# US 10,864,459 B2 · Methods to produce cannabinoid products from decarboxylated cannabinoid extracts > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 10,864,459 B2 - Document ID: US10864459B2 - Status: Granted - Kind: B2 - Application number: 16/683,055 - Filed: 2019-11-13 - Published: 2020-06-11 - Granted: 2020-12-15 - Earliest claimed: 2018-12-10 - Assignees: Natural Extraction Systems, LLC - Applicants: Natural Extraction Systems, LLC - Inventors: Robert C. Wagner; C. Russell Thomas; Douglas G. Metcalf - Web page: https://patentgrep.com/patent/US10864459B2 ## CPC - B01D 11/0492: {Applications, solvents used} - A61K 31/015: carbocyclic - A61K 31/658: {o-phenolic cannabinoids, e.g. cannabidiol, cannabigerolic acid, cannabichromene or tetrahydrocannabinol} - A61K 36/3482: {Cannabis} - B01D 11/0488: {Flow sheets} - C07C 29/84: by extractive distillation - C07C 37/72: by liquid-liquid treatment - C07D 311/80: Dibenzopyrans; Hydrogenated dibenzopyrans - A61K 2236/331: using water, e.g. cold water, infusion, tea, steam distillation or decoction - A61K 2236/39: Complex extraction schemes, e.g. fractionation or repeated extraction steps - A61K 2236/51: Concentration or drying of the extract, e.g. Lyophilisation, freeze-drying or spray-drying - A61K 2236/53: Liquid-solid separation, e.g. centrifugation, sedimentation or crystallization - A61K 2236/55: Liquid-liquid separation; Phase separation - B01D 9/0004: {cooling by heat exchange (by evaporation of components of the mixture to be separated B01D9/0013; refrigeration machines F25B)} - C07C 2601/16: the ring being unsaturated - B01D: SEPARATION (separating solids from solids by wet methods B03B, B03D; by pneumatic jigs or tables B03B; by other dry methods B07; magnetic or electrostatic separation of solid materials from solid materials or fluids, separation by high-voltage electric fields B03C; centrifuges, vortex apparatus B04; presses per se for squeezing-out liquid from liquid-containing material B30B9/02; treatment of water C02F, e.g. softening by ion-exchange C02F1/42; {arrangements of air intake cleaners in gas turbine plants F02C7/05} ; arrangements or mounting of filters in air-conditioning, air-humidification or ventilation F24F13/28) - A61K: PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES (devices or methods specially adapted for bringing pharmaceutical products into particular physical or administering forms A61J3/00; chemical aspects of, or use of materials for deodorisation of air, for disinfection or sterilisation, or for bandages, dressings, absorbent pads or surgical articles A61L; soap compositions C11D) - C07C: ACYCLIC OR CARBOCYCLIC COMPOUNDS - C07D: HETEROCYCLIC COMPOUNDS (macromolecular compounds C08) ## Abstract Various aspects of this patent application relate to methods to separate a cannabinoid molecule from other molecules of a decarboxylated cannabinoid extract. ## Claims ### Claim 1 A method to produce a cannabinoid glass from a decarboxylated cannabinoid extract, comprising: combining (a) a starting composition comprising a decarboxylated cannabinoid extract and (b) a solubility-regulating composition to produce a heterogeneous composition, in which: the starting composition comprises ethanol, a cannabinoid molecule, and a second molecule; the cannabinoid molecule is cannabidiol, cannabidivarin, cannabigerol, or cannabigerovarin; the second molecule is tetrahydrocannabinol, tetrahydrocannabivarin, or beta caryophyllene; the ethanol is a solvent of the starting composition; the cannabinoid molecule is a solute that is dissolved in the ethanol of the starting composition; the second molecule is a solute that is dissolved in the ethanol of the starting composition; the solubility-regulating composition comprises water; the heterogeneous composition comprises an aqueous phase and a lipid phase; the aqueous phase of the heterogeneous composition comprises at least 95 percent of the water of the heterogeneous composition; the aqueous phase of the heterogeneous composition comprises at least 95 percent of the ethanol of the heterogeneous composition; the second molecule has a solubility in the aqueous phase that is less than 10 grams per liter; the lipid phase comprises greater than 65 percent of the second molecule of the heterogeneous composition; the cannabinoid molecule has a solubility in the aqueous phase that is greater than 10 grams per liter; and the aqueous phase comprises greater than 65 percent of the cannabinoid molecule of the heterogeneous composition; (ii) separating the aqueous phase and the lipid phase to separate the cannabinoid molecule and the second molecule; and (iii) separating the cannabinoid molecule from both (a) at least 95 percent of the water of the aqueous phase and (b) at least 95 percent of the ethanol of the aqueous phase to produce a product, in which: the product consists essentially of the molecules of the aqueous phase that are separated from (a) the at least 95 percent of the water of the aqueous phase and (b) the at least 95 percent of the ethanol of the aqueous phase; the product lacks the second molecule at a concentration greater than 0.3 percent by mass; the cannabinoid molecule has a freezing point; the product comprises a glass; the glass comprises greater than 50 percent of the cannabinoid molecule of the product; the glass comprises the cannabinoid molecule at a concentration greater than 50 percent by mass; the glass has a glass-transition temperature that is less than the freezing point of cannabinoid molecule; the glass lacks a freezing point; and the glass lacks a melting point. ### Claim 2 (depends on 1) The method of claim 1, in which: the decarboxylated cannabinoid extract is a decarboxylated full spectrum industrial hemp extract, a decarboxylated broad spectrum industrial hemp extract, or a decarboxylated industrial hemp distillate. ### Claim 3 (depends on 1) The method of claim 1, in which: the decarboxylated cannabinoid extract comprises a plurality of cannabinoid molecules; the plurality of cannabinoid molecules comprises two or more of cannabidiol, cannabidivarin, cannabigerol, and cannabigerovarin; each cannabinoid molecule of the plurality of cannabinoid molecules is a solute that is dissolved in the ethanol of the starting composition; each cannabinoid molecule of the plurality of cannabinoid molecules has a solubility in the aqueous phase that is greater than 10 grams per liter; the aqueous phase comprises greater than 65 percent of each cannabinoid molecule of the plurality of cannabinoid molecules of the heterogeneous composition by mass; and the product comprises each cannabinoid molecule of the plurality of cannabinoid molecules. ### Claim 4 (depends on 1) The method of claim 1, in which the cannabinoid molecule is cannabigerol, and the second molecule is beta-caryophyllene. ### Claim 5 (depends on 1) The method of claim 1, in which separating the aqueous phase and the lipid phase to separate the cannabinoid molecule and the second molecule comprises gravity-assisted sedimentation of the heterogeneous composition. ### Claim 6 (depends on 1) The method of claim 1, in which: separating the cannabinoid molecule from both (a) the at least 95 percent of the water of the aqueous phase and (b) the at least 95 percent of the ethanol of the aqueous phase comprises combining the aqueous phase and a second solubility-regulating composition to (i) drive a portion of the cannabinoid molecule of the aqueous phase out of the aqueous phase and (ii) produce a second heterogeneous composition; the second heterogeneous composition comprises a residual aqueous phase and a second lipid phase; the residual aqueous phase is a liquid; the residual aqueous phase comprises greater than 95 percent of the ethanol of the second heterogeneous composition; the residual aqueous phase comprises greater than 95 percent of the water of the second heterogeneous composition; the cannabinoid molecule of the second heterogeneous composition has a solubility in the residual aqueous phase that is less than 10 grams per liter; the second lipid phase comprises greater than 80 percent of the cannabinoid molecule of the second heterogeneous composition; the separation of the cannabinoid molecule from both (a) the at least 95 percent of the water of the aqueous phase and (b) the at least 95 percent of the ethanol of the aqueous phase further comprises mechanically separating the residual aqueous phase of the second heterogeneous composition from the second lipid phase of the second heterogeneous composition; and the product consists essentially of the portion of the second lipid phase that is mechanically separated from the residual aqueous phase. ### Claim 7 A method to produce cannabinoid crystals from a decarboxylated cannabinoid extract, comprising: (i) combining (a) a starting composition comprising a decarboxylated cannabinoid extract and (b) a solubility-regulating composition to produce a heterogeneous composition, in which: the starting composition comprises ethanol, a cannabinoid molecule, and a second molecule; the cannabinoid molecule is cannabidiol, cannabidivarin, cannabigerol, or cannabigerovarin; the second molecule is tetrahydrocannabinol, tetrahydrocannabivarin, or beta caryophyllene; the ethanol is a solvent of the starting composition; the cannabinoid molecule is a solute that is dissolved in the ethanol of the starting composition; the second molecule is a solute that is dissolved in the ethanol of the starting composition; the solubility-regulating composition comprises water; the heterogeneous composition comprises an aqueous phase and a lipid phase; the aqueous phase of the heterogeneous composition comprises at least 95 percent of the water of the heterogeneous composition; the aqueous phase of the heterogeneous composition comprises at least 95 percent of the ethanol of the heterogeneous composition; the second molecule has a solubility in the aqueous phase that is less than 10 grams per liter; the lipid phase comprises greater than 65 percent of the second molecule of the heterogeneous composition; the cannabinoid molecule has a solubility in the aqueous phase that is greater than 10 grams per liter; and the aqueous phase comprises greater than 65 percent of the cannabinoid molecule of the heterogeneous composition; (ii) separating the aqueous phase and the lipid phase to separate the cannabinoid molecule and the second molecule; and (iii) separating the cannabinoid molecule from both (a) at least 95 percent of the water of the aqueous phase and (b) at least 95 percent of the ethanol of the aqueous phase to produce a product, in which: the product consists essentially of the molecules of the aqueous phase that are separated from (a) the at least 95 percent of the water of the aqueous phase and (b) the at least 95 percent of the ethanol of the aqueous phase; the product lacks the second molecule at a concentration greater than 0.3 percent by mass; the product comprises crystals; the crystals comprise greater than 50 percent of the cannabinoid molecule of the product; the crystals comprise the cannabinoid molecule at a concentration greater than 50 percent by mass; the crystals have a melting point; and the crystals lack a glass-transition temperature. ### Claim 8 (depends on 7) The method of claim 7, further comprising dissolving the decarboxylated cannabinoid extract in the ethanol to produce the starting composition. ### Claim 9 (depends on 7) The method of claim 7, in which: the decarboxylated cannabinoid extract comprises a plurality of second molecules; the plurality of second molecules comprises two or more of tetrahydrocannabinol, tetrahydrocannabivarin, cannabichromene, cannabichromevarin, and cannabinol; each second molecule of the plurality of second molecules is a solute that is dissolved in the ethanol of the starting composition; each second molecule of the plurality of second molecules has a solubility in the aqueous phase that is less than 10 grams per liter; the lipid phase comprises greater than 65 percent of each second molecule of the plurality of second molecules of the heterogeneous composition by mass; and the product lacks each second molecule of the plurality of second molecules at a concentration greater than 0.3 percent by mass. ### Claim 10 (depends on 7) The method of claim 7, in which the cannabinoid molecule is cannabidiol, and the second molecule is tetrahydrocannabinol. ### Claim 11 (depends on 7) The method of claim 7, in which separating the aqueous phase and the lipid phase to separate the cannabinoid molecule and the second molecule comprises centrifuging the heterogeneous composition. ### Claim 12 (depends on 7) The method of claim 7, in which: separating the cannabinoid molecule from both (a) the at least 95 percent of the water of the aqueous phase and (b) the at least 95 percent of the ethanol of the aqueous phase comprises (i) vaporizing the at least 95 percent of the water to produce water vapor, (ii) vaporizing the at least 95 percent of the ethanol to produce ethanol vapor, and (iii) removing both the water vapor and the ethanol vapor from the aqueous phase using a vacuum; the vaporizing and removing are performed under conditions that do not vaporize and remove the cannabinoid molecule of the aqueous phase from the aqueous phase; and the product consists of the portion of the aqueous phase that is not both vaporized and removed from the aqueous phase. ### Claim 13 (depends on 7) The method of claim 7, in which separating the cannabinoid molecule from both (a) the at least 95 percent of the water of the aqueous phase and (b) the at least 95 percent of the ethanol of the aqueous phase comprises removing (a) the at least 95 percent of the water of the aqueous phase and (b) the at least 95 percent of the ethanol of the aqueous phase under vacuum either in a rotary evaporator, in a vacuum oven, or by lyophilization. ### Claim 14 A method to produce a supercooled cannabinoid oil from a decarboxylated cannabinoid extract, comprising: (i) combining (a) a starting composition comprising a decarboxylated cannabinoid extract and (b) a solubility-regulating composition to produce a heterogeneous composition, in which: the starting composition comprises ethanol, a cannabinoid molecule, and a second molecule; the cannabinoid molecule is cannabidiol, cannabidivarin, cannabigerol, or cannabigerovarin; the second molecule is tetrahydrocannabinol, tetrahydrocannabivarin, or beta caryophyllene; the ethanol is a solvent of the starting composition; the cannabinoid molecule is a solute that is dissolved in the ethanol of the starting composition; the second molecule is a solute that is dissolved in the ethanol of the starting composition; the solubility-regulating composition comprises water; the heterogeneous composition comprises an aqueous phase and a lipid phase; the aqueous phase of the heterogeneous composition comprises at least 95 percent of the water of the heterogeneous composition; the aqueous phase of the heterogeneous composition comprises at least 95 percent of the ethanol of the heterogeneous composition; the second molecule has a solubility in the aqueous phase that is less than 10 grams per liter; the lipid phase comprises greater than 65 percent of the second molecule of the heterogeneous composition; the cannabinoid molecule has a solubility in the aqueous phase that is greater than 10 grams per liter; and the aqueous phase comprises greater than 65 percent of the cannabinoid molecule of the heterogeneous composition; (ii) separating the aqueous phase and the lipid phase to separate the cannabinoid molecule and the second molecule; and (iii) separating the cannabinoid molecule from both (a) at least 95 percent of the water of the aqueous phase and (b) at least 95 percent of the ethanol of the aqueous phase to produce a product, in which: the product consists essentially of the molecules of the aqueous phase that are separated from (a) the at least 95 percent of the water of the aqueous phase and (b) the at least 95 percent of the ethanol of the aqueous phase; the product lacks the second molecule at a concentration greater than 0.3 percent by mass; the product comprises an oil; the oil comprises greater than 50 percent of the cannabinoid molecule of the product; the oil comprises the cannabinoid molecule at a concentration greater than 50 percent by mass; the oil is a supercooled liquid; the oil has a freezing point; and the oil lacks a glass-transition temperature. ### Claim 15 (depends on 14) The method of claim 14, further comprising heating a cannabinoid extract to decarboxylate the cannabinoid extract and produce the decarboxylated cannabinoid extract. ### Claim 16 (depends on 14) The method of claim 14, in which: the decarboxylated cannabinoid extract comprises a plurality of second molecules; the plurality of second molecules comprises two or more of beta-caryophyllene, bisabolol, eucalyptol, guaiol, humulene, limonene, myrcene, nerolidol, ocimene, pinene, terpinolene, and linalool; each second molecule of the plurality of second molecules is a solute that is dissolved in the ethanol of the starting composition; each second molecule of the plurality of second molecules has a solubility in the aqueous phase that is less than 10 grams per liter; the lipid phase comprises greater than 65 percent of each second molecule of the plurality of second molecules of the heterogeneous composition by mass; and the product lacks each second molecule of the plurality of second molecules at a concentration greater than 0.3 percent by mass. ### Claim 17 (depends on 14) The method of claim 14, in which the cannabinoid molecule is cannabidivarin, and the second molecule is tetrahydrocannabivarin. ### Claim 18 (depends on 14) The method of claim 14, in which separating the aqueous phase and the lipid phase to separate the cannabinoid molecule and the second molecule comprises filtering the heterogeneous composition. ### Claim 19 (depends on 14) The method of claim 14, in which separating the cannabinoid molecule from both (a) the at least 95 percent of the water of the aqueous phase and (b) the at least 95 percent of the ethanol of the aqueous phase comprises spray drying the aqueous phase. ### Claim 20 A method to separate cannabidiol and tetrahydrocannabinol, comprising: (i) providing a starting composition comprising ethanol, cannabidiol, and tetrahydrocannabinol, in which: the starting composition comprises an alcohol phase; the alcohol phase is a liquid; the alcohol phase comprises (a) at least 90 percent of the ethanol of the starting composition, (b) at least 50 percent of the cannabidiol of the starting composition, and (c) at least some of the tetrahydrocannabinol of the starting composition; the ethanol of the alcohol phase is a solvent; the cannabidiol of the alcohol phase is a solute that is dissolved in the ethanol of the alcohol phase; the tetrahydrocannabinol of the alcohol phase is a solute that is dissolved in the ethanol of the alcohol phase; the ethanol of the alcohol phase is present in the alcohol phase at a concentration of at least 35 percent and no greater than 99 percent by mass; the starting composition comprises the cannabidiol at a concentration of at least 0.65 percent and no greater than 65 percent by mass; the starting composition comprises the tetrahydrocannabinol at a concentration of at least 0.065 percent by mass; the starting composition comprises the cannabidiol and the tetrahydrocannabinol at a cannabidiol-to-tetrahydrocannabinol ratio of less than 350:1 by mass; the cannabidiol of the starting composition has a solubility in the alcohol phase that is greater than 10 grams per liter; and the tetrahydrocannabinol of the starting composition has a solubility in the alcohol phase that is greater than 10 grams per liter; (ii) decreasing the solubility of the tetrahydrocannabinol in the alcohol phase of the starting composition by combining the alcohol phase and a solubility-regulating composition to (a) drive a portion of the tetrahydrocannabinol of the alcohol phase out of the alcohol phase and (b) produce a heterogeneous composition, in which: the solubility-regulating composition comprises water; the solubility-regulating composition comprises the water at a concentration by mass that is greater than the concentration by mass of any water that is present in the alcohol phase of the starting composition such that the combination of the alcohol phase and the solubility-regulating composition has a greater concentration of water than the alcohol phase of the starting composition; the heterogeneous composition comprises each of (a) the ethanol of the starting composition, (b) the cannabidiol of the starting composition, (c) the tetrahydrocannabinol of the starting composition, and (d) the water of the solubility-regulating composition; the heterogeneous composition comprises an aqueous phase and a tetrahydrocannabinol-enriched lipid phase; the aqueous phase is a liquid; the aqueous phase comprises greater than 50 percent of the cannabidiol of the heterogeneous composition; the aqueous phase comprises greater than 50 percent of the ethanol of the heterogeneous composition; the aqueous phase comprises at least 95 percent of the water of the heterogeneous composition; either (a) the ethanol of the aqueous phase is a solvent, and the water of the aqueous phase is a solute that is dissolved in the ethanol of the aqueous phase, or (b) the water of the aqueous phase is a solvent, and the ethanol of the aqueous phase is a cosolvent; the cannabidiol of the heterogeneous composition has a solubility in the aqueous phase that is greater than 10 grams per liter; the cannabidiol of the aqueous phase is a solute that is dissolved in the solvent of the aqueous phase; the tetrahydrocannabinol of the heterogeneous composition has a solubility in the aqueous phase that is less than 10 grams per liter; the aqueous phase comprises the cannabidiol of the aqueous phase and any tetrahydrocannabinol that is dissolved in the solvent of the aqueous phase at a cannabidiol-to-tetrahydrocannabinol ratio that is greater than 350:1 by mass; and the tetrahydrocannabinol-enriched lipid phase comprises greater than 50 percent of the tetrahydrocannabinol of the heterogeneous composition; (iii) selecting either a fraction or all of the heterogeneous composition for further processing to produce a fractionated heterogeneous composition, in which: the fractionated heterogeneous composition comprises a fractionated aqueous phase and a fractionated tetrahydrocannabinol-enriched lipid phase; the fractionated aqueous phase consists of either a fraction or all of the aqueous phase of the heterogeneous composition; the fractionated aqueous phase comprises either a fraction or all of the cannabidiol of the aqueous phase; the fractionated aqueous phase comprises either a fraction or all of the ethanol of the aqueous phase; the fractionated aqueous phase comprises either a fraction or all of the water of the aqueous phase; the fractionated tetrahydrocannabinol-enriched lipid phase consists of either a fraction or all of the tetrahydrocannabinol-enriched lipid phase of the heterogeneous composition; and the fractionated tetrahydrocannabinol-enriched lipid phase comprises either a fraction or all of the tetrahydrocannabinol of the tetrahydrocannabinol-enriched lipid phase of the heterogeneous composition; (iv) mechanically separating the fractionated aqueous phase of the fractionated heterogeneous composition from the fractionated tetrahydrocannabinol-enriched lipid phase of the fractionated heterogeneous composition to mechanically separate the cannabidiol of the fractionated aqueous phase from the tetrahydrocannabinol of the fractionated tetrahydrocannabinol-enriched lipid phase; (v) selecting either a fraction or all of the fractionated aqueous phase for further processing to produce a second fractionated aqueous phase, in which: the second fractionated aqueous phase comprises either a fraction or all of the cannabidiol of the fractionated aqueous phase; the second fractionated aqueous phase comprises either a fraction or all of the ethanol of the fractionated aqueous phase; and the second fractionated aqueous phase comprises either a fraction or all of the water of the fractionated aqueous phase; (vi) separating (a) a majority of the ethanol of the second fractionated aqueous phase and a majority of the water of the second fractionated aqueous phase from (b) a majority of the cannabidiol of the second fractionated aqueous phase to produce a product, in which: the product comprises cannabidiol; the product lacks tetrahydrocannabinol at a concentration greater than 0.3 percent by mass; the product comprises cannabidiol and any tetrahydrocannabinol at a cannabidiol-to tetrahydrocannabinol ratio that is greater that 350:1 by mass; the product lacks ethanol at a concentration greater than 5 percent by mass; and the product lacks water at a concentration greater than 5 percent by mass.