising the impurities present in the liquid fraction formed in the separator (Step 36);
optionally recycling the purified liquid back to the earlier step wherein MgO + solid impurities was slurried with the originally provided liquid (Step 36);
conveying (i) the N-O-H gas removed from the second and third reactors, and also (ii) the N-O-H gas produced in the evaporator (if any), and also (iii) the NO2-, O2- and H2O-containing N-O-H gas formed in the second furnace, to a gas mixer where the individual streams of gas intermingle (Step 37);
conveying the N-O-H gas from the gas mixer back to the first reactor, and/or to an eighth reactor where it is mixed into H2O to produce aqueous HNO3 that is subsequently sent back to the first reactor (Step 38).”
Regarding claim 5, Hunwick US 2017/0175228 teaches a process for extracting lithium, aluminum, and silicon materials (Hunwick, [0150], Eqn. 1) from lithium-containing aluminosilicate minerals, including spodumene (Hunwick, [0150-[0151]), LiAlSi2O6, comprising at least the steps of:
providing a hard-rock source in the form of a granular concentrate of one or more lithium-containing aluminosilicate minerals, including spodumene (Hunwick, [0144], α-spodumene as a filter cake) (Step 1);
calcining the concentrate at an elevated temperature sufficient to convert substantially all of the spodumene therein from its natural alpha (α) polymorphic crystal structure to a synthetic beta (β) crystal structure (Hunwick, [0144]) (Step 2);
providing an aqueous solution of nitric acid (HNO3) (Hunwick, [0148]-[0149]) (Step 3);
mixing the calcined concentrate with the aqueous solution of nitric acid (Hunwick, [0148]-[0149]), and then subjecting the resulting mixture to conditions sufficient to effect leaching of lithium (Li) and aluminum (Al) from the calcined concentrate in a first primary reactor (Hunwick, [0032], “This solution can contain essentially all of the lithium values leached from the calcined spodumene ore concentrates, along with some aluminum, iron and other metal values leached from the spodumene, as soluble nitrates.”) (Step 4);
optionally, further reacting the concentrate with nitric acid in one or more secondary reactor(s), to form a slurry (optional Step 5) (this step is optional and need not be met for the method of Hunwick to read on the claim);
separating the slurry into two fractions (Hunwick, [0031], “solids-liquids separation stage (e.g. a filtration stage)”), where one fraction contains leached granular β-spodumene (Hunwick, [0032], filter cake), and the other fraction is a LiNO3(aq)- and Al(NO3)3(aq)-containing liquid containing a small amount of entrained or suspended solid material (Hunwick, [0032], “This solution can contain essentially all of the lithium values leached from the calcined spodumene ore concentrates, along with some aluminum, iron and other metal values leached from the spodumene, as soluble nitrates.”), the leached granular β-spodumene-containing fraction being washed with high-purity water, separated from that washwater (Hunwick, [0032]), and then, [optionally, contacted with an aqueous solution of Na and/or K hydroxide under conditions sufficient to dissolve Li, Al, and SiO2, and then subjected to recovery of: (i) Li as one or more of Li2CO3, LiOH(aq), LiOH·xH2O (where x = 1, 2, 3, or 6), and/or Li2O·ySiO2 (where y = 1 or 2); (ii) Al as one or more of Al(OH)3, Al2O3 H2O, and/or Al2O3; and (iii) SiO2 as either retained in (Na,K)2SiO3(aq) and/or as precipitated silica and/or silica gel] (the preceding portion in brackets is interpreted to be optional, so Hunwick need not teach this portion to meet the claim limitations) (Step 8); and
combining the LiNO3(aq)- and Al(NO3)3(aq)-containing washwater from the mixer with the LiNO3(aq)- and Al(NO3)3(aq)-containing liquid fraction containing a small amount of entrained or suspended solid material in a third primary reactor (Hunwick, [0032], it is implicit that a third reactor receives the filtrate from the filtration stage and that the washings from the filter cake would be part of the received solution) (Step 9).
However, there is no teaching or suggestion from Hunwick regarding “…conveying the resulting acidic mixture to a second reactor to extract N-O-H gas, wherein, if necessary, ambient gas pressure is reduced to about 1 atm to form a substantially gas-depleted slurry (Steps 3 and 4);
conveying the substantially gas-depleted slurry from the second reactor through a cooling unit to a separator, where it is divided into two fractions, one fraction being rich in leached granular β-spodumene and the other fraction comprising an aqueous liquid that contains dissolved lithium nitrate (LiNO3) and dissolved aluminum nitrate (Al(NO3)3) (Steps 4 and 5);
transferring the LiNO3- and Al(NO3)3-containing aqueous liquid to a first liquid mixer (Step 6);
mixing the leached granular β-spodumene-rich fraction with water of sufficient purity, either prior to or after the leached granular β-spodumene-rich fraction enters a mixer-washer, to form a water-slurried leached granular β-spodumene-rich fraction, leading to mixing of the water of sufficient purity with the residual LiNO3- and Al(NO3)3-containing aqueous liquid formed during Li-Al leaching, to form a wash water containing dissolved LiNO3 and Al(NO3)3; (Steps 5–7);
conveying the water-slurried leached granular β-spodumene-rich fraction to a separator where the solids and liquid are divided into two fractions, one fraction comprising leached granular β-spodumene and the other fraction comprising the wash water containing LiNO3 and Al(NO3)3 (Step 7);
transferring the wash water to the first liquid mixer where it coalesces with the previously separated LiNO3- and Al(NO3)3-containing liquid that enters said first liquid mixer to form a LiNO3- and Al(NO3)3-containing aqueous liquid (Steps 7 and 8);
optionally, sending the water-washed leached granular solids to a ninth reactor, where they are mixed with (i) aqueous and/or crystalline sodium hydroxide (NaOH) and/or (ii) aqueous and/or crystalline potassium hydroxide (KOH) to produce a (Na and/or K,Li,Al,Si-O)-H2O liquid (Step 39);
transferring the liquid in the first liquid mixer to a third reactor (Step 8);
subjecting the LiNO3- and Al(NO3)3-containing aqueous liquid in the third reactor to treatment that results in formation of a H2O-containing aluminous precipitate (“Al(OH)3”) that contains amorphous Al-O-H solid material or amorphous Al-O-H solid material mixed with quasi-crystalline Al-O-H phases, that treatment comprising one or more of: (i) a heat treatment at a temperature sufficient to decompose the Al(NO3)3 dissolved in the liquid (Step 9a); (ii) reaction with an aqueous liquid that contains dissolved ammonium hydroxide, NH4OH (Step 9b); (iii) contact with aqueous ammonium carbonate, (NH4)2CO3 (Step 9c); and (iv) contact with solid (NH4)2CO3 (Step 9c), with the proviso that when only treatment (i) is used, the process steps further include cooling the slurry flowing out of the third reactor (Step 10);
transferring the slurry to a mixer-separator where it is sufficiently stirred and/or agitated and thereafter divided into two fractions, one fraction comprising the aluminous precipitate formed in the third reactor and the other fraction comprising an aqueous liquid that contains dissolved LiNO3 (Step 11);
transferring the fraction comprising an aqueous liquid that contains dissolved LiNO3- from the separator to a second liquid mixer (Step 11);
mixing the slurry containing Al(OH)3 with water of sufficient purity and conveying the resulting slurry to a mixer-washer where it is stirred and/or agitated prior to being divided into two fractions, one fraction being rich in Al(OH)3, and the other fraction comprising a wash water that contains dissolved LiNO3 (Steps 11 and 12);
conveying the separated fraction comprising the wash water to the second liquid mixer where it coalesces with the previously separated LiNO3-containing aqueous liquid transferred to that liquid mixer (Step 12);
converting the separated Al(OH)3 to one or more Al-O-H solids (Step 13 and optional Step 14);
transferring the coalesced LiNO3-containing aqueous liquid from the second liquid mixer to a fourth reactor (Step 15);
combining the coalesced LiNO3-containing aqueous liquid in the fourth reactor with NH3-CO2 gas and/or aqueous (NH4)2CO3 and/or solid (NH4)2CO3, thereby inducing precipitation of solid Li2CO3 with simultaneous formation of aqueous NH4NO3 to form a Li2CO3-, NH4NO3-, and (NH4)2CO3-containing aqueous slurry (Step 16);
transferring the Li2CO3-, NH4NO3-, and (NH4)2CO3-containing aqueous slurry from the fourth reactor to a fifth reactor where heating to a temperature of about 100 °C, and at a pressure of about 1 atm, results in the decomposition of substantially all remaining dissolved (NH4)2CO3, as evidenced by production of a NH3-CO2 off gas, to form a Li2CO3- and NH4NO3-containing slurry (Steps 16 and 17);
cooling the Li2CO3- and NH4NO3-containing slurry flowing out of the fifth reactor, and then transferring it to a mixer-separator where it is stirred and/or agitated, and thereafter divided into two fractions, one fraction comprising the solid Li2CO3 formed in the fourth reactor and the other fraction comprising a NH4NO3-containing aqueous liquid (Steps 18 and 19);
transferring the NH4NO3-containing aqueous liquid to a third liquid mixer, and mixing the fraction comprising the solid Li2CO3 with water of sufficient purity prior to sending it to a mixer-washer where it is stirred and/or agitated, the result being formation and separation, in a separator connected to the mixer-washer, of a wash water that contains dissolved NH4NO3 (Steps 19 and 20);
transferring the NH4NO3-containing wash water to the third liquid mixer where it coalesces with the previously-separated NH4NO3-containing aqueous liquid that enters that liquid mixer (Step 20);
optionally, conveying the moist Li2CO3 from the separator to a dryer, and optionally thereafter transferring the dried Li2CO3 to a chemical conversion system, or optionally transferring the moist Li2CO3 from the separator directly to the chemical conversion system where the chemical conversion system is used to convert or react Li2CO3 to produce aqueous LiOH and/or solid LiOH∙xH2O (x = 1, 2, 3, or 6) (Steps 20–22);
upon its exit from the third liquid mixer, optionally heating the NH4NO3-containing aqueous liquid to a temperature of about 120 °C as it flows toward an additional mixer where it is combined with an excess amount of solid magnesium oxide (MgO), the MgO optionally being preheated prior to its mixing with the NH4NO3-containing aqueous liquid, to form a multiphase material (Steps 23 and 24);
conveying the multiphase material from the additional mixer to a sixth reactor where its temperature is maintained at about 120 °C, which results in the formation of an aqueous slurry of magnesium nitrate (Mg(NO3)2) and magnesium hydroxide (Mg(OH)2), and NH3 gas (Steps 24 and 25);
conveying the NH3 to a gas mixer where it is combined with both provided CO2 and the NH3-CO2 gas produced in the fifth reactor (Steps 25 and 26);
conveying the mixed NH3-CO2 gas through a cooling unit, and thereafter recycling it back to precipitate additional Li2CO3 (Step 16), or optionally sending it to a seventh reactor where it is mixed with H2O to form aqueous (NH4)2CO3, the resulting (NH4)2CO3-containing aqueous liquid then being recycled back to precipitate additional Li2CO3 (Steps 26 and 27);
transferring the aqueous slurry co-produced in the sixth reactor—it comprising Mg(NO3)2, Mg(OH)2, and H2O—to a mixer where it is stirred and/or agitated and thereafter separated into two fractions, one fraction containing Mg(OH)2-rich solids and the other fraction being an aqueous liquid that contains dissolved Mg(NO3)2 (Steps 25 and 28);
conveying the Mg(NO3)2-containing aqueous liquid to a fourth liquid mixer (Step 28);
mixing the Mg(OH)2-rich solids with water, and then sending the resulting slurry to a mixer-washer where it is stirred and/or agitated, the result being formation of a wash water that contains dissolved Mg(NO3)2 (Steps 28 and 29);
transferring the Mg(OH)2- and Mg(NO3)2-containing aqueous slurry to a separator where it is divided into two fractions, one fraction comprising moist Mg(OH)2 plus any residual MgO, and the other fraction being the Mg(NO3)2-containing wash water formed in the mixer-washer (Step 29); transferring the Mg(NO3)2-containing wash water to the fourth liquid mixer where it coalesces with the previously-separated Mg(NO3)2-containing aqueous liquid which enters that liquid mixer (Step 29);
transferring a portion of the moist Mg(OH)2 ± MgO to a first furnace where it is heated to a maximum temperature of about 600 °C, the result being production of MgO and water vapor, the MgO being recycled back to Step 24 (Steps 29 and 33);
transferring the Mg(NO3)2-containing aqueous liquid from the fourth liquid mixer to an evaporator where it is heated to a temperature of about 150 °C, which initiates production of molten Mg(NO3)2·xH2O (x ≤ 6), water vapor, and any generated N-O-H gas (Steps 30 and 31);
after exiting the evaporator, conveying the H2O-depleted Mg(NO3)2·xH2O liquid to a mixer where it is blended with a portion of the moist Mg(OH)2 ± MgO produced previously (Step 29) (Steps 31 and 32);
transferring the Mg(NO3)2·xH2O-Mg(OH)2 ± MgO slurry from the mixer to a second furnace where it is heated up to a maximum temperature of about 600 °C, the purpose being to form MgO plus solid impurities, along with a NO2- and O2-containing N-O-H gas (Steps 32 and 34);
conveying the MgO + solid impurities to a mixer-washer where the solids are slurried with a liquid in which MgO is substantially insoluble, but also in which the solid impurities are substantially soluble (Steps 34 and 35);
stirring or agitating the MgO-containing slurry prior to sending it to a separator where it is divided into two fractions, one fraction comprising MgO, which is recycled back to Step 24, and the other fraction being the liquid that is enriched in impurities (Step 35);
optionally treating the liquid in a way that divides it into two fractions, one fraction being a purified liquid and the other fraction comprising the impurities present in the liquid fraction formed in the separator (Step 36);
optionally recycling the purified liquid back to the earlier step wherein MgO + solid impurities was slurried with the originally provided liquid (Step 36);
conveying (i) the N-O-H gas removed from the second and third reactors, and also (ii) the N-O-H gas produced in the evaporator (if any), and also (iii) the NO2-, O2- and H2O-containing N-O-H gas formed in the second furnace, to a gas mixer where the individual streams of gas intermingle (Step 37);
conveying the N-O-H gas from the gas mixer back to the first reactor, and/or to an eighth reactor where it is mixed into H2O to produce aqueous HNO3 that is subsequently sent back to the first reactor (Step 38).” Nor would it have been obvious to do so.
Conclusion
Any inquiry concerning this communication or earlier communications from the examiner should be directed to SYED TAHA IQBAL whose telephone number is (571)270-5857. The examiner can normally be reached M-F; 7-5.
Examiner interviews are available via telephone, in-person, and video conferencing using a USPTO supplied web-based collaboration tool. To schedule an interview, applicant is encouraged to use the USPTO Automated Interview Request (AIR) at http://www.uspto.gov/interviewpractice.
If attempts to reach the examiner by telephone are unsuccessful, the examiner’s supervisor, Anthony Zimmer can be reached at (571) 270-3591. The fax phone number for the organization where this application or proceeding is assigned is 571-273-8300.
Information regarding the status of published or unpublished applications may be obtained from Patent Center. Unpublished application information in Patent Center is available to registered users. To file and manage patent submissions in Patent Center, visit: https://patentcenter.uspto.gov. Visit https://www.uspto.gov/patents/apply/patent-center for more information about Patent Center and https://www.uspto.gov/patents/docx for information about filing in DOCX format. For additional questions, contact the Electronic Business Center (EBC) at 866-217-9197 (toll-free). If you would like assistance from a USPTO Customer Service Representative, call 800-786-9199 (IN USA OR CANADA) or 571-272-1000.
/SYED T IQBAL/Examiner, Art Unit 1736
/ANTHONY J ZIMMER/Supervisory Patent Examiner, Art Unit 1736
Prosecution Insights