WO2025101503A1 - Purifying precursor compounds and related systems and methods - Google Patents
Purifying precursor compounds and related systems and methods Download PDFInfo
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- WO2025101503A1 WO2025101503A1 PCT/US2024/054546 US2024054546W WO2025101503A1 WO 2025101503 A1 WO2025101503 A1 WO 2025101503A1 US 2024054546 W US2024054546 W US 2024054546W WO 2025101503 A1 WO2025101503 A1 WO 2025101503A1
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- crude product
- product solution
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- precursor compound
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D1/00—Evaporating
- B01D1/22—Evaporating by bringing a thin layer of the liquid into contact with a heated surface
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
- B01D3/34—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping with one or more auxiliary substances
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
- B01D3/42—Regulation; Control
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G19/00—Compounds of tin
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G33/00—Compounds of niobium
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G41/00—Compounds of tungsten
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/04—Purification; Separation; Use of additives by distillation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/04—Purification; Separation; Use of additives by distillation
- C07C7/05—Purification; Separation; Use of additives by distillation with the aid of auxiliary compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/22—Tin compounds
- C07F7/2296—Purification, stabilisation, isolation
Definitions
- the present disclosure relates to the field of distilling sensitive material from crude mixtures using high boiling point solvents and related systems and related methods.
- Some embodiments of the present disclosure relate to a method comprising: mixing a crude product solution with a first solvent, wherein the crude product solution comprises a precursor compound and at least one impurity; wherein a boiling point of the first solvent is greater than a boiling point of the crude product solution; feeding a mixture of at least the crude product solution and the first solvent to an evaporator; and collecting, from the evaporator, a distillate comprising the precursor compound, wherein a purity of the precursor compound in the distillate is greater than 95% as determined by 1 H NMR.
- Some embodiments relate to a system comprising a crude product solution comprising a precursor compound and at least one impurity; a first solvent having a boiling point that is greater than a boiling point of the crude product solution; and an evaporator, wherein, when a mixture of the crude product solution and the first solvent is fed to the evaporator, the evaporator is configured to product a distillate comprising the precursor compound, wherein a purity of the precursor compound in the distillate is greater than 95% as determined by 1 H NMR.
- FIG. 1 illustrates a flowchart of a method for distilling a precursor compound from a crude mixture using high boiling point solvents, according to some embodiments.
- FIG. 2 is a 1 H NMR spectra of the crude product solution and distillate fractions, according to some embodiments.
- Some embodiments relate to methods for purifying precursor compounds and related systems, methods, and compositions. Isolating precursor compounds from crude product solutions can be difficult due to challenges associated with decomposition of the precursor compound (i.e., product), presence of undesirable decomposition reaction byproducts, and/or undesirable interaction of the reaction byproducts with the precursor compound. In addition, when isolating or purifying the precursor compound, various residues in form of oils and solids, among others, which cannot flow through a system used for isolating and/or purifying the precursor compound, decompose to form other byproducts and thus also introduce impurities. As disclosed herein, to overcome these and other challenges, in some embodiments, a high-boiling point co-solvent is introduced into the system.
- the solvent can reduce solids deposition and formation, facilitate movement through the system of solid and viscous residues, and/or reduce or eliminate occurrence of undesirable reactions that produce undesirable byproducts. As disclosed herein, the solvent can result in improved yields and high purity levels, among numerous other advantages.
- FIG. 1 is a flowchart of a method for separating a precursor compound from a crude product solution, according to some embodiments. As shown in FIG.
- the method 100 for separating a precursor compound from a crude product solution may comprise one or more of the following steps: mixing 102 a crude product solution with a first solvent; feeding 104 a mixture of at least the crude product solution and the first solvent to an evaporator; and collecting 106, from the evaporator, a distillate comprising a precursor compound.
- the method further comprises collecting a residue comprising the at least one impurity.
- the method 102 comprises mixing a crude product solution with a first solvent.
- the mixing comprises contacting the crude product solution and the first solvent. In some embodiments, the mixing comprises bringing the crude product solution and the first solvent into immediate or close proximity. In some embodiments, the mixing comprises bringing the crude product solution and the first solvent into direct physical contact. In some embodiments, the mixing comprises agitating the crude product solution and the first solvent. In some embodiments, the mixing comprises stirring the crude product solution and the first solvent. In some embodiments, the mixing comprises combining the crude product solution and the first solvent. It will be appreciated that other techniques for mixing and/or contacting may be employed herein without departing from the scope of this disclosure.
- the first solvent is a high-boiling point solvent. In some embodiments, the first solvent is a co-solvent. In some embodiments, for example, the first solvent is a co-solvent because the crude product solution comprises at least one solvent. In some embodiments, for example, the crude product solution comprises a second solvent. In some embodiments, the crude product solution comprises a precursor compound. In some embodiments, the crude product solution comprises a precursor compound and at least one impurity. In some embodiments, the precursor compound is dissolved in the second solvent. In some embodiments, the at least one impurity is not dissolved in the second solvent. In some embodiments, the first solvent is inert with respect to the precursor compound.
- the at least one impurity is at least partially dissolved in the second solvent. In some embodiments, at least a portion of the precursor compound is dissolved in the second solvent. In some embodiments, at least a portion of the precursor compound is not dissolved in the second solvent. In embodiments, the at least one first solvent may serve as a carrier to keep residues, viscous oils, reaction byproducts, and/or at least one impurity mobile in the crude product solution and/or mixture.
- the first solvent may comprise a solvent having a boiling point that is greater than at least one of the crude product solution, the second solvent, or any combination thereof.
- a boiling point of the first solvent is greater than a boiling point of the crude product solution.
- the boiling point of the first solvent is at least 10%, at least 20%, at least 30%, at least 40%, at least 50%, at least 60%, at least 70%, at least 80%, at least 90% at least 100%, at least 200%, at least 300%, at least 400%, at least 500% greater than the boiling point of the crude product solution, or any range or subrange between 10% and 1000%.
- a boiling point of the first solvent is greater than a boiling point of the second solvent.
- the boiling point of the first solvent is at least 10%, at least 20%, at least 30%, at least 40%, at least 50%, at least 60%, at least 70%, at least 80%, at least 90% at least 100%, at least 200%, at least 300%, at least 400%, at least 500% greater than the boiling point of the second solvent, or any range or subrange between 10% and 1000%.
- the boiling point of the first solvent is 250 °C to 500 °C, or any range or subrange between 250 °C and 500 °C. In some embodiments, the boiling point of the first solvent is 275°C to 500°C, 300°C to 500°C, 325 °C to 500°C, 350°C to 500°C, 375°C to 500°C, 400°C to 500°C, 425°C to 500°C, 450°C to 500°C, 475°C to 500°C, 250°C to 475°C, 250°C to 450°C, 250°C to 425°C, 250°C to 400°C, 250°C to 375°C, 250°C to 350°C, 250°C to 325°C, 250°C to 300°C, or 250°C to 275°C.
- the boiling point of the crude product solution is lower than the boiling point of the at least one first solvent. In some embodiments, the boiling point of the crude product solution is 50°C to 245°C, or any range or subrange between 50°C and 245°C.
- the boiling point of the crude product solution is 50°C to 245°C, 50°C to 240°C, 50°C to 235°C, 50°C to 230°C, 50°C to 225°C, 50°C to 220°C, 50°C to 215°C, 50°C to 210°C, 50°C to 205°C, 50°C to 200°C, 50°C to 175°C, 50°C to 150°C, 50°C to 125°C, 50°C to 100°C, 50°C to 75°C.
- the first solvent can comprise solvent having a boiling point that is greater than a boiling point of the crude product solution and/or the second solvent; and/or that is inert with respect to the precursor compound. Accordingly, the first solvent may depend on the precursor compound.
- a first solvent comprises an isoparaffinic hydrocarbon fluid.
- the first solvent comprises at least one of a diphenyl ether fluid, a dimethyl sulfoxide fluid, a triethyl phosphate fluid, an isoparaffinic hydrocarbon fluid, or any combination thereof. It will be appreciated that other solvents can be used herein without departing from the scope of this disclosure.
- the second solvent can comprise a solvent in which the precursor compound is soluble and/or that has a boiling point that is less than a boiling point of the first solvent and/or a solvent in which the at least one impurity is not soluble.
- the second solvent include, without limitation, at least one of hydrocarbons, alkanes, alkenes, alkynes, cycloalkanes, aromatic hydrocarbons, heterocyclic compounds, or any combination thereof. It will be appreciated that other solvents can be used herein without departing from the scope of this disclosure.
- the precursor compound comprises at least one of a tin- containing compound, a niobium containing compound, a tungsten-containing compound, or any combination thereof.
- the precursor compound comprises at least one of alkyl substituted tin compounds (e.g., a monoalkyl tin (II) compound, a monoalkyl tin (IV) compound, etc.), tin halides, tin oxides, tin hydroxides, alkyl substituted niobium compounds, niobium halides, niobium oxides, niobium hydroxides, tungsten halides, tungsten oxides, tungsten hydroxides, or any combination thereof.
- alkyl substituted tin compounds e.g., a monoalkyl tin (II) compound, a monoalkyl tin (IV) compound, etc.
- tin halides e.g., a monoalkyl tin
- the at least one tin-containing compound comprises at least one of tin(ll) chloride (SnCh), tin(IV) chloride (SnCk), trimethyltin (MeaSn), triethyltin (EtsSn), tributyltin (BusSn), or any combination thereof.
- the at least one niobium-containing compound comprises at least one of niobium(V) chloride (NbCIs), niobium(V) oxychloride (NbOCh), niobium ethoxide (Nb(OC2H5)5), niobium(V) pentafluoride (NbFs), or any combination thereof.
- the at least one tungsten-containing compound comprises at least one of tungsten hexachloride (WCk), tungsten hexafluoride (WFe), tungsten hexaethoxide (W(OC2Hs)6), tungsten oxychloride (WOCk), or any combination thereof.
- WCk tungsten hexachloride
- WFe tungsten hexafluoride
- W(OC2Hs)6 tungsten hexaethoxide
- WOCk tungsten oxychloride
- the at least one impurity comprises a solid impurity. In some embodiments, the at least one impurity comprises at least one of a salt compound, a dialkyl compound, or any combination thereof. In some embodiments, the at least one impurity comprises at least one of a dialkyl tin compound, a dialkyl niobium compound, a dialkyl tungsten compound, or any combination thereof. In some embodiments, the at least one impurity comprises at least one solid impurity. In some embodiments, the at least one solid impurity comprises at least one salt compound or at least one dialkyl compound.
- the at least one salt compound comprises at least one of a sodium chloride (NaCI), an ammonium chloride, or any combination thereof.
- the at least one dialkyl compound comprises at least one of dimethyl sulfide, diethyl sulfide, dimethyl ether, diethyl ether, or any combination thereof.
- the method 100 comprises feeding a mixture of the crude product solution and the first solvent to an evaporator.
- the feeding comprises flowing the mixture of the crude product solution and the first solvent to the evaporator. In some embodiments, the feeding comprises supplying the mixture of the crude product solution and the first solvent to the evaporator. In some embodiments, the feeding comprises introducing the mixture of the crude product solution and the first solvent to the evaporator. In some embodiments, the feeding comprises pumping the mixture of the crude product solution and the first solvent to the evaporator. In some embodiments, the feeding comprises introducing the mixture of the crude product solution and the first solvent in the evaporator. In some embodiments, the feeding comprises disposing the mixture of the crude product solution and the first solvent in the evaporator.
- the evaporator comprises at least one of a wiped film evaporator, a stirrer evaporator, a rising film evaporator, a circulation evaporator, a falling film evaporator, or any combination thereof.
- the wiped film evaporator comprises concentrating, distilling, stripping, dehydrating, deodorization or any combination thereof.
- the mixture comprises 1 % to 99% by volume of the first solvent based on the total volume of the mixture, or any range or subrange between 1 % and 99%.
- the mixture comprises 1 % to 90%, 1 % to 80%, 1 % to 70%, 1 % to 60%, 1 % to 50%, 1 % to 40%, 1 % to 30%, 1 % to 20%, 1 % to 10%, 1 % to 9%, 1 % to 8%, 1 % to 7%, 1 % to 6%, 1 % to 5%, 1 % to 4%, 1 % to 3%, 1 % to 2%, 10% to 99%, 20% to 99%, 30% to 99%, 40% to 99%, 50% to 99%, 60% to 99%, 70% to 99%, 80% to 99%, or 90% to 99% by volume of the first solvent based on the total volume of the mixture.
- the mixture comprises 1 % to 99% by volume of the crude product solution based on a total volume of the mixture, or any range or subrange between 1 % and 99%.
- the mixture comprises 1 % to 98%, 1 % to 97%, 1 % to 96%, 1 % to 95%, 1 % to 94%, 1 % to 93%, 1 % to 92%, 1 % to 91 %, 1 % to 90%, 1 % to 80%, 1 % to 70%, 1 % to 60%, 1 % to 50%, 1 % to 40%, 1 % to 30%, 1 % to 20%, 1 % to 10%, 10% to 99%, 20% to 99%, 30% to 99%, 40% to 99%, 50% to 99%, 60% to 99%, 70% to 99%, 80% to 99%, or 90% to 99% by volume of the crude product solution based on the total volume of the mixture.
- the mixture comprises 1 % to 99% by volume of the second solvent based on a total volume of the mixture, or any range or subrange between 1 % and 99%.
- the mixture comprises 1 % to 98%, 1 % to 97%, 1 % to 96%, 1 % to 95%, 1 % to 94%, 1 % to 93%, 1 % to 92%, 1 % to 91 %, 1 % to 90%, 1 % to 80%, 1% to 70%, 1 % to 60%, 1 % to 50%, 1 % to 40%, 1 % to 30%, 1 % to 20%, 1 % to 10%, 10% to 99%, 20% to 99%, 30% to 99%, 40% to 99%, 50% to 99%, 60% to 99%, 70% to 99%, 80% to 99%, or 90% to 99% by volume of the second solvent based on the total volume of the mixture.
- the method 100 comprises collecting, from the evaporator, a distillate comprising the precursor compound.
- the collecting comprises recovering the distillate comprising the precursor compound in a flask or other container. In some embodiments, the collecting comprises disposing the distillate comprising the precursor compound in a collector. In some embodiments, the collector is under heating and/or cooling. It will be appreciated that other techniques for collecting the distillate may be employed without departing from the scope of this disclosure. [0034] In some embodiments, prior to feeding a mixture of the crude product solution and the at least one first solvent to an evaporator, the precursor compound (e.g., in the crude product solution) has a purity of 95% or less as determined by 1 H NMR.
- the precursor compound has a purity of less than 90%, less than 85%, less than 80%, less than 75%, less than 70%, less than 65%, less than 60%, less than 55%, less than 50%, less than 45%, less than 40%, less than 35%, less than 30%, less than 25%, less than 20%, less than 15%, less than 10%, less than 5%, less than 4%, less than 3%, less than 2%, less than 1 %, less than 0.5%, less than 0.4%, less than 0.4% or less than 0.3%, less than 0.2%, less than 0.1% in the crude product solution.
- a purity of the precursor compound in the distillate is greater than 95% as determined by 1 H NMR. That is, in some embodiments, upon collecting a distillate comprising a precursor compound, a purity of the precursor compound in the distillate is greater than 95% as determined by 1 H NMR. In some embodiments, the precursor compound has a purity of least 95%, at least 96%, at least 97%, at least 98%, at least 99%, at least 99.9%, at least 99.999%, at least 99.9999% as determined by 1 H NMR. In some embodiments, a purity of precursor compound in the distillate is 95% to 99.9999%, as determined by 1 H NMR, or any range or subrange between 95% and 99.9999%.
- a purity of the precursor compound in the distillate is 95% to 96%, 95% to 97%, 95% to 98%, 95% to 99%, 95% to 99.9%, 95% to 99.99%, 95% to 99.999%, 95% to 99.9999%, 99.999% to 99.9999%, 99.99% to 99.9999%, 99.9% to 99.9999%, 99% to 99.9999%, 98% to 99.9999%, 97% to 99.9999%, 96% to 99.9999%, or 95% to 99.9999%, as determined by 1 H NMR.
- the system comprises a crude product solution, a first solvent, and an evaporator.
- the crude product solution comprises at least one of a precursor compound, at least one impurity, a second solvent, or any combination thereof.
- the first solvent has a boiling point that is greater than a boiling point of the crude product solution and/or second solvent.
- the evaporator comprises at least one of wiped film evaporator, a stirrer evaporator, a rising film evaporator, a circulation evaporator, a falling film evaporator, or any combination thereof.
- the evaporator when a mixture of the crude product solution and the first solvent is fed to the evaporator, the evaporator is configured to produce a distillate comprising the precursor compound. In some embodiments, a purity of the precursor compound in the distillate is greater than 95% as determined by 1 H NMR. It will be appreciated that any of the crude product solutions, first solvents, evaporators, precursor compounds, at least one impurities, second solvents, etc. may be employed herein without departing from the scope of this disclosure.
- a crude product solution containing a tin-containing precursor compound was purified using a wiped film distillation system and process.
- the conditions included heating at 55 °C to 65 °C at 2.5 Torr at a distillation rate of 0.4 kg per hour.
- a 13% by volume of an isoparaffinic hydrocarbon fluid (Isopar V) was added to the crude product based on a total volume of the resulting mixture.
- the resulting 1 H NMR is presented in FIG. 2.
- the wiped film distillation system and process produced a distillate comprising the tin-containing precursor compound at a purity of greater than 97% (WFE Fraction 1 ) and a purity of greater than 99% (WFE Fraction 2).
- Each WFE fraction had less dialkyl impurity than a comparative reboiler distillation.
- a rate of distillation was greater than the comparative reboiler distillation.
- a method comprising: mixing a crude product solution with a first solvent, wherein the crude product solution comprises a precursor compound and at least one impurity; wherein a boiling point of the first solvent is greater than a boiling point of the crude product solution; feeding a mixture of at least the crude product solution and the first solvent to an evaporator; and collecting, from the evaporator, a distillate comprising the precursor compound, wherein a purity of the precursor compound in the distillate is greater than 95% as determined by 1 H NMR.
- Aspect 2 The method according to Aspect 1 , wherein the crude product solution further comprises a second solvent, wherein the precursor compound is dissolved in the second solvent.
- Aspect 3 The method according to Aspect 2, wherein the at least one impurity is not dissolved in the second solvent.
- Aspect 4 The method according to any one of Aspects 1 -3, wherein a purity of the precursor compound in the crude product solution is 95% or less as determined by 1 H NMR.
- Aspect 5 The method according to any one of Aspects 1 -4, wherein a purity of the precursor compound in the crude product solution is 90% to 95% as determined by 1 H NMR.
- Aspect s The method according to any one of Aspects 1 -5, wherein the precursor compound comprises a tin-containing compound.
- Aspect 7 The method according to any one of Aspects 1 -6, wherein the precursor compound comprises a niobium-containing compound.
- Aspect s The method according to any one of Aspects 1 -7, wherein the precursor compound comprises a tungsten-containing compound.
- Aspect 9 The method according to any one of Aspects 1 -8, wherein the first solvent is inert with respect to the precursor compound.
- Aspect 10 The method according to any one of Aspects 1 -9, wherein the boiling point of the first solvent is at least 10% greater than a boiling point of the crude product solution.
- Aspect 11 The method according to any one of Aspects 1 -10, wherein the boiling point of the first solvent is 250 °C to 500 °C.
- Aspect 12 The method according to any one of Aspects 1 -11 , wherein the boiling point of the crude product solution is 50 °C to 200 °C.
- Aspect 13 The method according to any one of Aspects 1 -12, wherein the first solvent comprises an isoparaffinic hydrocarbon fluid.
- Aspect 14 The method according to any one of Aspects 1 -13, wherein the at least one impurity comprises at least one solid impurity.
- Aspect 15 The method according to any one of Aspects 1 -14, wherein the at least one impurity comprises at least one of a salt compound, a dialkyl compound, or any combination thereof.
- Aspect 16 The method according to any one of Aspects 1 -15, wherein the purity of the precursor compound in the distillate is at least 99%.
- Aspect 17 The method according to any one of Aspects 1 -16, wherein the evaporator comprises at least one of a wiped film evaporator, a stirrer evaporator, a rising film evaporator, a circulation evaporator, a falling film evaporator, or any combination thereof.
- Aspect 18 The method according to any one of Aspects 1 -17, further comprising collecting a residue comprising the at least one impurity.
- a system comprising: a crude product solution comprising a precursor compound and at least one impurity; a first solvent having a boiling point that is greater than a boiling point of the crude product solution; and an evaporator, wherein, when a mixture of the crude product solution and the first solvent is fed to the evaporator, the evaporator is configured to produce a distillate comprising the precursor compound, wherein a purity of the precursor compound in the distillate is greater than 95% as determined by 1 H NMR.
- Aspect 20 The system according to Aspect 19, wherein the evaporator comprises at least one of wiped film evaporator, a stirrer evaporator, a rising film evaporator, a circulation evaporator, a falling film evaporator, or any combination thereof.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202480073828.1A CN122249269A (en) | 2023-11-06 | 2024-11-05 | Purification of precursor compounds and related systems and methods |
| KR1020267017338A KR20260105894A (en) | 2023-11-06 | 2024-11-05 | Purification of precursor compounds and related systems and methods |
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| US202363547452P | 2023-11-06 | 2023-11-06 | |
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| US (1) | US20250144545A1 (en) |
| KR (1) | KR20260105894A (en) |
| CN (1) | CN122249269A (en) |
| TW (1) | TWI924206B (en) |
| WO (1) | WO2025101503A1 (en) |
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- 2024-11-05 WO PCT/US2024/054546 patent/WO2025101503A1/en active Pending
- 2024-11-05 CN CN202480073828.1A patent/CN122249269A/en active Pending
- 2024-11-05 US US18/937,784 patent/US20250144545A1/en active Pending
- 2024-11-06 TW TW113142500A patent/TWI924206B/en active
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| US4876380A (en) * | 1988-08-31 | 1989-10-24 | The Dow Chemical Company | Color reduction of polymeric isocyanates via multiple solvent fractionation |
| WO1999011639A1 (en) * | 1997-09-02 | 1999-03-11 | Arco Chemical Technology, L.P. | Separation of methanol and propylene oxide from a reaction mixture |
| US20020065425A1 (en) * | 2000-11-29 | 2002-05-30 | Ikuyo Ikeno | Method for purifying fluoroaryl metal compound |
| US8961794B2 (en) * | 2010-07-29 | 2015-02-24 | Phillips 66 Company | Metal impurity and high molecular weight components removal of biomass derived biocrude |
| CN102660030A (en) * | 2012-05-14 | 2012-09-12 | 浙江理工大学 | Preparation method of Si-C-N ceramic precursor |
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| TWI924206B (en) | 2026-05-01 |
| CN122249269A (en) | 2026-06-19 |
| KR20260105894A (en) | 2026-07-07 |
| TW202528026A (en) | 2025-07-16 |
| US20250144545A1 (en) | 2025-05-08 |
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