Water-resistant and durable biochar pellets, and methods for manufacturing and using the same.

Abstract

A biochar pellet that is water-resistant, highly durable, and high-density is described. In several variations, a method for producing biochar pellets includes: pyrolysis of a biomass-containing raw material in a pyrolysis reactor to produce a solid biochar-containing material and pyrolysis vapor; introducing the pyrolysis vapor into a separation system configured to recover the pyrolysis condensate in liquid form separated from the non-condensable gas; capturing the pyrolysis condensate as a polyphenol material; contacting the solid biochar-containing material with the polyphenol material to produce an intermediate mixture; introducing the intermediate mixture into a densification unit to produce a biochar pellet precursor; and at least partially drying the biochar pellet precursor to produce biochar pellets characterized by a 24-hour water absorption rate of about 20% by weight or less, as measured at 25°C and 1 bar. The biochar pellets can be piled up outdoors, which is logistically convenient at manufacturing sites such as industrial steel mills that supply biochar pellets to the process.

Description

[Technical Field]

[0001] (Cross-reference of related applications) This application claims the benefit of priority of U.S. Provisional Patent Application 63 / 541,997, filed on 2 October 2023, which is incorporated herein by reference in its entirety.

[0002] (Technical field) The present invention relates, in general, to biochar pellets optimized for various chemical and physical properties (e.g., water resistance), as well as to methods for manufacturing and using such biochar pellets. [Background technology]

[0003] (background) Carbon is a platform element in a wide variety of industries, with a vast number of chemical, material, and fuel applications. It is an excellent fuel for generating energy, including electricity. Carbon has chemical value for a wide range of commodities and advanced materials, including metals, alloys, composites, carbon fibers, electrodes, and catalyst supports. In steelmaking, carbon is useful as a reactant to reduce metal oxides to metals during processing; as a fuel to provide heat for processing; and as a component of alloys. Historically, carbon in the form of coal has been widely used for industrial purposes. Coal remains the world's largest energy source for power generation and steelmaking. However, coal is considered the single largest contributor to the climate crisis. [Overview of the Initiative]

[0004] (overview) This invention addresses the aforementioned needs in the art.

[0005] In some modifications, the present invention provides a method for producing biochar pellets. In one modification, the method for producing biochar pellets is: (a) to thermally decompose a biomass-containing raw material in a thermal decomposition reactor, thereby generating thermal decomposition steam containing solid biochar-containing material and polyphenol material; (b) Introducing pyrolysis vapor into a thermally controlled multistage separation system configured to separate pyrolysis condensates in liquid form from a non-condensable gas (where the pyrolysis condensates contain polyphenol material); (c) Contacting a solid biochar-containing material with a polyphenol material to produce an intermediate mixture; (d) Introducing the intermediate mixture into a densification unit to generate a biochar pellet precursor; and (e) to at least partially dry the biochar pellet precursor, thereby producing biochar pellets. : includes, Here, the biochar pellets are characterized by a 24-hour water absorption rate of approximately 20% by weight or less, as measured at 25°C and 1 bar.

[0006] In some embodiments, the biomass-containing raw material is selected from coniferous wood chips, hardwood chips, wood harvest residues, tree branches, tree stumps, leaves, bark, sawdust, corn, corn stover, wheat, wheat straw, rice, rice straw, sugarcane, sugarcane bagasse, sugarcane straw, energy cane, sugar beet, sugar beet pulp, sunflower, sorghum, canola, algae, Japanese pampas grass, alfalfa, switchgrass, fruits, fruit shells, fruit stems, fruit peels, fruit seeds, vegetables, vegetable shells, vegetable stems, vegetable peels, vegetable seeds, grape pomace, almond shells, pecan shells, coconut shells, coffee grounds, food waste, commercial waste, grass pellets, hay pellets, wood pellets, cardboard, paper, paper pulp, paper packaging, paper scraps, food packaging, construction or demolition waste, railway sleepers, lignin, animal manure, municipal solid waste, municipal sewage, or a combination thereof.

[0007] In some embodiments, the solid biochar-containing material contains about 65% to about 95% by weight of fixed carbon. In some embodiments, the solid biochar-containing material contains about 70% to about 90% by weight of fixed carbon.

[0008] In some embodiments, a thermally controlled multistage separation system comprises one or more filters, an absorption bed having a solid medium, an absorption bed having a liquid medium, an adsorption bed having a solid medium, a dry scrubber, a wet scrubber, a venturi scrubber, a centrifuge, a cyclone, a quench unit, a reactive condenser, a distillation column, a reactive distillation column, an evaporator, a reactive evaporator, a heat exchanger, a fan separator, an electrostatic precipitator, a demister, or a combination thereof, configured to produce pyrolysis condensate and a gas stream from pyrolysis vapor.

[0009] In some embodiments, a thermally controlled multistage separation system comprises a cyclone unit configured to separate solid biochar-containing material from pyrolysis steam.

[0010] In some embodiments, the quench unit is configured to expose pyrolysis vapor to water, thereby generating pyrolysis condensates.

[0011] In some embodiments, the thermally controlled multistage separation system further comprises a demister unit configured to recover residual liquid from the gas stream. In some embodiments, the residual liquid is combined with the pyrolysis condensate. The thermally controlled multistage separation system may be configured to capture multiple liquid fractions. The thermally controlled multistage separation system may be configured to capture multiple liquid fractions according to molecular weight, boiling point, polarity, or a combination thereof.

[0012] In some embodiments, the polyphenol material contains about 20% to about 80% by weight of fixed carbon. In some embodiments, the polyphenol material contains about 40% to about 60% by weight of fixed carbon.

[0013] The polyphenol material may be characterized by a weight-average molecular weight of approximately 75 g / mol to approximately 50,000 g / mol. In one embodiment, the polyphenol material has a weight-average molecular weight of approximately 75 g / mol to approximately 1,000 g / mol. In another embodiment, the polyphenol material has a weight-average molecular weight of approximately 1,000 g / mol to approximately 50,000 g / mol.

[0014] The polyphenol material may be characterized by a viscosity of about 1 cP to about 1000 cP at 25°C. In one embodiment, the polyphenol material has a viscosity of about 10 cP to about 500 cP at 25°C.

[0015] The polyphenol material may contain about 1% to about 60% by weight of water. In one embodiment, the polyphenol material contains about 5% to about 40% by weight of water.

[0016] In some embodiments, the intermediate mixture has a weight ratio of polyphenol material to solid biochar-containing material selected from about 0.01 to about 5. In some embodiments, the intermediate mixture has a weight ratio of polyphenol material to solid biochar-containing material selected from about 0.05 to about 2, for example, about 0.1 to about 1, or about 0.2 to about 0.8.

[0017] In some embodiments, the polyphenol material is heated before contact with the solid biochar-containing material. For example, the polyphenol material may be heated to a temperature of at least about 150°C, at least about 200°C, or at least about 250°C.

[0018] In some embodiments, the solid biochar-containing material is heated before contact with the polyphenol material. For example, the solid biochar-containing material may be at a temperature within ±100°C or ±50°C of the pyrolysis reactor temperature before contact with the polyphenol material. Typically, the solid biochar-containing material is slightly cooled after the pyrolysis reactor, so its temperature when in contact with the polyphenol material is usually somewhat lower than the pyrolysis temperature; however, heating can be used to raise the temperature of the solid biochar-containing material even higher than the pyrolysis temperature.

[0019] In some embodiments, the intermediate mixture is heated before step (d).

[0020] In some embodiments, the densification unit is selected from an extruder, a bricketer, a pellet mill, or a combination thereof. The densification unit can essentially consist of, for example, an extruder, a bricketer, a pellet mill, or a combination thereof. In some embodiments, the densification unit is an extruder. The densification unit can be operated at a densification temperature higher than 100°C, for example, at least 150°C or at least 200°C.

[0021] In some embodiments, in step (d), the densification unit is configured to generate a concentrated concentration of polyphenol material on the outer shell of the biochar pellet precursor.

[0022] In some embodiments, steps (d) and (e) are combined, and the densification unit is also configured for drying the biochar pellet precursor.

[0023] In some embodiments, the biochar pellets have a water content of 0% to about 10% by weight. For example, the biochar pellets may have a water content of 0% to about 5% by weight, or the biochar pellets may have a water content of 0% to about 2% by weight. In some embodiments, the biochar pellets have a water content of 0% to about 20% by weight. In one embodiment, the biochar pellets have a water content of 0% to about 10% by weight, or 0% to about 5% by weight, or 0% to about 2% by weight, or 0% to about 1% by weight.

[0024] In some embodiments, the biochar pellets have a fixed carbon content of about 50% to about 99% by weight of fixed carbon on a dry basis. In some embodiments, the biochar pellets have a fixed carbon content of about 60% to about 90% or about 70% to about 80% by weight of fixed carbon on a dry basis.

[0025] In some embodiments, the 24-hour water absorption rate of the biochar pellets is approximately 10% by weight or less, measured at 25°C and 1 bar. In one embodiment, the 24-hour water absorption rate of the biochar pellets is approximately 6% by weight or less, measured at 25°C and 1 bar.

[0026] In some embodiments, the biochar pellets are at least about 100 lb at 25°C. f / in 2 It is characterized by a pellet compressive strength of at least about 200 lb at 25°C. In one embodiment, the biochar pellets are characterized by a pellet compressive strength of at least about 200 lb at 25°C. f / in 2 It is characterized by its pellet compressive strength.

[0027] In some embodiments, the biochar pellets are at least about 100 lb f / in 2The immersion / drying pellet compressive strength is characterized by the immersion / drying pellet compressive strength, which is measured by immersing the biochar pellets in water at 25°C for 24 hours, and then drying the biochar pellets in air at 105°C for 24 hours. In one embodiment, the biochar pellets are at least about 200 lb f / in 2 It is characterized by the immersion / drying pellet compressive strength.

[0028] In some embodiments, the biochar pellets do not contain any pellet binders other than polyphenol materials.

[0029] In some embodiments, the biochar pellets further contain wood powder.

[0030] In some embodiments, the biochar pellets are subjected to further thermal decomposition to increase the fixed carbon content of the biochar pellets.

[0031] Other variations of the present invention presuppose the addition of a polyphenol material after densification of a solid biochar-containing material. Some variations are methods for producing biochar pellets, (a) to thermally decompose a biomass-containing raw material in a thermal decomposition reactor, thereby generating thermal decomposition steam containing solid biochar-containing material and polyphenol material; (b) Introducing pyrolysis vapor into a thermally controlled multistage separation system configured to separate pyrolysis condensates in liquid form from a non-condensable gas (where the pyrolysis condensates contain polyphenol material); (c) Introducing solid biochar-containing material into a densification unit to generate a first biochar pellet precursor; (d) Adding a polyphenol material to the first biochar pellet precursor to produce a second biochar pellet precursor; and (e) to at least partially dry the second biochar pellet precursor, thereby producing biochar pellets. : includes, Here, we provide a method for biochar pellets characterized by a 24-hour water absorption rate of approximately 20% by weight or less, as measured at 25°C and 1 bar.

[0032] In some embodiments, the biomass-containing raw material is selected from coniferous wood chips, hardwood chips, wood harvest residues, tree branches, tree stumps, leaves, bark, sawdust, corn, corn stover, wheat, wheat straw, rice, rice straw, sugarcane, sugarcane bagasse, sugarcane straw, energy cane, sugar beet, sugar beet pulp, sunflower, sorghum, canola, algae, Japanese pampas grass, alfalfa, switchgrass, fruits, fruit shells, fruit stems, fruit peels, fruit seeds, vegetables, vegetable shells, vegetable stems, vegetable peels, vegetable seeds, grape pomace, almond shells, pecan shells, coconut shells, coffee grounds, food waste, commercial waste, grass pellets, hay pellets, wood pellets, cardboard, paper, paper pulp, paper packaging, paper scraps, food packaging, construction or demolition waste, railway sleepers, lignin, animal manure, municipal solid waste, municipal sewage, or a combination thereof.

[0033] Solid biochar-containing materials contain approximately 65% ​​to 95% by weight of fixed carbon or approximately 70% to 90% by weight of fixed carbon.

[0034] A thermally controlled multistage separation system may comprise one or more filters, an absorption bed with a solid medium, an absorption bed with a liquid medium, an adsorption bed with a solid medium, a dry scrubber, a wet scrubber, a venturi scrubber, a centrifuge, a cyclone, a quench unit, a reactive condenser, a distillation column, a reactive distillation column, an evaporator, a reactive evaporator, a heat exchanger, a fan separator, an electrostatic precipitator, a demister, or a combination thereof, configured to produce pyrolysis condensate and a gas stream from pyrolysis vapor.

[0035] In some cases, a thermally controlled multistage separation system comprises a cyclone unit configured to separate solid biochar-containing material from pyrolysis steam.

[0036] The quench unit may be configured to expose pyrolysis vapor to water to produce pyrolysis condensates.

[0037] The thermally controlled multistage separation system may further comprise a demister unit configured to recover residual liquid from the gas stream. The residual liquid can be combined with the pyrolysis condensate.

[0038] In some embodiments, a thermally controlled multistage separation system is configured to capture multiple liquid fractions. The thermally controlled multistage separation system may be configured to capture multiple liquid fractions according to molecular weight, boiling point, polarity, or a combination thereof.

[0039] The pyrolysis condensate may contain at least two of the multiple liquid fractions in a combined form. In some embodiments, at least one of the multiple liquid fractions is recovered as a light byproduct that does not form part of the pyrolysis condensate.

[0040] In some embodiments, the polyphenol material contains about 20% to about 80% by weight of fixed carbon or about 40% to about 60% by weight of fixed carbon.

[0041] In some embodiments, the polyphenol material has a weight-average molecular weight of approximately 75 g / mol to approximately 50,000 g / mol, approximately 75 g / mol to approximately 1,000 g / mol, or approximately 1,000 g / mol to approximately 50,000 g / mol.

[0042] In some embodiments, the polyphenol material has a viscosity of about 1 cP to about 1000 cP at 25°C, for example, about 10 cP to about 500 cP.

[0043] In some embodiments, the polyphenol material contains about 1% to about 60% by weight of water, for example, about 5% to about 40% by weight of water.

[0044] In some embodiments, the second biochar pellet precursor has a weight ratio of polyphenol material to the first biochar pellet precursor selected from about 0.01 to about 5, for example, about 0.05 to about 2, or about 0.2 to about 0.8.

[0045] The polyphenol material can be heated before contact with the first biochar pellet precursor. The polyphenol material can be heated to a temperature of at least about 150°C, at least about 200°C, or at least about 250°C.

[0046] The first biochar pellet precursor can be heated before contact with the polyphenol material.

[0047] The densification unit may comprise an extruder, a bricketer, a pellet mill, or a combination thereof. Essentially, the densification unit may consist of an extruder, a bricketer, a pellet mill, or a combination thereof.

[0048] The densification unit can be operated at a densification temperature higher than 100°C, for example, at least 150°C or at least 200°C.

[0049] In some embodiments, the biochar pellets have a water content of 0% to about 20% by weight, 0% to about 10% by weight, 0% to about 5% by weight, 0% to about 2% by weight, or 0% to about 1% by weight.

[0050] In some embodiments, the biochar pellets have a fixed carbon content of about 50% by weight to about 99% by weight on a dry basis, for example, about 60% by weight to about 90% by weight, or about 70% by weight to about 80% by weight.

[0051] In some embodiments, the 24-hour water absorption rate of the biochar pellets, measured at 25°C and 1 bar, is about 10 wt% or less. In certain embodiments, the 24-hour water absorption rate of the biochar pellets, measured at 25°C and 1 bar, is about 6 wt% or less.

[0052] In some embodiments, the biochar pellets have at least about 100 lb at 25°C f / in 2 pellet compressive strength. In certain embodiments, the biochar pellets have at least about 200 lb at 25°C f / in 2 pellet compressive strength.

[0053] In some embodiments, the biochar pellets are characterized by an immersion / drying pellet compressive strength of at least about 100 lb f / in 2 , wherein the immersion / drying pellet compressive strength is measured by immersing the biochar pellets in water at 25°C for 24 hours, and then drying the biochar pellets in air at 105°C for 24 hours. In certain embodiments, the immersion / drying pellet compressive strength is at least about 200 lb f / in 2 .

[0054] In some embodiments, the biochar pellets are characterized by a bulk density of at least about 40 lb / ft 3 , at least about 45 lb / ft 3 , or at least about 50 lb / ft 3 .

[0055] In some embodiments, the biochar pellets contain no pellet binder other than polyphenolic materials.

[0056] In some embodiments, the biochar pellets further comprise wood flour.

[0057] In some embodiments, the biochar pellets are subjected to further thermal decomposition to increase the fixed carbon content of the biochar pellets.

[0058] Further modifications provide a method for producing biochar pellets, wherein the method is: (a) to thermally decompose a biomass-containing raw material in a thermal decomposition reactor, thereby generating a solid biochar-containing material and thermal decomposition steam; (b) To provide polyphenol materials; (c) Introducing solid biochar-containing material into a densification unit to generate a first biochar pellet precursor; (d) Adding a polyphenol material to the first biochar pellet precursor to produce a second biochar pellet precursor; and (e) to at least partially dry the second biochar pellet precursor, thereby producing biochar pellets. : can include, Here, the biochar pellets are characterized by a 24-hour water absorption rate of approximately 20% by weight or less, as measured at 25°C and 1 bar.

[0059] Further modifications provide a method for producing biochar pellets, wherein the method is: (a) to thermally decompose a biomass-containing raw material in a thermal decomposition reactor, thereby generating a solid biochar-containing material and thermal decomposition steam; (b) To provide polyphenol materials; (c) Contacting a solid biochar-containing material with a polyphenol material to produce an intermediate mixture; (d) Introducing the intermediate mixture into a densification unit to generate a biochar pellet precursor; and (e) to at least partially dry the biochar pellet precursor, thereby producing biochar pellets. : can include, Here, the biochar pellets are characterized by a 24-hour water absorption rate of approximately 20% by weight or less, as measured at 25°C and 1 bar.

[0060] In some embodiments, the biomass-containing raw materials include coniferous wood chips, hardwood wood chips, wood harvesting residues, tree branches, tree stumps, leaves, bark, sawdust, corn, corn stover, wheat, wheat straw, rice, rice straw, sugarcane, sugarcane bagasse, sugarcane straw, energy cane, sugar beet, sugar beet pulp, sunflower, sorghum, canola, algae, Japanese pampas grass, alfalfa, switchgrass, fruits, and fruit shells. Fruit stems, fruit peels, fruit seeds, vegetables, vegetable shells, vegetable stems, vegetable peels, vegetable seeds, grape pomace, almond shells, pecan shells, coconut shells, coffee grounds, food waste, commercial waste, grass pellets, hay pellets, wood pellets, cardboard, paper, paper pulp, paper packaging, paper scraps, food packaging, construction or demolition waste, railway sleepers, lignin, animal manure, municipal solid waste, municipal sewage, or any combination thereof may be selected.

[0061] Solid biochar-containing materials may contain approximately 65% ​​to 95% by weight of fixed carbon, for example, approximately 70% to 90% by weight of fixed carbon.

[0062] The polyphenol material may contain approximately 20% to 80% by weight of fixed carbon, for example, approximately 40% to 60% by weight of fixed carbon.

[0063] The polyphenol material may have a weight-average molecular weight of approximately 75 g / mol to approximately 50,000 g / mol, for example, approximately 75 g / mol to approximately 1,000 g / mol, or approximately 1,000 g / mol to approximately 50,000 g / mol.

[0064] Polyphenol materials can have a viscosity of approximately 1 cP to 1000 cP at 25°C, for example, approximately 10 cP to 500 cP.

[0065] The polyphenol material may contain approximately 1% to 60% by weight of water, for example, approximately 5% to 40% by weight of water.

[0066] In some methods, the intermediate mixture has a weight ratio of polyphenol material to solid biochar-containing material selected from about 0.01 to about 5. In other methods, the intermediate mixture has a weight ratio of polyphenol material to solid biochar-containing material selected from about 0.05 to about 2, for example, about 0.1 to about 1, or about 0.2 to about 0.8.

[0067] In some methods, the polyphenol material is heated before contact with the solid biochar-containing material. The polyphenol material can be heated to a temperature of, for example, at least about 150°C, at least about 200°C, or at least about 250°C.

[0068] In some methods, the solid biochar-containing material is heated before contact with the polyphenol material. The solid biochar-containing material can be controlled to be within ±100°C or ±50°C of the pyrolysis reactor temperature before contact with the polyphenol material.

[0069] In some methods, the intermediate mixture is heated before step (d).

[0070] In some ways, the densification unit comprises an extruder, a bricketer, a pellet mill, or a combination thereof. In some ways, the densification unit essentially consists of an extruder, a bricketer, a pellet mill, or a combination thereof. In one way, the densification unit is an extruder.

[0071] The densification unit can be operated at a densification temperature higher than 100°C, for example, at least 150°C or at least 200°C.

[0072] In some embodiments, in step (d), the densification unit is configured to generate a concentrated concentration of polyphenol material on the outer shell of the biochar pellet precursor.

[0073] In some methods, steps (d) and (e) are combined, and the densification unit is also configured for drying the biochar pellet precursor.

[0074] In some cases, the biochar pellets have a water content of 0% to about 20% by weight of water, for example, 0% to about 10% by weight of water, or 0% to about 5% by weight of water, or 0% to about 2% by weight of water, or 0% to about 1% by weight of water.

[0075] In some methods, the biochar pellets have a fixed carbon content of approximately 50% to 99% by weight of fixed carbon on a dry basis. In other methods, the biochar pellets have a fixed carbon content of approximately 60% to 90% by weight of fixed carbon on a dry basis, or approximately 70% to 80% by weight of fixed carbon on a dry basis.

[0076] In some methods, the 24-hour water absorption rate of biochar pellets is approximately 10% by weight or less, measured at 25°C and 1 bar. In another method, the 24-hour water absorption rate of biochar pellets is approximately 6% by weight or less, measured at 25°C and 1 bar.

[0077] In some methods, biochar pellets are at least about 100 lb at 25°C. f / in 2 It is characterized by a pellet compressive strength of at least about 200 lb at 25°C. In one method, the biochar pellets are characterized by a pellet compressive strength of at least about 200 lb at 25°C. f / in 2 It is characterized by its pellet compressive strength.

[0078] In some embodiments, the biochar pellets are at least about 100 lb f / in 2 The immersion / drying pellet compressive strength is characterized by the immersion / drying pellet compressive strength, which is measured by immersing the biochar pellets in water at 25°C for 24 hours, and then drying the biochar pellets in air at 105°C for 24 hours. In one embodiment, the biochar pellets are at least about 200 lbf / in 2 It is characterized by the immersion / drying pellet compressive strength.

[0079] In some cases, biochar pellets are at least about 40 lb / ft 3 It is characterized by a bulk density of at least about 45 lb / ft. 3 Or at least about 50 lbs / ft 3 It is characterized by its bulk density.

[0080] In some methods, biochar pellets do not contain pellet binders other than polyphenol materials.

[0081] In some methods, the biochar pellets further contain wood powder.

[0082] In some methods, biochar pellets are subjected to further thermal decomposition to increase the fixed carbon content of the biochar pellets.

[0083] Some variations of the present invention are (a) to thermally decompose a biomass-containing raw material in a thermal decomposition reactor, thereby generating thermal decomposition steam containing solid biochar-containing material and polyphenol material; (b) Introducing pyrolysis vapor into a thermally controlled multistage separation system configured to recover pyrolysis condensates in liquid form separated from non-condensable gases; (c) Contacting a solid biochar-containing material with a polyphenol material to produce an intermediate mixture; (d) Introducing the intermediate mixture into a densification unit to generate a biochar pellet precursor; and (e) to at least partially dry the biochar pellet precursor, thereby producing biochar pellets. We provide biochar pellets manufactured by a method including: Here, the biochar pellets are characterized by a 24-hour water absorption rate of approximately 20% by weight or less, as measured at 25°C and 1 bar.

[0084] In some embodiments, the solid biochar-containing material contains about 65% to about 95% by weight of fixed carbon. Biochar pellets may contain, for example, about 60% to about 90% by weight of fixed carbon.

[0085] In some embodiments, the intermediate mixture has a weight ratio of polyphenol material to solid biochar-containing material selected from about 0.01 to about 5.

[0086] In some embodiments, the 24-hour water absorption rate of the biochar pellets is approximately 10% by weight or less, as measured at 25°C and 1 bar.

[0087] In some embodiments, the biochar pellets are at least about 40 lb / ft 3 It is characterized by its bulk density.

[0088] In some embodiments, the biochar pellets are at least about 100 lb at 25°C. f / in 2 It is characterized by its pellet compressive strength.

[0089] In some embodiments, the biochar pellets are at least about 100 lb f / in 2 The immersion / drying pellet compressive strength is characterized by the following: the immersion / drying pellet compressive strength is measured by immersing the biochar pellets in water at 25°C for 24 hours, and then drying the biochar pellets in air at 105°C for 24 hours.

[0090] Some variations of the present invention are (a) to thermally decompose a biomass-containing raw material in a thermal decomposition reactor, thereby generating a solid biochar-containing material and thermal decomposition steam; (b) Providing polyphenol material (e.g., from an external source); (c) Contacting a solid biochar-containing material with a polyphenol material to produce an intermediate mixture; (d) Introducing the intermediate mixture into a densification unit to generate a biochar pellet precursor; and (e) to at least partially dry the biochar pellet precursor, thereby producing biochar pellets. We provide biochar pellets manufactured by a method including: Here, the biochar pellets are characterized by a 24-hour water absorption rate of approximately 20% by weight or less, as measured at 25°C and 1 bar.

[0091] In some embodiments, the solid biochar-containing material contains about 65% to about 95% by weight of fixed carbon, or the intermediate mixture has a weight ratio of polyphenol material to solid biochar-containing material selected from about 0.01 to about 5.

[0092] In some embodiments, the 24-hour water absorption rate of the biochar pellets is about 10% by weight or less, measured at 25°C and 1 bar; the biochar pellets have a water content of at least about 40 lb / ft 3 Characterized by a bulk density; or the biochar pellets are at least about 100 lb at 25°C. f / in 2 It is characterized by its pellet compressive strength.

[0093] Some embodiments of the present invention are (a) Solid biochar-containing materials; (b) Polyphenol materials; (c) Optionally, ash content; and (d) Optionally, water We provide biochar pellets that include: Here, the weight ratio of the polyphenol material to the solid biochar-containing material is selected from approximately 0.01 to approximately 5; Here, the biochar pellets contain approximately 50% to 99% fixed carbon by weight; and Here, the biochar pellets are characterized by a 24-hour water absorption rate of approximately 20% by weight or less, as measured at 25°C and 1 bar.

[0094] Further variations of the present invention include: (a) Solid biochar-containing materials; (b) Polyphenol materials; (c) Optionally, ash content; and (d) Optionally, water : Essentially derived from, providing biochar pellets, Here, the weight ratio of the polyphenol material to the solid biochar-containing material is selected from approximately 0.01 to approximately 5; Here, the biochar pellets contain approximately 50% to 99% fixed carbon by weight; and Here, the biochar pellets are characterized by a 24-hour water absorption rate of approximately 20% by weight or less, as measured at 25°C and 1 bar.

[0095] Another variation of the present invention provides biochar pellets. In such a variation, the biochar pellets are (a) Solid biochar-containing materials; (b) Polyphenol materials; (c) Optionally, ash content; and (d) Optionally, water : includes, Here, the biochar pellets do not contain any external binders other than polyphenol materials; Here, the weight ratio of the polyphenol material to the solid biochar-containing material is selected from approximately 0.01 to approximately 5; Here, the biochar pellets contain approximately 50% to 95% fixed carbon by weight; and Here, the biochar pellets are characterized by a 24-hour water absorption rate of approximately 20% by weight or less, as measured at 25°C and 1 bar.

[0096] In some embodiments of the biochar pellets, the biochar pellets contain about 60% to about 90% by weight of fixed carbon, for example, about 65% to about 85% by weight of fixed carbon, or about 70% to about 80% by weight of fixed carbon.

[0097] In some embodiments of the biochar pellets, the polyphenol material has a weight-average molecular weight of about 75 g / mol to about 50,000 g / mol, for example, about 75 g / mol to about 1,000 g / mol, or about 1,000 g / mol to about 50,000 g / mol.

[0098] In some embodiments of the biochar pellets, the polyphenol material has a viscosity of about 1 cP to about 1000 cP at 25°C, for example, about 10 cP to about 500 cP.

[0099] In some embodiments of biochar pellets, the total carbon in the polyphenol material is 14 C / 12 As determined from measurements of 14C isotope ratios, it is at least 50%, at least 75%, at least 90%, or 100% regenerative.

[0100] In some embodiments of the biochar pellets, the weight ratio of the polyphenol material to the solid biochar-containing material is selected from about 0.05 to about 2. In one embodiment of the biochar pellets, the weight ratio of the polyphenol material to the solid biochar-containing material is selected from about 0.2 to about 0.8.

[0101] In some embodiments of biochar pellets, the ash content of the biochar pellets is less than 5% by weight, for example, less than 3% by weight or less than 1% by weight.

[0102] In some embodiments of the biochar pellets, the moisture content of the biochar pellets is less than 20% by weight, for example, less than 15% by weight, less than 10% by weight, less than 5% by weight, or less than 1% by weight.

[0103] In some embodiments of biochar pellets, the 24-hour water absorption rate of the biochar pellets is approximately 10% by weight or less, measured at 25°C and 1 bar. In some embodiments of biochar pellets, the 24-hour water absorption rate of the biochar pellets is approximately 6% by weight or less, measured at 25°C and 1 bar.

[0104] In some embodiments of biochar pellets, the biochar pellets are at least about 100 lb at 25°C. f / in 2 It is characterized by a pellet compressive strength of at least about 200 lb at 25°C. In one embodiment, the biochar pellets are characterized by a pellet compressive strength of at least about 200 lb at 25°C. f / in 2 It is characterized by its pellet compressive strength.

[0105] In some embodiments of biochar pellets, the biochar pellets are at least about 100 lb f / in 2 The immersion / drying pellet compressive strength is characterized by the immersion / drying pellet compressive strength, which is measured by immersing the biochar pellets in water at 25°C for 24 hours, and then drying the biochar pellets in air at 105°C for 24 hours. In one embodiment, the immersion / drying pellet compressive strength is at least about 200 lb f / in 2 That is the case.

[0106] In some embodiments of biochar pellets, the biochar pellets have a density of at least approximately 40 lb / ft 3 It is characterized by a bulk density of at least about 45 lb / ft. 3 Or at least about 50 lbs / ft 3 It is characterized by its bulk density.

[0107] In some embodiments of biochar pellets, the biochar pellet has a concentrated polyphenol material in its outer shell and a concentrated solid biochar-containing material in its inner core.

[0108] In some embodiments of biochar pellets, the biochar pellets further contain wood powder.

[0109] In some embodiments of biochar pellets, the total carbon in the biochar pellet is the total carbon 14 C / 12 As determined from the measurement of the 1C isotope ratio, at least 50% is renewable. In one embodiment, the total carbon in the biochar pellet is the total carbon 14 C / 12 As determined from the measurement of the 1C isotope ratio, at least 90% is renewable. In a specific embodiment, the total carbon in the biochar pellet is the total carbon 14 C / 12 It is 100% regenerative, as determined by the measurement of the 1C isotope ratio.

[0110] In some embodiments, the 24-hour water absorption rate of the biochar pellets is approximately 6% by weight or less, measured at 25°C and 1 bar, and the total carbon content in the biochar pellets is 14 C / 12 As determined from the measurement of the 1C isotope ratio, it is at least 90% renewable. In some embodiments, the 24-hour water absorption rate of the biochar pellets is less than or equal to about 6% by weight, measured at 25°C and 1 bar, and the total carbon in the biochar pellets is less than or equal to the total carbon 14 C / 12 It is 100% regenerative, as determined by the measurement of the 1C isotope ratio.

[0111] In some embodiments of biochar pellets, the biochar pellets have a pellet shape selected from the group consisting of spheres, cylinders, cubes, octagons, hexagons, honeycomb shapes, ellipses, cylindrical shapes, rod shapes, pillow shapes, lens shapes, amorphous granules, and combinations thereof.

[0112] In some embodiments of the biochar pellets, the biochar pellets have a pellet size selected from about 1 mm to about 10 cm, which is calculated as the effective diameter of the biochar pellet.

[0113] In some embodiments of biochar pellets, the biochar pellets are characterized by low odor in accordance with ASTM D1296.

[0114] In some embodiments of biochar pellets, the biochar pellets are characterized as non-self-heating when subjected to a self-heating test in accordance with the Manual of Tests and Criteria, 7th Revision, 2019, United Nations, page 375, 33.4.6, Test N.4: "Test method for self-heating substances".

[0115] In some embodiments of biochar pellets, the biochar pellets are characterized by a negative slope of the 24-hour water absorption rate of the biochar pellets with respect to the fixed carbon content of the biochar pellets.

[0116] In some embodiments of biochar pellets, the biochar pellets are characterized by a parameter c selected from about 200 to about 1000, for example, about 400 to about 1000 or about 200 to about 800, where c is

number

[0117] In some embodiments of biochar pellets, the biochar pellets are characterized by a parameter x selected from about 500 to about 5000, for example, about 800 to about 4000 or about 1000 to about 2000, where x is

number

[0118] Other variations of the present invention presuppose the addition of a polyphenol material after densification of a solid biochar-containing material. Some variations are methods for producing biochar pellets, (a) to thermally decompose a biomass-containing raw material in a thermal decomposition reactor, thereby generating thermal decomposition steam containing solid biochar-containing material and polyphenol material; (b) Introducing pyrolysis vapor into a thermally controlled multistage separation system configured to separate pyrolysis condensates in liquid form from a non-condensable gas (where the pyrolysis condensates contain polyphenol material); (c) Introducing solid biochar-containing material into a densification unit to generate a first biochar pellet precursor; (d) Adding a polyphenol material to the first biochar pellet precursor to produce a second biochar pellet precursor; and (e) to at least partially dry the second biochar pellet precursor, thereby producing biochar pellets. : includes, Here, we provide a method for biochar pellets characterized by a 24-hour water absorption rate of approximately 20% by weight or less, as measured at 25°C and 1 bar.

[0119] In some embodiments, the biomass-containing raw material is selected from coniferous wood chips, hardwood chips, wood harvest residues, tree branches, tree stumps, leaves, bark, sawdust, corn, corn stover, wheat, wheat straw, rice, rice straw, sugarcane, sugarcane bagasse, sugarcane straw, energy cane, sugar beet, sugar beet pulp, sunflower, sorghum, canola, algae, Japanese pampas grass, alfalfa, switchgrass, fruits, fruit shells, fruit stems, fruit peels, fruit seeds, vegetables, vegetable shells, vegetable stems, vegetable peels, vegetable seeds, grape pomace, almond shells, pecan shells, coconut shells, coffee grounds, food waste, commercial waste, grass pellets, hay pellets, wood pellets, cardboard, paper, paper pulp, paper packaging, paper scraps, food packaging, construction or demolition waste, railway sleepers, lignin, animal manure, municipal solid waste, municipal sewage, or a combination thereof.

[0120] Solid biochar-containing materials contain approximately 65% ​​to 95% by weight of fixed carbon, or approximately 70% to 90% by weight of fixed carbon.

[0121] A thermally controlled multistage separation system may comprise one or more filters, an absorption bed with a solid medium, an absorption bed with a liquid medium, an adsorption bed with a solid medium, a dry scrubber, a wet scrubber, a venturi scrubber, a centrifuge, a cyclone, a quench unit, a reactive condenser, a distillation column, a reactive distillation column, an evaporator, a reactive evaporator, a heat exchanger, a fan separator, an electrostatic precipitator, a demister, or a combination thereof, configured to produce pyrolysis condensate and a gas stream from pyrolysis vapor.

[0122] In some cases, a thermally controlled multistage separation system comprises a cyclone unit configured to separate solid biochar-containing material from pyrolysis steam.

[0123] The quench unit may be configured to expose pyrolysis vapor to water to produce pyrolysis condensates.

[0124] The thermally controlled multistage separation system may further comprise a demister unit configured to recover residual liquid from the gas stream. The residual liquid can be combined with the pyrolysis condensate.

[0125] In some embodiments, a thermally controlled multistage separation system is configured to capture multiple liquid fractions. The thermally controlled multistage separation system may be configured to capture multiple liquid fractions according to molecular weight, boiling point, polarity, or a combination thereof.

[0126] The pyrolysis condensate may contain at least two of the multiple liquid fractions in a combined form. In some embodiments, at least one of the multiple liquid fractions is recovered as a light byproduct that does not form part of the pyrolysis condensate.

[0127] In some embodiments, the polyphenol material contains about 20% to about 80% by weight of fixed carbon or about 40% to about 60% by weight of fixed carbon.

[0128] In some embodiments, the polyphenol material has a weight-average molecular weight of approximately 75 g / mol to approximately 50,000 g / mol, approximately 75 g / mol to approximately 1,000 g / mol, or approximately 1,000 g / mol to approximately 50,000 g / mol.

[0129] In some embodiments, the polyphenol material has a viscosity of about 1 cP to about 1000 cP at 25°C, for example, about 10 cP to about 500 cP.

[0130] In some embodiments, the polyphenol material contains about 1% to about 60% by weight of water, for example, about 5% to about 40% by weight of water.

[0131] In some embodiments, the second biochar pellet precursor has a weight ratio of polyphenol material to the first biochar pellet precursor selected from about 0.01 to about 5, for example, about 0.05 to about 2, or about 0.2 to about 0.8.

[0132] The polyphenol material can be heated before contact with the first biochar pellet precursor. The polyphenol material can be heated to a temperature of at least about 150°C, at least about 200°C, or at least about 250°C.

[0133] The first biochar pellet precursor can be heated before contact with the polyphenol material.

[0134] The densification unit may comprise an extruder, a bricketer, a pellet mill, or a combination thereof. Essentially, the densification unit may consist of an extruder, a bricketer, a pellet mill, or a combination thereof.

[0135] The densification unit can be operated at a densification temperature higher than 100°C, for example, at least 150°C or at least 200°C.

[0136] In some embodiments, the biochar pellets have a water content of 0% to about 20% by weight, 0% to about 10% by weight, 0% to about 5% by weight, 0% to about 2% by weight, or 0% to about 1% by weight.

[0137] In some embodiments, the biochar pellets have a fixed carbon content of about 50% by weight to about 99% by weight on a dry basis, for example, about 60% by weight to about 90% by weight or about 70% by weight to about 80% by weight.

[0138] In some embodiments, the 24-hour water absorption rate of the biochar pellets is approximately 10% by weight or less, measured at 25°C and 1 bar. In one embodiment, the 24-hour water absorption rate of the biochar pellets is approximately 6% by weight or less, measured at 25°C and 1 bar.

[0139] In some embodiments, the biochar pellets are at least about 100 lb at 25°C. f / in 2 It is characterized by a pellet compressive strength of at least about 200 lb at 25°C. In one embodiment, the biochar pellets are characterized by a pellet compressive strength of at least about 200 lb at 25°C. f / in 2 It is characterized by its pellet compressive strength.

[0140] In some embodiments, the biochar pellets are at least about 100 lb f / in 2 The immersion / drying pellet compressive strength is characterized by the immersion / drying pellet compressive strength, which is measured by immersing the biochar pellets in water at 25°C for 24 hours, and then drying the biochar pellets in air at 105°C for 24 hours. In one embodiment, the immersion / drying pellet compressive strength is at least about 200 lb f / in 2 That is the case.

[0141] In some embodiments, the biochar pellets are at least about 40 lb / ft 3 , at least about 45 lb / ft 3 , or at least about 50 lb / ft 3 It is characterized by its bulk density.

[0142] In some embodiments, the biochar pellets do not contain any pellet binders other than polyphenol materials.

[0143] In some embodiments, the biochar pellets further contain wood powder.

[0144] In some embodiments, the biochar pellets are subjected to further thermal decomposition to increase the fixed carbon content of the biochar pellets.

[0145] Other variations include: (a) to thermally decompose a biomass-containing raw material in a thermal decomposition reactor, thereby generating thermal decomposition steam containing solid biochar-containing material and polyphenol material; (b) Introducing pyrolysis vapor into a thermally controlled multistage separation system configured to separate pyrolysis condensates in liquid form from a non-condensable gas (where the pyrolysis condensates contain polyphenol material); (c) Introducing solid biochar-containing material into a densification unit to generate a first biochar pellet precursor; (d) Adding a polyphenol material to the first biochar pellet precursor to produce a second biochar pellet precursor; and (e) to at least partially dry the second biochar pellet precursor, thereby producing biochar pellets. : includes, Here, we provide biochar pellets manufactured by a method characterized by a 24-hour water absorption rate of approximately 20% by weight or less, as measured at 25°C and 1 bar.

[0146] Some variations are methods for producing biochar pellets, (a) to thermally decompose a biomass-containing raw material in a thermal decomposition reactor, thereby generating a solid biochar-containing material and thermal decomposition steam; (b) To provide polyphenol materials; (c) Introducing solid biochar-containing material into a densification unit to generate a first biochar pellet precursor; (d) Adding a polyphenol material to the first biochar pellet precursor to produce a second biochar pellet precursor; and (e) to at least partially dry the second biochar pellet precursor, thereby producing biochar pellets. : includes, Here, we provide a method for biochar pellets characterized by a 24-hour water absorption rate of approximately 20% by weight or less, as measured at 25°C and 1 bar.

[0147] In some embodiments, the solid biochar-containing material contains approximately 70% to 90% by weight of fixed carbon.

[0148] In some embodiments, the polyphenol material contains approximately 20% to 80% by weight of fixed carbon.

[0149] In some embodiments, the polyphenol material contains approximately 40% to 60% by weight of fixed carbon.

[0150] In some embodiments, the polyphenol material has a weight-average molecular weight of approximately 75 g / mol to approximately 50,000 g / mol, approximately 75 g / mol to approximately 1,000 g / mol, or approximately 1,000 g / mol to approximately 50,000 g / mol.

[0151] In some embodiments, the polyphenol material has a viscosity of about 1 cP to about 1000 cP at 25°C, for example, about 10 cP to about 500 cP.

[0152] In some embodiments, the polyphenol material contains about 1% to about 60% by weight of water, for example, about 5% to about 40% by weight of water.

[0153] In some embodiments, the second biochar pellet precursor has a weight ratio of polyphenol material to the first biochar pellet precursor selected from about 0.01 to about 5, for example, about 0.05 to about 2, or about 0.2 to about 0.8.

[0154] The densification unit may comprise an extruder, a bricketer, a pellet mill, or a combination thereof. Essentially, the densification unit may consist of an extruder, a bricketer, a pellet mill, or a combination thereof.

[0155] The densification unit can be operated at a densification temperature higher than 100°C, for example, at least 150°C or at least 200°C.

[0156] In some embodiments, the biochar pellets have a water content of 0% to about 20% by weight, 0% to about 10% by weight, 0% to about 5% by weight, 0% to about 2% by weight, or 0% to about 1% by weight.

[0157] Biochar pellets may have a fixed carbon content of approximately 50% by weight to approximately 99% by weight on a dry basis, for example, approximately 60% by weight to approximately 90% by weight, or approximately 70% by weight to approximately 80% by weight.

[0158] In some embodiments, the 24-hour water absorption rate of the biochar pellets is approximately 10% by weight or less, measured at 25°C and 1 bar. In one embodiment, the 24-hour water absorption rate of the biochar pellets is approximately 6% by weight or less, measured at 25°C and 1 bar.

[0159] In some embodiments, the biochar pellets are at least about 100 lb at 25°C. f / in 2It is characterized by a pellet compressive strength of at least about 200 lb at 25°C. In one embodiment, the biochar pellets are characterized by a pellet compressive strength of at least about 200 lb at 25°C. f / in 2 It is characterized by its pellet compressive strength.

[0160] In some embodiments, the biochar pellets are at least about 100 lb f / in 2 The immersion / drying pellet compressive strength is characterized by the immersion / drying pellet compressive strength, which is measured by immersing the biochar pellets in water at 25°C for 24 hours, and then drying the biochar pellets in air at 105°C for 24 hours. In one embodiment, the immersion / drying pellet compressive strength is at least about 200 lb f / in 2 That is the case.

[0161] In some embodiments, the biochar pellets are at least about 40 lb / ft 3 , at least about 45 lb / ft 3 , or at least about 50 lb / ft 3 It is characterized by its bulk density.

[0162] In some embodiments, the biochar pellets do not contain any pellet binders other than polyphenol materials.

[0163] In some embodiments, the biochar pellets further contain wood powder.

[0164] In some embodiments, the biochar pellets are subjected to further thermal decomposition to increase the fixed carbon content of the biochar pellets. [Brief explanation of the drawing]

[0165] (Brief explanation of the drawing) [Figure 1]Figure 1 is a simplified block flow diagram of a method for producing biochar pellets from biomass using internally generated polyphenol material derived from the condensation and separation of pyrolysis steam, in several embodiments.

[0166] [Figure 2] Figure 2 is a simplified block flow diagram of a method for producing biochar pellets from biomass using externally supplied polyphenol material in several embodiments.

[0167] [Figure 3] Figure 3 is a photograph of the polyphenol material produced in Example 1 from biomass pyrolysis and the subsequent reaction and condensation of the pyrolysis vapor.

[0168] [Figure 4] Figure 4 is a photograph of the biochar pellets (extruded) produced in Example 2.

[0169] [Figure 5] Figure 5A is a photograph of biochar pellets immersed in liquid water in Example 2 to measure their water absorption rate and mechanical durability.

[0170] Figure 5B is a photograph of the biochar pellets after they were removed from immersion in liquid water in Example 2. [Modes for carrying out the invention]

[0171] (Detailed explanation) This description will enable those skilled in the art to manufacture and use the present invention, and it describes several embodiments, adaptations, modifications, alternatives, and uses of the present invention. These and other embodiments, features, and advantages of the present invention will become apparent to those skilled in the art upon consideration with reference to the following detailed description of the invention in conjunction with the accompanying drawings.

[0172] As used herein and in the appended claims, the singular forms "a," "an," and "the" refer to multiple subjects unless the context clearly indicates otherwise. Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those generally understood by those skilled in the art to which the invention pertains.

[0173] Unless otherwise indicated, all numerical values ​​used in this specification and the appended claims to represent reaction conditions, stoichiometry, component concentrations, etc., should be understood in all cases to be modified by the term "approximately." Therefore, unless otherwise indicated, the numerical parameters described in the following specification and the appended claims are approximations that may vary depending at least on the specific analytical method.

[0174] The term "comprising," which is synonymous with "including," "containing," or "characterized by," is comprehensive or open-ended and does not exclude additional unlisted elements or steps of the method. "Comprising" is a technical term used in the language of claims, meaning that the elements of the named claim are essential, but additional elements of other claims may still form a configuration within the scope of the claim.

[0175] As used herein, the phrase "consists of" excludes any element, process, or component not specified in the claim. If "consists of" (or a variation thereof) appears in a phrase in the body of the claim rather than immediately following the preamble, it limits only the element described in that phrase; other elements are not excluded from the claim as a whole. As used herein, the phrase "essentially consists of" limits the scope of the claim to the specified element or process of the method and any that does not substantially affect the fundamental and novel features of the claimed subject matter.

[0176] With respect to the terms “contains,” “consistes of,” and “essentially consists of,” if any of these three terms is used herein, the subject matter now disclosed and claimed may include the use of any of the other two terms, except in the case of the Markush group. Thus, in some embodiments not expressly enumerated elsewhere, any example of “contains” may be replaced by “consistes of,” or instead by “essentially consists of.”

[0177] Where used herein, unless expressly stated otherwise, “or” refers to an inclusive “or” and not an exclusive “or.” Unless the word “or” is expressly limited to meaning only a single item that is exclusive from the other items in a list of two or more items, the use of “or” in such a list should be interpreted as including (a) any single item in the list, (b) all items in the list, or (c) any combination of items in the list. Where used herein, the phrase “or,” as seen in “A or B,” refers to A only, B only, and both A and B. Where the context allows, singular or plural terms may also include plural or singular terms, respectively.

[0178] As used herein, total carbon refers to fixed carbon and unfixed carbon present in volatile matter. In some embodiments, the weight percentages of components are absolute and are assumed unless otherwise specified. In other embodiments, the weight percentages of components are based on an anhydrous, ash-free standard.

[0179] For the purpose of making a practical technical disclosure, various explanations, hypotheses, theories, speculations, and assumptions are disclosed. This invention does not rely on any of these to be actually true. None of the explanations, hypotheses, theories, speculations, or assumptions in this detailed description shall be construed as limiting the scope of this invention in any way.

[0180] For the purposes of this text, "biogenic" is intended to mean materials (whether raw materials, products, or intermediates) containing elements such as carbon that are renewable on a timescale of months, years, or decades. Non-biogenic materials may be non-renewable or renewable on a geological timescale of hundreds, thousands, millions, or even longer. It should be noted that biogenic materials may include mixtures of biogenic and non-biogenic sources.

[0181] For the purposes of this text, “reagent” is intended to mean material in its broadest sense; a reagent may be a fuel, chemical, material, compound, additive, blend component, solvent, etc. A reagent is not necessarily a chemical agent that causes or participates in a chemical reaction. A reagent may or may not be a chemical reactant; it may or may not be consumed in a reaction. A reagent may be a chemical catalyst for a particular reaction. A reagent may cause or participate in the modification of the mechanical, physical, or hydrodynamic properties of a material to which the reagent can be added. For example, a reagent may be introduced into a metal to impart a particular strength property to it. A reagent may be a substance of sufficient purity (typically carbon purity in this context) to be used in chemical analysis or physical testing.

[0182] For this purpose, the "polyphenol material" is a material that contains one or more phenol groups and may have many other functional groups (e.g., carboxyl groups, alkyl groups, ether groups, etc.), and may contain non-polymerizable compounds (e.g., monomeric phenols) or polymerizable compounds that are not polyphenol compounds (e.g., polyphenyl compounds that do not have -OH groups).

[0183] Some modifications of the disclosed invention are based on recovering the pyrolysis condensate as a polyphenol material, combining the pyrolysis condensate with solid biochar derived from biomass pyrolysis, densifying it, and drying it to produce biochar pellets with a remarkably low water absorption rate.

[0184] Carbon is a platform element in a wide variety of industries and has a vast number of chemical, material, and fuel uses. Carbon is an excellent fuel for generating energy, including electricity. Carbon also has tremendous chemical value for various commodities and advanced materials, including metals, alloys, composite materials, carbon fibers, electrodes, and catalyst supports. In the case of ironmaking, carbon is useful as a reactant for reducing metal oxides to metals during processing; as a fuel for providing heat for processing; and as a component of alloys. Historically, carbon in the form of coal has been widely used for industrial purposes. Coal remains the world's largest energy source for power generation and ironmaking. However, coal is considered to be the single largest contributor to the climate crisis.

[0185] Carbon can in principle be produced from virtually any carbonaceous material. Carbonaceous materials generally include fossil resources such as natural gas, petroleum, coal, and lignite; as well as renewable resources such as lignocellulosic biomass and various waste materials rich in carbon. To mitigate the rising economic, environmental, and social costs associated with fossil resources, renewable biomass can be utilized to produce carbon-based reagents.

[0186] Biomass is a term used to describe any biologically produced substance, i.e., biogenic material. The chemical energy contained in biomass is derived from solar energy using the natural process of photosynthesis. Photosynthesis is a process by which plants take in carbon dioxide and water from their surroundings and use energy from sunlight to convert them into sugars, starches, cellulose, hemicellulose, and lignin. Among all renewable energy sources, biomass is unique in that it is effectively stored solar energy. Furthermore, biomass is the only renewable source of carbon.

[0187] Various conversion technologies exist for transforming biomass raw materials into high-carbon materials. Pyrolysis is a thermal conversion process of solid materials in the absence of an oxidizing agent (air or oxygen) or in a supply so limited that oxidation does not occur to a visible degree. Depending on the process conditions and additives, biomass pyrolysis can be adjusted to produce greatly varying amounts of gas, liquid, and solid. Historically, the slow pyrolysis of wood has been carried out in large piles using simple batch processes without emission control. Traditional charcoal production techniques are not only energy inefficient but also highly polluting.

[0188] Coal typically arrives at power plants by railcars, barges, trucks, or conveyor belts. Once the coal arrives at the plant site, it is either sent directly to the plant via conveyor belts or stored in piles. A typical coal-fired power plant stores about 75 days' worth of coal on site (US Energy Information Administration, Electricity Monthly Update, "Electric Power Sector Coal Stocks: November 2017," January 24, 2018). Coal piles expose the coal to atmospheric conditions such as rainfall. Coal piles are generally left uncovered due to the need for frequent loading and unloading (Schulz et al., "Modelling of dust emissions induced by flow over stockpiles and through packed beds," Particuology 2020, 59, 55-63). When it rains on the surface of an uncovered stockpile, the water either permeates into the pile, evaporates and returns to the atmosphere, or flows down the surface as runoff (Campbell, "Moisture retention and migration in a coal product stockpile," Proceedings of the IMPC 2014, Santiago, Chile, 2014).

[0189] When coal is replaced by biochar, it is desirable that the biochar has a similar water absorption rate to coal so that it can be stored in open piles on the plant site and that frequent loading and unloading can be facilitated. If biochar absorbs too much water, it may impair its chemical or physical properties, and its calorific value will decrease. While pure carbon is known to be hydrophobic, biochar usually contains oxygen-containing surface groups that are inherently more hydrophilic. In fact, conventional biochar from pyrolysis is inherently hydrophilic.

[0190] Furthermore, conventional biochar produced from pyrolysis has low bulk density and low mechanical strength. For many commercial applications of biochar, low bulk density and strength, coupled with hydrophilicity, are serious drawbacks.

[0191] Therefore, there is a strong need for improved or optimized biochar pellets and methods for producing them that can maintain or improve the density and durability of the pellets while simultaneously improving their water resistance.

[0192] (Method for producing biochar pellets) In some modifications, the present invention provides a method for producing biochar pellets. In one modification, the method for producing biochar pellets is (a) to thermally decompose a biomass-containing raw material in a thermal decomposition reactor, thereby generating thermal decomposition steam containing solid biochar-containing material and polyphenol material; (b) Introducing pyrolysis vapor into a thermally controlled multistage separation system configured to separate pyrolysis condensates in liquid form from a non-condensable gas (where the pyrolysis condensates contain polyphenol material); (c) Contacting a solid biochar-containing material with a polyphenol material to produce an intermediate mixture; (d) Introducing the intermediate mixture into a densification unit to generate a biochar pellet precursor; and (e) to at least partially dry the biochar pellet precursor, thereby producing biochar pellets. : includes, Here, the biochar pellets are characterized by a 24-hour water absorption rate of approximately 20% by weight or less, as measured at 25°C and 1 bar.

[0193] Figure 1 is a simplified block flow diagram of a method for producing biochar pellets from biomass using internally generated polyphenol material derived from the condensation and separation of pyrolysis steam, in several embodiments.

[0194] In some embodiments, the biomass-containing raw material is selected from coniferous wood chips, hardwood chips, wood harvest residues, tree branches, tree stumps, leaves, bark, sawdust, corn, corn stover, wheat, wheat straw, rice, rice straw, sugarcane, sugarcane bagasse, sugarcane straw, energy cane, sugar beet, sugar beet pulp, sunflower, sorghum, canola, algae, Japanese pampas grass, alfalfa, switchgrass, fruits, fruit shells, fruit stems, fruit peels, fruit seeds, vegetables, vegetable shells, vegetable stems, vegetable peels, vegetable seeds, grape pomace, almond shells, pecan shells, coconut shells, coffee grounds, food waste, commercial waste, grass pellets, hay pellets, wood pellets, cardboard, paper, paper pulp, paper packaging, paper scraps, food packaging, construction or demolition waste, railway sleepers, lignin, animal manure, municipal solid waste, municipal sewage, or a combination thereof.

[0195] In some embodiments, the solid biochar-containing material contains about 65% to about 95% by weight of fixed carbon. In some embodiments, the solid biochar-containing material contains about 70% to about 90% by weight of fixed carbon.

[0196] In some embodiments, a thermally controlled multistage separation system comprises one or more filters, an absorption bed having a solid medium, an absorption bed having a liquid medium, an adsorption bed having a solid medium, a dry scrubber, a wet scrubber, a venturi scrubber, a centrifuge, a cyclone, a quench unit, a reactive condenser, a distillation column, a reactive distillation column, an evaporator, a reactive evaporator, a heat exchanger, a fan separator, an electrostatic precipitator, a demister, or a combination thereof, configured to produce pyrolysis condensate and a gas stream from pyrolysis vapor.

[0197] In some embodiments, a thermally controlled multistage separation system comprises a cyclone unit configured to separate solid biochar-containing material from pyrolysis steam.

[0198] In some embodiments, the quench unit is configured to expose pyrolysis vapor to water, thereby generating pyrolysis condensates.

[0199] In some embodiments, the thermally controlled multistage separation system further comprises a demister unit configured to recover residual liquid from the gas stream. In some embodiments, the residual liquid is combined with the pyrolysis condensate. The thermally controlled multistage separation system may be configured to capture multiple liquid fractions. The thermally controlled multistage separation system may be configured to capture multiple liquid fractions according to molecular weight, boiling point, polarity, or a combination thereof.

[0200] In some embodiments, the thermally controlled multistage separation system further comprises a demister unit configured to recover residual liquid from a gas stream derived from pyrolysis vapor. The residual liquid is optionally combined with pyrolysis condensate.

[0201] In some embodiments, the thermally controlled multistage separation system is configured to capture multiple liquid fractions. These liquid fractions can be separated according to, for example, molecular weight, boiling point, polarity, water content, or a combination thereof. The pyrolysis condensate may contain at least two of the multiple liquid fractions in a combined form. In some embodiments, at least one of the multiple liquid fractions is recovered as a light byproduct that does not form part of the pyrolysis condensate.

[0202] In some embodiments, the polyphenol material contains about 20% to about 80% by weight of fixed carbon. In some embodiments, the polyphenol material contains about 40% to about 60% by weight of fixed carbon. In various embodiments, the polyphenol material contains about, at least about, or at most about 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, or 80% by weight of fixed carbon, including any intervening range.

[0203] In some embodiments, the polyphenol material has a weight-average molecular weight M ranging from approximately 75 g / mol to approximately 50,000 g / mol. w It has. In one embodiment, the polyphenol material is M, which is about 75 g / mol to about 1,000 g / mol. w It has. In one embodiment, the polyphenol material has a concentration of about 1,000 g / mol to about 50,000 g / mol. w In various embodiments, the polyphenol material has a concentration of approximately, at least approximately, or at most approximately 100, 200, 300, 400, 500, 1,000, 1,500, 2,000, 2,500, 3,000, 4,000, 5,000, 10,000, 15,000, 20,000, 25,000, 30,000, 35,000, 40,000, 45,000, or 50,000 g / mol, including any intervening range. w It has a high M. Due to the polycondensation reaction, which is thermodynamically and kinetically accelerated by the removal of water during drying and results in a large number of monomer units within the polymer chain, the polyphenol material has a high M. w It is believed that it may possess this characteristic.

[0204] In some embodiments, the polyphenolic material has a viscosity of about 1 cP to about 1000 cP at 25°C. In certain embodiments, the polyphenolic material has a viscosity of about 10 cP to about 500 cP at 25°C. In various embodiments, the polyphenolic material has a viscosity of about or at least about 1, 2, 3, 4, 5, 10, 15, 20, 25, 50, 75, 100, 150, 200, 250, 300, 400, 500, 600, 700, 800, 900, or 1000 cP at 25°C. An exemplary polyphenolic material with high viscosity is shown in Figure 3.

[0205] In some embodiments, the polyphenolic material contains from about 1 wt% to about 60 wt% water. This water content refers to bulk free water as well as adsorbed water (·H₂O), but does not refer to potential water formation from the -H and -OH components in the polyphenolic material. In certain embodiments, the polyphenolic material contains from about 5 wt% to about 25 wt% water. In various embodiments, the polyphenolic material contains about, at least about, or at most about 0.1, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, or 70 wt% water, including any intervening ranges. Certain embodiments utilize a polyphenolic material that is a relatively dry pyrolysis condensate fraction. Such polyphenolic materials may contain no more than about 5 wt% water, no more than about 4 wt% water, no more than about 3 wt% water, no more than about 2 wt% water, or no more than about 1 wt% water. In principle, a polyphenolic material that is essentially free of water can be recovered, for example, by using a molecular sieve.

[0206] In some embodiments, the intermediate mixture has a weight ratio of polyphenol material to solid biochar-containing material selected from about 0.01 to about 5. (For example) A weight ratio of 0.5 means 1 part polyphenol material to 2 parts solid biochar-containing material by weight. In some embodiments, the intermediate mixture has a weight ratio of polyphenol material to solid biochar-containing material selected from about 0.05 to about 2, for example, about 0.1 to about 1, or about 0.2 to about 0.8. In some embodiments, the intermediate mixture has a weight ratio of polyphenol material to solid biochar-containing material greater than 5, provided that the polyphenol material is sufficiently dried before the intermediate mixture is produced.

[0207] The densification unit may comprise, for example, an extruder, a briquette, a pellet mill, or a combination thereof. The densification unit may essentially consist of, for example, an extruder, a briquette, a pellet mill, or a combination thereof. In some embodiments, the densification unit is an extruder, such as a single-screw or twin-screw extruder. When an extruder is used as the densification unit, the biochar pellets may be called extruded articles, one example of which is shown in Figure 4 (photograph of a cylindrical extruded article).

[0208] In some methods, the polyphenol material is heated before contact with the solid biochar-containing material. The polyphenol material can be heated to a temperature of, for example, at least about 150°C, at least about 200°C, or at least about 250°C.

[0209] In some methods, the solid biochar-containing material is heated before contact with the polyphenol material. The temperature of the solid biochar-containing material can be controlled to be within ±100°C or ±50°C of the pyrolysis reactor before contact with the polyphenol material. Typically, the solid biochar-containing material is slightly cooled after the pyrolysis reactor, so its temperature upon contact with the polyphenol material is usually somewhat lower than the pyrolysis temperature; however, heating can be used to raise the temperature of the solid biochar-containing material even higher than the pyrolysis temperature.

[0210] In some methods, the intermediate mixture is heated before step (d).

[0211] The densification unit can be operated at a densification temperature higher than 100°C, for example, at least 150°C or at least 200°C. In various embodiments, the densification temperature is about, at least about, or at most about 100°C, 110°C, 120°C, 130°C, 140°C, 150°C, 160°C, 170°C, 180°C, 190°C, 200°C, 210°C, 220°C, 230°C, 240°C, 250°C, 260°C, 270°C, 280°C, 290°C, or 300°C, including any intervening range.

[0212] The densification unit can be operated at densification pressures of approximately, at least approximately, or at most approximately 1 bar, 2 bar, 3 bar, 4 bar, 5 bar, 10 bar, 15 bar, 20 bar, 25 bar, 30 bar, 35 bar, 40 bar, 45 bar, or 50 bar, including any intervening areas.

[0213] The densification unit can be operated for densification times of approximately, at least approximately, or at most approximately 1 minute, 5 minutes, 10 minutes, 15 minutes, 30 minutes, or 60 minutes, including any intervening areas.

[0214] In some embodiments, in step (d), the densification unit is configured to generate a concentrated concentration of polyphenol material on the outer shell of the biochar pellet precursor.

[0215] In one embodiment, steps (d) and (e) are combined, and the densification unit is configured not only for densification but also for drying the biochar pellet precursor.

[0216] In some embodiments, the biochar pellets have a water content of 0% to about 20% by weight. In some embodiments, the biochar pellets have a water content of 0% to about 10% by weight, or 0% to about 5% by weight, or 0% to about 2% by weight, or 0% to about 1% by weight. In some embodiments, the biochar pellets have a water content of about 1% to about 2% by weight. In various embodiments, the biochar pellets have a water content of about or at most about 0.1, 0.2, 0.5, 1, 1.5, 2, 2.5, 3, 4, 5, 6, 7, 8, 9, or 10% by weight, including any intervening ranges.

[0217] In some embodiments, the biochar pellets have a total ash content of 1% to about 5% by weight. In some embodiments, the biochar pellets have an ash content of about or at most about 0.1, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10% by weight, including any intervening ranges.

[0218] In some embodiments, the biochar pellets have a fixed carbon content of about 50% to about 99% by weight of fixed carbon on a dry basis. In some embodiments, the biochar pellets have a fixed carbon content of about 60% to about 90% or about 70% to about 80% by weight of fixed carbon on a dry basis.

[0219] As used herein, the 24-hour water absorption rate is measured by completely immersing a sample of biochar pellets in liquid deionized water at 25°C and 1 bar for 24 hours, and then measuring the weight change of the biochar pellets. In the context related to the water absorption rate of biochar pellets, "about 20% by weight" is intended to encompass a water absorption rate as high as 20.49% by weight. In some embodiments, the 24-hour water absorption rate of the biochar pellets, measured at 25°C and 1 bar, is no more than about 10% by weight. In certain embodiments, the 24-hour water absorption rate of the biochar pellets, measured at 25°C and 1 bar, is no more than about 6% by weight. In certain embodiments, the 24-hour water absorption rate of the biochar pellets, measured at 25°C and 1 bar, is greater than 20% by weight, greater than 25% by weight, greater than 30% by weight, or greater than 35% by weight. In various embodiments, the 24-hour water absorption rate of the biochar pellets, measured at 25°C and 1 bar, including any intervening ranges (e.g., 6 to 15% by weight), is about or at most about 40, 39, 38, 37, 36, 35, 34, 33, 32, 31, 30, 29, 28, 27, 26, 25, 24, 23, 22, 21, 20, 19, 18, 17, 16, 15, 14, 13, 12, 11, 10, 9.5, 9, 8.5, 8, 7.5, 7, 6.5, 6, 5.5, or 5% by weight.

[0220] In some embodiments, the biochar pellets have at least about 100 lb at 25°C f / in 2 of pellet compressive strength. In certain embodiments, the biochar pellets have at least about 200 lb at 25°C f / in 2 of pellet compressive strength. In various embodiments, the biochar pellets have, including any intervening ranges, about or at least about 50, 75, 100, 125, 150, 175, 200, 225, 250, 275, or 300 lb at 25°C f / in 2 of pellet compressive strength.

[0221] In some embodiments, the biochar pellets have at least about 100 lb f / in2 is characterized by a soak / dry pellet compressive strength, wherein the soak / dry pellet compressive strength is measured by immersing the biochar pellets in water at 25°C for 24 hours, and then drying the biochar pellets in air at 105°C for 24 hours. In certain embodiments, the biochar pellets have at least about 200 lb f / in 2 of soak / dry pellet compressive strength. In various embodiments, the soak / dry pellet compressive strength is about or at least about 50, 75, 100, 125, 150, 175, 200, 225, 250, 275, or 300 lb, including any intervening ranges f / in 2 .

[0222] In some embodiments, the biochar pellets are characterized by a bulk density of at least about 40 lb / ft 3 . In certain embodiments, the biochar pellets are characterized by a bulk density of at least about 45 lb / ft 3 or at least about 50 lb / ft 3 . In various embodiments, the biochar pellets are characterized by a bulk density of about or at least about 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, or 50 lb / ft, including any intervening ranges 3 .

[0223] In some embodiments, the biochar pellets contain no pellet binder other than polyphenolic materials. In these embodiments, the polyphenolic materials may or may not explicitly function as chemical binders. In other embodiments, the biochar pellets contain a pellet binder. The pellet binders are discussed later herein.

[0224] In some embodiments, the biochar pellets further contain wood flour. The wood flour consists of relatively small particles of hardwood or softwood, which can range, for example, from about 1 micron to about 1000 microns, or from about 10 microns to about 500 microns. Typically, wood flour can be added to biomass-containing raw materials, solid biochar-containing materials, intermediate mixtures, biochar pellet precursors, or biochar pellets. In some embodiments using wood flour, it is added to the intermediate mixture so that the fine powder is compressed and densified within the pellet precursor. In some embodiments, the wood flour itself is first coated with a polyphenol material before being introduced into the process. In these embodiments, the polyphenol material may be the same as that captured in step (c), or it may be a polyphenol material from a different source.

[0225] In some embodiments, the biochar pellets are subjected to further thermal decomposition to increase the fixed carbon content of the biochar pellets. Further thermal decomposition may be particularly effective in increasing the fixed carbon content of the portion of the biochar pellets containing polyphenol material.

[0226] In some modifications, the present invention provides a method for producing biochar pellets. In one modification, the method for producing biochar pellets is (a) to thermally decompose a biomass-containing raw material in a thermal decomposition reactor, thereby generating a solid biochar-containing material and thermal decomposition steam; (b) To provide polyphenol materials; (c) Contacting a solid biochar-containing material with a polyphenol material to produce an intermediate mixture; (d) Introducing the intermediate mixture into a densification unit to generate a biochar pellet precursor; and (e) to at least partially dry the biochar pellet precursor, thereby producing biochar pellets. : includes, Here, the biochar pellets are characterized by a 24-hour water absorption rate of approximately 20% by weight or less, as measured at 25°C and 1 bar.

[0227] Figure 2 is a simplified block flow diagram of a method for producing biochar pellets from biomass using externally supplied polyphenol material in several embodiments.

[0228] Biomass-containing raw materials may be selected from coniferous wood chips, hardwood chips, wood harvest residues, tree branches, tree stumps, leaves, bark, sawdust, corn, corn stover, wheat, wheat straw, rice, rice straw, sugarcane, sugarcane bagasse, sugarcane straw, energy cane, sugar beet, sugar beet pulp, sunflower, sorghum, canola, algae, Japanese pampas grass, alfalfa, switchgrass, fruits, fruit shells, fruit stems, fruit peels, fruit seeds, vegetables, vegetable shells, vegetable stems, vegetable peels, vegetable seeds, grape pomace, almond shells, pecan shells, coconut shells, coffee grounds, food waste, commercial waste, grass pellets, hay pellets, wood pellets, cardboard, paper, paper pulp, paper packaging, paper scraps, food packaging, construction or demolition waste, railway sleepers, lignin, animal manure, municipal solid waste, municipal sewage, or combinations thereof.

[0229] Solid biochar-containing materials may contain approximately 65% ​​to 95% by weight of fixed carbon, for example, approximately 70% to 90% by weight of fixed carbon.

[0230] Polyphenol materials can be produced in situ from the processes already described above; that is, pyrolysis condensates can be recovered as polyphenol materials. Alternatively, polyphenol materials may be supplied from an external source. The external source may be a place where any of the processes disclosed herein are carried out. The external source may be a commercial chemical company. The external source may be a biofinery that produces lignin or lignin-derived by-products. Lignin is the most abundant natural polyphenol. Lignin can be obtained from a biofinery plant using pyrolysis, gasification, acid hydrolysis, enzymatic hydrolysis, chemical pulping, mechanical pulping, thermochemical pulping, or other processes. Another external source of polyphenol materials may be a food or nutritional supplement manufacturing plant, for example, a manufacturing plant that processes blueberries, plums, cherries, apples, strawberries, blackcurrants, black olives, dark chocolate, black tea, coffee, hazelnuts, or pecans, all of which are relatively rich in polyphenols. Another external source of polyphenol materials may be a dye manufacturing plant.

[0231] The polyphenol material may contain approximately 20% to 80% by weight of fixed carbon, for example, approximately 40% to 60% by weight of fixed carbon.

[0232] The polyphenol material may have a weight-average molecular weight of approximately 75 g / mol to approximately 50,000 g / mol, for example, approximately 75 g / mol to approximately 1,000 g / mol, or approximately 1,000 g / mol to approximately 50,000 g / mol.

[0233] Polyphenol materials can have a viscosity of approximately 1 cP to 1000 cP at 25°C, for example, approximately 10 cP to 500 cP.

[0234] The polyphenol material may contain approximately 1% to 60% by weight of water, for example, approximately 5% to 40% by weight of water.

[0235] In some methods, the intermediate mixture has a weight ratio of polyphenol material to solid biochar-containing material selected from about 0.01 to about 5. In other methods, the intermediate mixture has a weight ratio of polyphenol material to solid biochar-containing material selected from about 0.05 to about 2, for example, about 0.1 to about 1, or about 0.2 to about 0.8.

[0236] In some methods, the polyphenol material is heated before contact with the solid biochar-containing material. The polyphenol material can be heated to a temperature of, for example, at least about 150°C, at least about 200°C, or at least about 250°C.

[0237] In some methods, the solid biochar-containing material is heated before contact with the polyphenol material. The solid biochar-containing material can be controlled to be within ±100°C or ±50°C of the pyrolysis reactor temperature before contact with the polyphenol material.

[0238] In some methods, the intermediate mixture is heated before step (d).

[0239] In some ways, the densification unit comprises an extruder, a bricketer, a pellet mill, or a combination thereof. In some ways, the densification unit essentially consists of an extruder, a bricketer, a pellet mill, or a combination thereof. In one way, the densification unit is an extruder.

[0240] The densification unit can be operated at a densification temperature higher than 100°C, for example, at least 150°C or at least 200°C.

[0241] In some methods, in step (d), the densification unit is configured to generate a concentrated concentration of polyphenol material in the outer shell of the biochar pellet precursor. In these embodiments, the concentration of the polyphenol material in the outer shell is, for example, at least 1%, 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, or 50% higher than the concentration of the polyphenol material in the inner core. The outer shell can be defined as a shell having a thickness of 1%, 5%, or 10% of the effective diameter of the biochar pellet precursor.

[0242] In some methods, steps (d) and (e) are combined, and the densification unit is configured for both drying and densifying the biochar pellet precursor. For example, a vented extruder can be used to remove water from the extrusion zone, thereby drying the material being densified.

[0243] In some cases, the biochar pellets have a water content of 0% to about 20% by weight of water, for example, 0% to about 10% by weight of water, or 0% to about 5% by weight of water, or 0% to about 2% by weight of water, or 0% to about 1% by weight of water.

[0244] In some methods, the biochar pellets have a fixed carbon content of approximately 50% to 99% by weight of fixed carbon on a dry basis. In other methods, the biochar pellets have a fixed carbon content of approximately 60% to 90% by weight of fixed carbon on a dry basis, or approximately 70% to 80% by weight of fixed carbon on a dry basis.

[0245] In some methods, the 24-hour water absorption rate of biochar pellets is approximately 10% by weight or less, measured at 25°C and 1 bar. In another method, the 24-hour water absorption rate of biochar pellets is approximately 6% by weight or less, measured at 25°C and 1 bar.

[0246] In some methods, biochar pellets are at least about 100 lb at 25°C. f / in2 It is characterized by a pellet compressive strength of at least about 200 lb at 25°C. In one method, the biochar pellets are characterized by a pellet compressive strength of at least about 200 lb at 25°C. f / in 2 It is characterized by its pellet compressive strength.

[0247] In some embodiments, the biochar pellets are at least about 100 lb f / in 2 The immersion / drying pellet compressive strength is characterized by the immersion / drying pellet compressive strength, which is measured by immersing the biochar pellets in water at 25°C for 24 hours, and then drying the biochar pellets in air at 105°C for 24 hours. In one embodiment, the biochar pellets are at least about 200 lb f / in 2 It is characterized by the immersion / drying pellet compressive strength.

[0248] In some cases, biochar pellets are at least about 40 lb / ft 3 It is characterized by a bulk density of at least about 45 lb / ft. 3 Or at least about 50 lbs / ft 3 It is characterized by its bulk density.

[0249] In some methods, biochar pellets do not contain pellet binders other than polyphenol materials.

[0250] In some methods, the biochar pellets further contain wood powder.

[0251] In some methods, biochar pellets are subjected to further thermal decomposition to increase the fixed carbon content of the biochar pellets.

[0252] Some variations of the present invention are (a) to thermally decompose a biomass-containing raw material in a thermal decomposition reactor, thereby generating thermal decomposition steam containing solid biochar-containing material and polyphenol material; (b) Introducing pyrolysis vapor into a thermally controlled multistage separation system configured to recover pyrolysis condensates in liquid form separated from non-condensable gases; (c) Contacting a solid biochar-containing material with a polyphenol material to produce an intermediate mixture; (d) Introducing the intermediate mixture into a densification unit to generate a biochar pellet precursor; and (e) to at least partially dry the biochar pellet precursor, thereby producing biochar pellets. We provide biochar pellets manufactured by a process that includes: Here, the biochar pellets are characterized by a 24-hour water absorption rate of approximately 20% by weight or less, as measured at 25°C and 1 bar.

[0253] In some embodiments, the solid biochar-containing material contains about 65% to about 95% by weight of fixed carbon. Biochar pellets may contain, for example, about 60% to about 90% by weight of fixed carbon.

[0254] In some embodiments, the intermediate mixture has a weight ratio of polyphenol material to solid biochar-containing material selected from about 0.01 to about 5.

[0255] In some embodiments, the 24-hour water absorption rate of the biochar pellets is approximately 10% by weight or less, as measured at 25°C and 1 bar.

[0256] In some embodiments, the biochar pellets are at least about 40 lb / ft 3 It is characterized by its bulk density.

[0257] In some embodiments, the biochar pellets are at least about 100 lb at 25°C. f / in 2 It is characterized by its pellet compressive strength.

[0258] In some embodiments, the biochar pellets are at least about 100 lbf / in 2 The immersion / drying pellet compressive strength is characterized by the following: the immersion / drying pellet compressive strength is measured by immersing the biochar pellets in water at 25°C for 24 hours, and then drying the biochar pellets in air at 105°C for 24 hours.

[0259] Some variations of the present invention are (a) to thermally decompose a biomass-containing raw material in a thermal decomposition reactor, thereby generating a solid biochar-containing material and thermal decomposition steam; (b) Providing polyphenol material (e.g., from an external source); (c) Contacting a solid biochar-containing material with a polyphenol material to produce an intermediate mixture; (d) Introducing the intermediate mixture into a densification unit to generate a biochar pellet precursor; and (e) to at least partially dry the biochar pellet precursor, thereby producing biochar pellets. We provide biochar pellets manufactured by a process that includes: Here, the biochar pellets are characterized by a 24-hour water absorption rate of approximately 20% by weight or less, as measured at 25°C and 1 bar.

[0260] In some embodiments, the solid biochar-containing material contains about 65% to about 95% by weight of fixed carbon, or the intermediate mixture has a weight ratio of polyphenol material to solid biochar-containing material selected from about 0.01 to about 5.

[0261] In some embodiments, the 24-hour water absorption rate of the biochar pellets is less than or equal to about 10% by weight, measured at 25°C and 1 bar; the biochar pellets have a water content of at least about 40 lb / ft 3 Characterized by a bulk density; or the biochar pellets are at least about 100 lb at 25°C. f / in 2 It is characterized by its pellet compressive strength.

[0262] Further variations of the present invention include: (a) Solid biochar-containing materials; (b) Polyphenol materials; (c) Optionally, ash content; and (d) Optionally, water : Provides biochar pellets that include, essentially consist of, or comprise these Here, the weight ratio of the polyphenol material to the solid biochar-containing material is selected from approximately 0.01 to approximately 5; Here, the biochar pellets contain approximately 50% to 99% fixed carbon by weight; and Here, the biochar pellets are characterized by a 24-hour water absorption rate of approximately 20% by weight or less, as measured at 25°C and 1 bar.

[0263] Another variation of the present invention is: (a) Solid biochar-containing materials; (b) Polyphenol materials; (c) Optionally, ash content; and (d) Optionally, water We provide biochar pellets that include: Here, the biochar pellets do not contain any external binders other than polyphenol materials; Here, the weight ratio of the polyphenol material to the solid biochar-containing material is selected from approximately 0.01 to approximately 5; Here, the biochar pellets contain approximately 50% to 95% fixed carbon by weight; and Here, the biochar pellets are characterized by a 24-hour water absorption rate of approximately 20% by weight or less, as measured at 25°C and 1 bar.

[0264] An example of biochar pellets is shown in Figure 4 (see Example 2 in this specification).

[0265] In some embodiments of biochar pellets, the biochar pellets contain about 60% to about 90% by weight of fixed carbon, for example, about 65% to about 85% by weight of fixed carbon, or about 70% to about 80% by weight of fixed carbon. These concentration values ​​are on a dry basis and represent the percentage of biochar pellets that are fixed carbon, not the percentage of carbon that is fixed carbon. In various embodiments, the biochar pellets contain, on a dry basis, fixed carbon at concentrations of about, at least about, or at most about 60, 65, 70, 75, 80, 85, 90, or 95% by weight, including any intervening ranges.

[0266] In some embodiments of biochar pellets, the biochar pellets contain about 60% to about 99% by weight of total carbon, including fixed carbon and volatile carbon (e.g., furfural). These concentration values ​​are based on dryness. In various embodiments, the biochar pellets contain, on a dry basis, total carbon at concentrations of about, at least about, or at most about 60, 65, 70, 75, 80, 85, 90, 91, 92, 93, 94, 95, 96, 97, 98, or 99% by weight, including any intervening ranges.

[0267] In various embodiments of biochar pellets, the polyphenol material has a weight-average molecular weight M ranging from approximately 75 g / mol to approximately 50,000 g / mol. w It has. In one embodiment, the polyphenol material is M, which is about 75 g / mol to about 1,000 g / mol. w It has. In one embodiment, the polyphenol material has a concentration of about 1,000 g / mol to about 50,000 g / mol. w In various embodiments, the polyphenol material has a concentration of approximately, at least approximately, or at most approximately 100, 200, 300, 400, 500, 1,000, 1,500, 2,000, 2,500, 3,000, 4,000, 5,000, 10,000, 15,000, 20,000, 25,000, 30,000, 35,000, 40,000, 45,000, or 50,000 g / mol, including any intervening range. w It has.

[0268] In some embodiments of biochar pellets, the polyphenol material has a viscosity of about 1 cP to about 1000 cP at 25°C, for example, about 10 cP to about 500 cP. In various embodiments, the polyphenol material has a viscosity of about or at least about 1, 2, 3, 4, 5, 10, 15, 20, 25, 50, 75, 100, 150, 200, 250, 300, 400, 500, 600, 700, 800, 900, or 1000 cP at 25°C.

[0269] In some embodiments of biochar pellets, the total carbon in the polyphenol material is 14 C / 12 As determined from measurements of 14C isotope ratios, it is at least 50%, at least 75%, at least 90%, or 100% regenerative.

[0270] In some embodiments of the biochar pellets, the weight ratio of the polyphenol material to the solid biochar-containing material is selected from about 0.05 to about 2. In one embodiment of the biochar pellets, the weight ratio of the polyphenol material to the solid biochar-containing material is selected from about 0.2 to about 0.8.

[0271] In some embodiments of biochar pellets, the ash content of the biochar pellets is less than 5% by weight, for example, less than 3% by weight or less than 1% by weight. In various embodiments, the ash content of the biochar pellets is about or at most about 0.1, 0.5, 1, 2, 3, 4, or 5% by weight, including any intervening range.

[0272] In some embodiments of the biochar pellets, the moisture content of the biochar pellets is less than 20% by weight, for example, less than 15% by weight, less than 10% by weight, less than 5% by weight, or less than 1% by weight. In various embodiments, the moisture content of the biochar pellets is about or at most about 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, or 15% by weight, including any intervening range (e.g., 2-8% by weight of H2O).

[0273] The 24-hour water absorption rate of biochar pellets, measured at 25°C and 1 bar, may be approximately 20% by weight or less. Here, "approximately 20% by weight" is intended to encompass a water absorption rate of approximately 20.49% by weight. In some embodiments, the 24-hour water absorption rate of biochar pellets, measured at 25°C and 1 bar, is approximately 10% by weight or less. In some embodiments, the 24-hour water absorption rate of biochar pellets, measured at 25°C and 1 bar, is approximately 6% by weight or less. In various embodiments, the 24-hour water absorption rate of biochar pellets, measured at 25°C and 1 bar, is approximately or at most approximately 20, 19, 18, 17, 16, 15, 14, 13, 12, 11, 10, 9.5, 9, 8.5, 8, 7.5, 7, 6.5, 6, 5.5, or 5% by weight, including any intervening range. As mentioned earlier, in one embodiment, the 24-hour water absorption rate of the biochar pellets, measured at 25°C and 1 bar, is greater than 20% by weight, which may be acceptable in some circumstances.

[0274] Biochar pellets can be exceptionally mechanically durable. In some embodiments, biochar pellets can withstand at least about 100 lb at 25°C. f / in 2 The pellet is characterized by its compressive strength. The compressive strength of the pellet is calculated by dividing the compressive force at the time of pellet fracture by the lateral surface area of ​​the biochar pellet. The lateral surface area of ​​the biochar pellet is the area along the length of the pellet exposed to the compressive force, and does not include the sides of the pellet that are not exposed to the compressive force. For perfectly spherical pellets, the lateral surface area is the surface area of ​​the sphere. For cylindrical pellets, the lateral surface area is the area along the length of the cylinder, and does not include the areas at both ends of the cylinder. The compressive strength of the pellet can be measured, for example, using a laboratory tensile and compressive load tester. Pellet fracture, also known as pellet breakage or pellet crushing, can be automatically detected by a laboratory tensile and compressive load tester.

[0275] In one embodiment, the biochar pellets are at least about 150 lb at 25°C. f / in 2 The pellets are characterized by a compressive strength of approximately 50, 75, 100, 125, 150, 175, 200, 225, 250, 275, or 300 lb at 25°C, including any intervening range. f / in 2 It is characterized by the pellet compressive strength of lb. f / in 2 The unit (psi) is pounds of force per square inch.

[0276] In some embodiments of biochar pellets, the biochar pellets are at least about 100 lb f / in 2 The immersion / drying pellet compressive strength is characterized by the immersion / drying pellet compressive strength, which is measured by immersing the biochar pellets in water at 25°C for 24 hours, and then drying the biochar pellets in air at 105°C for 24 hours. In one embodiment, the immersion / drying pellet compressive strength is at least about 200 lb f / in 2 That is the case.

[0277] Pellet compressive strength can also be measured after thermal exposure, which may be important for understanding the mechanical durability of the pellets in use at high temperatures. For example, pellet compressive strength can be measured after thermal exposure at 900°C for 20 minutes in a low-oxygen environment. The pellet compressive strength after thermal exposure can be measured, for example, using a laboratory tensile and compressive load tester after the test sample has cooled to room temperature (approximately 25°C). In some embodiments, the pellet compressive strength after 20 minutes at 900°C is at least approximately 30 lb, which is measured after cooling to 25°C. f / in 2 Or at least about 60 lb f / in 2In various embodiments, the pellet compressive strength after 20 minutes at 900°C is approximately or at least approximately 10, 20, 30, 40, 50, 60, 70, 80, or 90 lb, including any intervening range. f / in 2 That is the case.

[0278] In some embodiments, the biochar pellets are at least about 40 lb / ft 3 It is characterized by a bulk density of at least about 45 lb / ft. 3 Or at least about 50 lbs / ft 3 The bulk density is characterized by a certain density. In various embodiments, the biochar pellets, including any intervening range, have a bulk density of approximately or at least approximately 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, or 50 lb / ft. 3 It is characterized by its bulk density.

[0279] In some embodiments, the biochar pellets do not contain any pellet binder other than the polyphenol material. In these embodiments, the polyphenol material may or may not explicitly function as a chemical binder. In other embodiments, the biochar pellets contain a pellet binder, which will be discussed later in this specification.

[0280] In some embodiments of biochar pellets, the biochar pellet has a concentrated polyphenol material in its outer shell and a concentrated solid biochar-containing material in its inner core.

[0281] In some embodiments of the biochar pellets, the biochar pellets further contain wood flour. If the biochar pellets contain wood flour, the weight percentage of wood flour may be about, at least about, or at most about 1, 2, 3, 4, 5, 10, 15, 20, 25, 30, 35, 40, 45, or 50% by weight of wood flour, based on the dry basis of the wood flour and the dry basis of the biochar pellets.

[0282] Wood powder may be characterized by an average wood powder particle size of approximately 1 micron to approximately 500 microns, for example, approximately 10 microns to approximately 200 microns. Wood powder may be characterized by an average wood powder particle size of approximately, at least approximately, or at most approximately 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 15, 20, 25, 30, 35, 40, 44, 45, 50, 60, 70, 80, 90, 100, 125, 150, 175, 200, 225, 250, 275, 300, 350, 400, 450, or 500 microns, including any intervening ranges. Even when the average wood powder particle size is within the range of approximately 1 to 500 microns, wood powder smaller than 1 micron or larger than 500 microns may be present.

[0283] Particle size can be measured by various techniques, including dynamic light scattering, laser diffraction, image analysis, or sieving. Dynamic light scattering is a non-invasive and well-established technique for measuring particle size and size distribution, typically in the submicron range, and in modern techniques down to 1 nanometer. Laser diffraction is a widely used particle sizing technique for materials ranging in size from several hundred nanometers to several millimeters. Exemplary dynamic light scattering and laser diffraction devices for measuring particle size are available from Malvern Instruments, Worcestershire, UK. Image analysis for estimating particle size and distribution can be performed directly on micrographs, scanning electron microscope images, or other images. Finally, sieving is a conventional technique for separating particles by size.

[0284] Wood powder can be spherical or non-spherical. It may be characterized by particle shapes selected from spheres, ellipsoids, cylinders, needle-like structures, plate-like structures, polyhedra, amorphous structures, or combinations thereof. Wood powder can exist in a non-aggregated state, i.e., as individual particles.

[0285] The wood powder can be uniformly dispersed throughout the biogenic matrix. Uniform dispersion of the wood powder means that, statistically speaking, the concentration of wood powder (e.g., about 5% by weight) is nearly identical at any point within the biochar pellet. In some embodiments, the wood powder is present at a higher concentration in the bulk phase (inside the pellet) compared to the pellet surface. In other embodiments, the wood powder is present at a lower concentration in the bulk phase compared to the pellet surface. In one embodiment, the wood powder is present at nearly the same concentration in the bulk phase and on the pellet surface.

[0286] The wood flour may be characterized by an average ash content of about 5% by weight or less on a dry basis. In some embodiments, the wood flour is characterized by an average ash content of about 4% by weight or less on a dry basis. In one embodiment, the wood flour is characterized by an average ash content of about 2% by weight or less on a dry basis. In one embodiment, the wood flour is characterized by an average ash content of about 1% by weight or less on a dry basis.

[0287] In some embodiments of biochar pellets, the total carbon in the biochar pellet is the total carbon 14 C / 12 As determined from the measurement of the 1C isotope ratio, at least 50% is renewable. In one embodiment, the total carbon in the biochar pellet is the total carbon 14 C / 12 As determined from the measurement of the 1C isotope ratio, at least 90% is renewable. In a specific embodiment, the total carbon in the biochar pellet is the total carbon 14 C / 12 It is 100% regenerative, as determined by the measurement of the 1C isotope ratio.

[0288] In some embodiments, the 24-hour water absorption rate of the biochar pellets is approximately 6% by weight or less, measured at 25°C and 1 bar, and the total carbon content in the biochar pellets is 14 C / 12As determined from the measurement of the 1C isotope ratio, it is at least 90% renewable. In some embodiments, the 24-hour water absorption rate of the biochar pellets is less than or equal to about 6% by weight, measured at 25°C and 1 bar, and the total carbon in the biochar pellets is less than or equal to the total carbon 14 C / 12 It is 100% regenerative, as determined by the measurement of the 1C isotope ratio.

[0289] In some embodiments of biochar pellets, the biochar pellets have a pellet shape selected from the group consisting of spheres, cylinders, cubes, octagons, hexagons, honeycomb shapes, ellipses, cylindrical shapes, rod shapes, pillow shapes, lens shapes, amorphous granules, and combinations thereof.

[0290] In some embodiments of biochar pellets, the biochar pellets have a pellet size selected from about 1 mm to about 10 cm, which is calculated as the effective diameter of the biochar pellet. In various embodiments, the biochar pellets have an effective diameter of about, at least about, or at most about 1 mm, 2 mm, 3 mm, 4 mm, 5 mm, 6 mm, 7 mm, 8 mm, 9 mm, 10 mm, 15 mm, 2 cm, 3 cm, 4 cm, 5 cm, 6 cm, 7 cm, 8 cm, 9 cm, or 10 cm, including any intervening range.

[0291] In some embodiments of biochar pellets, the biochar pellets are characterized by low odor in accordance with ASTM D1296. Other relevant odor tests, including simple qualitative tests for odor, can be utilized. An olfactometer can be used to measure odor.

[0292] In some embodiments of biochar pellets, the biochar pellets are characterized as non-self-heating when subjected to a self-heating test in accordance with the Manual of Tests and Criteria, 7th Revision, 2019, United Nations, page 375, 33.4.6, Test N.4: "Test method for self-heating substances".

[0293] In some embodiments of biochar pellets, the biochar pellets are characterized by a negative slope of the 24-hour water absorption rate of the biochar pellets with respect to the fixed carbon content of the biochar pellets.

[0294] In some embodiments of biochar pellets, the biochar pellets are characterized by a parameter c selected from about 200 to about 1000, for example, about 400 to about 1000 or about 200 to about 800, where c is

number

[0295] In various embodiments, c is approximately, at least approximately, or at most approximately 200, 250, 300, 350, 400, 450, 500, 550, 600, 650, 700, 750, 800, 850, 900, 950, or 1000, including any intervening range.

[0296] In some embodiments of biochar pellets, the biochar pellets are characterized by a parameter x selected from about 500 to about 5000, for example, about 800 to about 4000 or about 1000 to about 2000, where x is

number

[0297] In various embodiments, x is approximately, at least approximately, or at most approximately 500, 600, 700, 800, 900, 1000, 1500, 2000, 2500, 3000, 3500, 4000, 4500, or 5000, including any intervening range.

[0298] Other variations of the present invention presuppose the addition of a polyphenol material after densification of a solid biochar-containing material. Some variations are methods for producing biochar pellets, (a) to thermally decompose a biomass-containing raw material in a thermal decomposition reactor, thereby generating thermal decomposition steam containing solid biochar-containing material and polyphenol material; (b) Introducing pyrolysis vapor into a thermally controlled multistage separation system configured to separate pyrolysis condensates in liquid form from a non-condensable gas (where the pyrolysis condensates contain polyphenol material); (c) Introducing solid biochar-containing material into a densification unit to generate a first biochar pellet precursor; (d) Adding a polyphenol material to the first biochar pellet precursor to produce a second biochar pellet precursor; and (e) to at least partially dry the second biochar pellet precursor, thereby producing biochar pellets. : includes, Here, we provide a method for biochar pellets characterized by a 24-hour water absorption rate of approximately 20% by weight or less, as measured at 25°C and 1 bar.

[0299] In some embodiments, the biomass-containing raw material is selected from coniferous wood chips, hardwood chips, wood harvest residues, tree branches, tree stumps, leaves, bark, sawdust, corn, corn stover, wheat, wheat straw, rice, rice straw, sugarcane, sugarcane bagasse, sugarcane straw, energy cane, sugar beet, sugar beet pulp, sunflower, sorghum, canola, algae, Japanese pampas grass, alfalfa, switchgrass, fruits, fruit shells, fruit stems, fruit peels, fruit seeds, vegetables, vegetable shells, vegetable stems, vegetable peels, vegetable seeds, grape pomace, almond shells, pecan shells, coconut shells, coffee grounds, food waste, commercial waste, grass pellets, hay pellets, wood pellets, cardboard, paper, paper pulp, paper packaging, paper scraps, food packaging, construction or demolition waste, railway sleepers, lignin, animal manure, municipal solid waste, municipal sewage, or a combination thereof.

[0300] Solid biochar-containing materials contain approximately 65% ​​to 95% by weight of fixed carbon or approximately 70% to 90% by weight of fixed carbon.

[0301] A thermally controlled multistage separation system may comprise one or more filters, an absorption bed with a solid medium, an absorption bed with a liquid medium, an adsorption bed with a solid medium, a dry scrubber, a wet scrubber, a venturi scrubber, a centrifuge, a cyclone, a quench unit, a reactive condenser, a distillation column, a reactive distillation column, an evaporator, a reactive evaporator, a heat exchanger, a fan separator, an electrostatic precipitator, a demister, or a combination thereof, configured to produce pyrolysis condensate and a gas stream from pyrolysis vapor.

[0302] In some cases, a thermally controlled multistage separation system comprises a cyclone unit configured to separate solid biochar-containing material from pyrolysis steam.

[0303] The quench unit may be configured to expose pyrolysis vapor to water to produce pyrolysis condensates.

[0304] The thermally controlled multistage separation system may further comprise a demister unit configured to recover residual liquid from the gas stream. The residual liquid can be combined with the pyrolysis condensate.

[0305] In some embodiments, a thermally controlled multistage separation system is configured to capture multiple liquid fractions. The thermally controlled multistage separation system may be configured to capture multiple liquid fractions according to molecular weight, boiling point, polarity, or a combination thereof.

[0306] The pyrolysis condensate may contain at least two of the multiple liquid fractions in a combined form. In some embodiments, at least one of the multiple liquid fractions is recovered as a light byproduct that does not form part of the pyrolysis condensate.

[0307] In some embodiments, the polyphenol material contains about 20% to about 80% by weight of fixed carbon or about 40% to about 60% by weight of fixed carbon.

[0308] In some embodiments, the polyphenol material has a weight-average molecular weight of approximately 75 g / mol to approximately 50,000 g / mol, approximately 75 g / mol to approximately 1,000 g / mol, or approximately 1,000 g / mol to approximately 50,000 g / mol.

[0309] In some embodiments, the polyphenol material has a viscosity of about 1 cP to about 1000 cP at 25°C, for example, about 10 cP to about 500 cP.

[0310] In some embodiments, the polyphenol material contains about 1% to about 60% by weight of water, for example, about 5% to about 40% by weight of water.

[0311] In some embodiments, the second biochar pellet precursor has a weight ratio of polyphenol material to the first biochar pellet precursor selected from about 0.01 to about 5, for example, about 0.05 to about 2, or about 0.2 to about 0.8.

[0312] The polyphenol material can be heated before contact with the first biochar pellet precursor. The polyphenol material can be heated to a temperature of at least about 150°C, at least about 200°C, or at least about 250°C.

[0313] The first biochar pellet precursor can be heated before contact with the polyphenol material.

[0314] The densification unit may comprise an extruder, a bricketer, a pellet mill, or a combination thereof. Essentially, the densification unit may consist of an extruder, a bricketer, a pellet mill, or a combination thereof.

[0315] The densification unit can be operated at a densification temperature higher than 100°C, for example, at least 150°C or at least 200°C.

[0316] In some embodiments, the biochar pellets have a water content of 0% to about 20% by weight, 0% to about 10% by weight, 0% to about 5% by weight, 0% to about 2% by weight, or 0% to about 1% by weight.

[0317] In some embodiments, the biochar pellets have a fixed carbon content of about 50% by weight to about 99% by weight on a dry basis, for example, about 60% by weight to about 90% by weight, or about 70% by weight to about 80% by weight.

[0318] In some embodiments, the 24-hour water absorption rate of the biochar pellets is approximately 10% by weight or less, measured at 25°C and 1 bar. In one embodiment, the 24-hour water absorption rate of the biochar pellets is approximately 6% by weight or less, measured at 25°C and 1 bar.

[0319] In some embodiments, the biochar pellets are at least about 100 lb at 25°C. f / in 2It is characterized by a pellet compressive strength of at least about 200 lb at 25°C. In one embodiment, the biochar pellets are characterized by a pellet compressive strength of at least about 200 lb at 25°C. f / in 2 It is characterized by its pellet compressive strength.

[0320] In some embodiments, the biochar pellets are at least about 100 lb f / in 2 The immersion / drying pellet compressive strength is characterized by the immersion / drying pellet compressive strength, which is measured by immersing the biochar pellets in water at 25°C for 24 hours, and then drying the biochar pellets in air at 105°C for 24 hours. In one embodiment, the immersion / drying pellet compressive strength is at least about 200 lb f / in 2 That is the case.

[0321] In some embodiments, the biochar pellets are at least about 40 lb / ft 3 , at least about 45 lb / ft 3 , or at least about 50 lb / ft 3 It is characterized by its bulk density.

[0322] In some embodiments, the biochar pellets do not contain any pellet binders other than polyphenol materials.

[0323] In some embodiments, the biochar pellets further contain wood powder.

[0324] In some embodiments, the biochar pellets are subjected to further thermal decomposition to increase the fixed carbon content of the biochar pellets.

[0325] Other variations include: (a) to thermally decompose a biomass-containing raw material in a thermal decomposition reactor, thereby generating thermal decomposition steam containing solid biochar-containing material and polyphenol material; (b) Introducing pyrolysis vapor into a thermally controlled multistage separation system configured to separate pyrolysis condensates in liquid form from a non-condensable gas (where the pyrolysis condensates contain polyphenol material); (c) Introducing solid biochar-containing material into a densification unit to generate a first biochar pellet precursor; (d) Adding a polyphenol material to the first biochar pellet precursor to produce a second biochar pellet precursor; and (e) to at least partially dry the second biochar pellet precursor, thereby producing biochar pellets. We provide biochar pellets manufactured by a method including: Here, the biochar pellets are characterized by a 24-hour water absorption rate of approximately 20% by weight or less, as measured at 25°C and 1 bar.

[0326] Some variations are methods for producing biochar pellets, (a) to thermally decompose a biomass-containing raw material in a thermal decomposition reactor, thereby generating a solid biochar-containing material and thermal decomposition steam; (b) To provide polyphenol materials; (c) Introducing solid biochar-containing material into a densification unit to generate a first biochar pellet precursor; (d) Adding a polyphenol material to the first biochar pellet precursor to produce a second biochar pellet precursor; and (e) to at least partially dry the second biochar pellet precursor, thereby producing biochar pellets. : includes, Here, we provide a method for biochar pellets characterized by a 24-hour water absorption rate of approximately 20% by weight or less, as measured at 25°C and 1 bar.

[0327] In some embodiments, the solid biochar-containing material contains approximately 70% to 90% by weight of fixed carbon.

[0328] In some embodiments, the polyphenol material contains approximately 20% to 80% by weight of fixed carbon.

[0329] In some embodiments, the polyphenol material contains approximately 40% to 60% by weight of fixed carbon.

[0330] In some embodiments, the polyphenol material has a weight-average molecular weight of approximately 75 g / mol to approximately 50,000 g / mol, approximately 75 g / mol to approximately 1,000 g / mol, or approximately 1,000 g / mol to approximately 50,000 g / mol.

[0331] In some embodiments, the polyphenol material has a viscosity of about 1 cP to about 1000 cP at 25°C, for example, about 10 cP to about 500 cP.

[0332] In some embodiments, the polyphenol material contains about 1% to about 60% by weight of water, for example, about 5% to about 40% by weight of water.

[0333] In some embodiments, the second biochar pellet precursor has a weight ratio of polyphenol material to the first biochar pellet precursor selected from about 0.01 to about 5, for example, about 0.05 to about 2, or about 0.2 to about 0.8.

[0334] The densification unit may comprise an extruder, a bricketer, a pellet mill, or a combination thereof. The densification unit may be selected from the group consisting of extruders, bricketers, pellet mills, and combinations thereof.

[0335] The densification unit can be operated at a densification temperature higher than 100°C, for example, at least 150°C or at least 200°C.

[0336] In some embodiments, the biochar pellets have a water content of 0% to about 20% by weight, 0% to about 10% by weight, 0% to about 5% by weight, 0% to about 2% by weight, or 0% to about 1% by weight.

[0337] Biochar pellets may have a fixed carbon content of approximately 50% by weight to approximately 99% by weight on a dry basis, for example, approximately 60% by weight to approximately 90% by weight, or approximately 70% by weight to approximately 80% by weight.

[0338] In some embodiments, the 24-hour water absorption rate of the biochar pellets is approximately 10% by weight or less, measured at 25°C and 1 bar. In one embodiment, the 24-hour water absorption rate of the biochar pellets is approximately 6% by weight or less, measured at 25°C and 1 bar.

[0339] In some embodiments, the biochar pellets are at least about 100 lb at 25°C. f / in 2 It is characterized by a pellet compressive strength of at least about 200 lb at 25°C. In one embodiment, the biochar pellets are characterized by a pellet compressive strength of at least about 200 lb at 25°C. f / in 2 It is characterized by its pellet compressive strength.

[0340] In some embodiments, the biochar pellets are at least about 100 lb f / in 2 The immersion / drying pellet compressive strength is characterized by the immersion / drying pellet compressive strength, which is measured by immersing the biochar pellets in water at 25°C for 24 hours, and then drying the biochar pellets in air at 105°C for 24 hours. In one embodiment, the immersion / drying pellet compressive strength is at least about 200 lb f / in 2 That is the case.

[0341] In some embodiments, the biochar pellets are at least about 40 lb / ft 3 , at least about 45 lb / ft3 , or at least about 50 lb / ft 3 It is characterized by its bulk density.

[0342] In some embodiments, the biochar pellets do not contain any pellet binders other than polyphenol materials.

[0343] In some embodiments, the biochar pellets further contain wood powder.

[0344] In some embodiments, the biochar pellets are subjected to further thermal decomposition to increase the fixed carbon content of the biochar pellets.

[0345] As mentioned earlier, in addition to polyphenol materials, a pellet binder may also be present in biochar pellets. The pellet binder, if present, may include, or may essentially consist of, starch, thermoplastic starch, cross-linked starch, starch polymer, cellulose, cellulose ether, hemicellulose, methylcellulose, chitosan, lignin, lactose, sucrose, glucose, maltodextrin, banana flour, wheat flour, wheat starch, soy flour, corn flour, wood flour, coal tar, coal granules, metcoke, asphalt, coal tar pitch, petroleum pitch, bitumen, pyrolysis tar, gilsonite, bentonite clay, borax, limestone, lime, wax, vegetable wax, baking soda, baking powder, sodium hydroxide, potassium hydroxide, iron ore concentrate, silica fume, gypsum, Portland cement, guar gum, xanthan gum, polyvidone, polyacrylamide, polylactide, phenol formaldehyde resin, vegetable resin, recycled single, recycled tire, recycled cardboard, recycled paper, derivatives thereof, or combinations thereof.

[0346] The pellet binder, if present, may be selected from the group consisting of starch, thermoplastic starch, cross-linked starch, starch polymer, cellulose, cellulose ether, hemicellulose, methylcellulose, chitosan, lignin, lactose, sucrose, glucose, maltodextrin, banana flour, wheat flour, wheat starch, soy flour, corn flour, wood flour, coal tar, coal powder, metcoke, asphalt, coal tar pitch, petroleum pitch, bitumen, pyrolysis tar, gilsonite, bentonite clay, borax, limestone, lime, wax, vegetable wax, baking soda, baking powder, sodium hydroxide, potassium hydroxide, iron ore concentrate, silica fume, gypsum, Portland cement, guar gum, xanthan gum, polyvidone, polyacrylamide, polylactide, phenol formaldehyde resin, vegetable resin, recycled single, recycled tire, recycled cardboard, recycled paper, derivatives thereof, or any combination thereof.

[0347] In some embodiments, the pellet binder may include, or be essentially, starch, thermoplastic starch, crosslinked starch, starch polymers, derivatives thereof, and any combination thereof. The pellet binder may optionally be crosslinked thermoplastic starch. The thermoplastic starch may be a reaction product of starch and polyol. The polyol may include, or be essentially, ethylene glycol, propylene glycol, glycerol, butanediol, butanetriol, erythritol, xylitol, sorbitol, and combinations thereof. The reaction product may be formed from an acid-catalyzed reaction. The acid may include, or be essentially, formic acid, acetic acid, lactic acid, citric acid, oxalic acid, uronic acid, glucuronic acid, or combinations thereof.

[0348] In some embodiments, the pellet binder is selected from the group consisting of starch, thermoplastic starch, crosslinked starch, starch polymers, derivatives thereof, and any combination thereof. The pellet binder may optionally be crosslinked thermoplastic starch. The thermoplastic starch may be the reaction product of starch and polyol. The polyol may be selected from the group consisting of ethylene glycol, propylene glycol, glycerol, butanediol, butanetriol, erythritol, xylitol, sorbitol, and combinations thereof. The reaction product may be formed from a reaction catalyzed by an acid. The acid may be selected from the group consisting of formic acid, acetic acid, lactic acid, citric acid, oxalic acid, uronic acid, glucuronic acid, and combinations thereof. Alternatively, the reaction product may be formed from a reaction catalyzed by a base.

[0349] The total carbon in biochar pellets is 14 C / 12 As determined from the measurement of the 1C isotope ratio, it may be at least 50% renewable. The total carbon in the biochar pellets is the total carbon 14 C / 12 As determined from measurements of the 1C isotope ratio, it may be at least 75% renewable. Surprisingly, the total carbon in the biochar pellets is the total carbon 14 C / 12 As determined from the measurement of the 1C isotope ratio, it may be at least 90% renewable. In various embodiments, the total carbon in the biochar pellet is the total carbon 14 C / 12 As determined from the measurement of the 1C isotope ratio, approximately or at least approximately 50%, 55%, 60%, 65%, 70%, 75%, 80%, 81%, 82%, 83%, 84%, 85%, 86%, 87%, 88%, 89%, 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98%, 99%, 99.5%, and 99.9% are renewable. In some embodiments, carbon 14 C / 12 The measurement of 1C isotope ratios will be performed using ASTM D6866.

[0350] Biochar pellets may have a Hard Globe Grinding Index (HGI) of at least about 30, at least about 40, or at least about 50. In various embodiments, biochar pellets have a Hard Globe Grinding Index of about 30 to about 100. In various embodiments, biochar pellets have a Hard Globe Grinding Index of about, at least about, or at most about 20, 30, 40, 50, 60, 70, 80, 90, 100, 110, or 120, including any intervening range.

[0351] Biochar pellets may have a Pellet Durability Index (PDI) of at least about 80, at least about 85, at least about 90%, or at least about 95%. In various embodiments, biochar pellets may have a Pellet Durability Index of about, at least about, or at most about 70%, 75%, 80%, 85%, 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98%, or 99%, including any intervening range.

[0352] Biochar pellets may contain one or more additives for various purposes, for example, to reduce flammability. Biochar pellets can be characterized as non-self-heating when subjected to a self-heating test in accordance with the Manual of Tests and Criteria, 7th Revision, 2019, United Nations, page 375, 33.4.6, Test N.4: "Test method for self-heating substances," which is incorporated herein by reference.

[0353] The presence of one or more additives can reduce the reactivity of biochar pellets compared to equivalent biochar pellets that do not contain one or more additives. Reactivity can be thermal reactivity. For example, a biochar composition containing one or more additives may have lower self-heating compared to equivalent biochar pellets that do not contain one or more additives. Alternatively or additionally, reactivity can be chemical reactivity with oxygen, water, hydrogen, carbon monoxide, or metals (e.g., iron).

[0354] In various embodiments, the concentration of additives in the biochar pellets may be about, at least about, or at most about 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 15, 20, 25, 30, 35, 40, 45, or 50% by weight, including any intervening range. If additives are used, they do not need to be uniformly dispersed throughout the pellet composition.

[0355] In some embodiments, the type or concentration of the additive is selected to optimize the energy content associated with the biochar pellets. In some embodiments, the type or concentration of the additive is selected to optimize the bulk density associated with the biochar pellets. In some embodiments, the type or concentration of the additive is selected to optimize the hydrophobicity associated with the biochar pellets. In some embodiments, the type or concentration of the additive is selected to optimize the pore size associated with the biochar pellets. In some embodiments, the type or concentration of the additive is selected to optimize the pore size ratio associated with the biochar pellets. In some embodiments, the type or concentration of the additive is selected to optimize the surface area associated with the biochar pellets. In some embodiments, the type or concentration of the additive is selected to optimize the reactivity associated with the biochar pellets. In some embodiments, the type or concentration of the additive is selected to optimize the ion exchange capacity associated with the biochar pellets. In some embodiments, the type or concentration of the additive is selected to optimize the hard-glove pulverability index associated with the pellets. In some embodiments, the type or concentration of the additive is selected to optimize the pellet durability index associated with the pellets.

[0356] Biochar pellets can be analyzed using imaging and spectroscopy. Imaging techniques include, but are not limited to, optical microscopy, dark-field microscopy, scanning electron microscopy (SEM), transmission electron microscopy (TEM), and X-ray tomography (XRT). Spectroscopic techniques include, but are not limited to, energy-dispersive X-ray spectroscopy (EDS), X-ray fluorescence (XRF), infrared (IR) spectroscopy, and nuclear magnetic resonance (NMR) spectroscopy.

[0357] In some process embodiments, step (a) is carried out at a thermal decomposition temperature selected from approximately 250°C to approximately 1250°C, for example, approximately 300°C to approximately 700°C. In some embodiments, step (a) is carried out for a thermal decomposition time selected from approximately 10 seconds to approximately 24 hours.

[0358] Optionally, the pyrolysis off-gas is at least partially oxidized to generate heat, which can be optionally used within the process. This use of heat within the process could, for example, be to supply heat to the pyrolysis reactor.

[0359] In one embodiment, the pyrolysis off-gas is at least partially oxidized to generate a reducing gas containing hydrogen or carbon monoxide.

[0360] In some embodiments, biogenic carbon from biomass pyrolysis is subjected to grinding. Grinding may be carried out using mechanical equipment comprising a hammer mill, extruder, attrition mill, disc mill, pin mill, ball mill, cone crusher, jaw crusher, or a combination thereof. Grinding may be carried out using mechanical equipment selected from the group consisting of hammer mills, extruders, attrition mills, disc mills, pin mills, ball mills, cone crushers, jaw crushers, and combinations thereof.

[0361] In some methods, the mixing of biogenic carbon and polyphenol materials utilizes mechanical processing equipment comprising hammer mills, extruders, attrition mills, disc mills, pin mills, ball mills, cone crushers, jaw crushers, and combinations thereof. In some embodiments, the mixing utilizes relatively simple equipment comprising tumblers, convection blenders, hopper blenders, fluidizing mixers, or combinations thereof. In some embodiments, the mixing utilizes relatively simple equipment selected from the group comprising tumblers, convection blenders, hopper blenders, fluidizing mixers, and combinations thereof.

[0362] Additives can be introduced at any point in the process. Additives may include organic or inorganic additives. In some embodiments, one or more additives include renewable materials. In some embodiments, one or more additives include materials that can be partially oxidized or combustible.

[0363] In some methods, one or more additives include or are essentially made up of binders. When binders are incorporated to produce pellets, the process may utilize a pelletizing apparatus. The pelletizing apparatus may comprise or essentially consist of an extruder, a ring-die pellet mill, a flat-die pellet mill, a roll compactor, a roll briquette, a wet flocculation mill, a dry flocculation mill, or a combination thereof. In some embodiments, the pelletizing apparatus may be selected from the group consisting of an extruder, a ring-die pellet mill, a flat-die pellet mill, a roll compactor, a roll briquette, a wet flocculation mill, a dry flocculation mill, and combinations thereof.

[0364] The binder may include, or may essentially consist of, starch, thermoplastic starch, cross-linked starch, starch polymer, cellulose, cellulose ether, hemicellulose, methylcellulose, chitosan, lignin, lactose, sucrose, glucose, maltodextrin, banana flour, wheat flour, wheat starch, soy flour, corn flour, wood flour, coal tar, coal powder, metcoke, asphalt, coal tar pitch, petroleum pitch, bitumen, pyrolysis tar, gilsonite, bentonite clay, borax, limestone, lime, wax, vegetable wax, baking soda, baking powder, sodium hydroxide, potassium hydroxide, iron ore concentrate, silica fume, gypsum, Portland cement, guar gum, xanthan gum, polyvidone, polyacrylamide, polylactide, phenol formaldehyde resin, vegetable resin, recycled singles, recycled tires, or derivatives thereof, or combinations thereof.

[0365] The binder may be selected from the group consisting of starch, thermoplastic starch, cross-linked starch, starch polymer, cellulose, cellulose ether, hemicellulose, methylcellulose, chitosan, lignin, lactose, sucrose, glucose, maltodextrin, banana flour, wheat flour, wheat starch, soy flour, corn flour, wood flour, coal tar, coal powder, metcoke, asphalt, coal tar pitch, petroleum pitch, bitumen, pyrolysis tar, gilsonite, bentonite clay, borax, limestone, lime, wax, vegetable wax, baking soda, baking powder, sodium hydroxide, potassium hydroxide, iron ore concentrate, silica fume, gypsum, Portland cement, guar gum, xanthan gum, polyvidone, polyacrylamide, polylactide, phenol formaldehyde resin, vegetable resin, recycled single, recycled tire, or derivatives thereof, and any combination thereof.

[0366] In some cases, the binder comprises or is essentially composed of starch, thermoplastic starch, crosslinked starch, starch polymers, derivatives thereof, or any combination thereof. In some cases, the binder is selected from the group consisting of starch, thermoplastic starch, crosslinked starch, starch polymers, derivatives thereof, and any combination thereof. The binder may optionally be crosslinked thermoplastic starch. Thermoplastic starch may be a reaction product of starch and polyol. In some embodiments, the polyol may be selected from the group consisting of ethylene glycol, propylene glycol, glycerol, butanediol, butanetriol, erythritol, xylitol, sorbitol, and combinations thereof. The reaction product may be formed from a reaction catalyzed by an acid. In some embodiments, the acid may be selected from the group consisting of formic acid, acetic acid, lactic acid, citric acid, oxalic acid, uronic acid, glucuronic acid, and combinations thereof. Alternatively, the reaction product may be formed from a reaction catalyzed by a base.

[0367] The presence of one or more additives can reduce the reactivity of biochar pellets compared to equivalent biochar pellets that do not contain one or more additives. Reactivity can be thermal reactivity. For example, biochar pellets containing one or more additives may have lower self-heating compared to equivalent biochar pellets that do not contain one or more additives. Alternatively or additionally, reactivity can be chemical reactivity with oxygen, water, hydrogen, carbon monoxide, or metals (e.g., iron).

[0368] In some cases, biochar pellets are characterized as non-self-heating when subjected to a self-heating test in accordance with the Manual of Tests and Criteria, 7th Revision, 2019, United Nations, page 375, 33.4.6, Test N.4: "Test method for self-heating substances".

[0369] The Hard Grove Grindability Index ("HGI") is a measure of the grindability of materials such as biomass or coal. The HGI parameter of coal is important in power generation applications such as pulverized coal boilers, where coal is pulverized and burned in a suspended state, and in iron production such as pulverized coal blowing, where pulverized coal is blown into a blast furnace through a lance, and the pulverized coal replaces coke in the blast furnace to reduce iron ore into metallic iron.

[0370] The ability to adjust the HGI of biochar pellets is beneficial because downstream applications utilizing biochar pellets (e.g., coal replacement in boilers) have diverse HGI requirements. The ability to adjust HGI industrially addresses well-known problems: the difficulty of crushing raw biomass and the difficulty of crushing pellets. Furthermore, since there are numerous downstream applications for biochar pellets, each with its own unique requirements, the ability to adjust the pellet's pulverizability is highly advantageous. It is desirable to be able to adjust HGI to suit specific applications such as combustion in boilers, metal production, or gasification for synthesis gas production.

[0371] In some applications, pellets may be preferred over powder (isolated biomass particles) due to considerations of transportation, storage, and safety. Ultimately, pellets may need to be reduced to powder, or at least smaller particles, at some point. Therefore, the pulverability of pellets is often a critical parameter that affects operating and capital costs.

[0372] In some cases, such as when a boiler or gasifier utilizes a fluidized bed or a suspension of carbon particles, pellets need to be ground or pulverized into a powder. Another example is the blowing of pulverized coal into a blast furnace to reduce metal ore into metal. In these cases, high pellet pulverability is desired, but not so high that the pellets fall apart during transport and handling. In other cases, it is desirable to supply the pellets themselves to processes such as metal production processes. In these cases, lower pulverability may be desirable because a certain degree of pellet strength may be required to support the material bed in the reactor. Different technologies have different pellet pulverability requirements.

[0373] The hardgrove grindability index of biochar pellets may be at least 30, at least 40, at least 50, at least 60, at least 70, at least 80, at least 90, or at least 100. In some embodiments, the hardgrove grindability index is about 30 to about 50 or about 50 to about 70. ASTM standard D 409 / D 409M, "Standard Test Method for Grindability of Coal by the Hardgrove-Machine Method," is incorporated herein by reference in its entirety. Unless otherwise indicated, all references to the hardgrove grindability index or HGI in this disclosure refer to ASTM standard D 409 / D 409M.

[0374] In various embodiments, the hard glove crushability index is approximately, at least approximately, or at most approximately 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, including all intervening ranges (e.g., 25-40, 30-60, etc.). The values ​​are 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, and 100.

[0375] In some embodiments, the process includes pre-selecting a hard globe pulverability index, adjusting process conditions based on the pre-selected hard globe pulverability index, and achieving within ±20% of the pre-selected hard globe pulverability index for the biochar pellets, where adjusting process conditions includes adjusting one or more of the following: pyrolysis temperature, pyrolysis time, mechanical processing conditions, pelletizing conditions, binder type, binder concentration, bonding conditions, and drying. In some embodiments, the process can achieve within ±10% or ±5% of the pre-selected hard globe pulverability index for the biochar pellets.

[0376] Biochar pellets may feature a pellet durability index of at least 80%, at least 85%, at least 90%, at least 95%, or at least 99%. Biochar pellets may feature a pellet durability index of less than 99%, less than 95%, less than 90%, less than 85%, or less than 80%. Unless otherwise indicated, all references to pellet durability indices in this disclosure relate to ISO 17831-1:2015, “Solid biofuels - Determination of mechanical durability of pellets and briquettes - Part 1: Pellets,” which is incorporated herein by reference in its entirety.

[0377] In some embodiments of the present invention, biochar pellets are used as a starting material for producing smaller objects, which can also be called biochar pellets, as the term "pellets" does not limit the geometric shape. For example, initial biochar pellets with an average pellet diameter of 10 mm can be produced. These initial biochar pellets can then be crushed using various mechanical means (e.g., using a hammer mill). The crushed pellets can then be separated according to size, for example, by sieving. In this way, smaller biochar pellets can be produced, for example, having an average pellet diameter of about, at least about, or at most about 50, 100, 150, 200, 300, 400, 500, 600, 700, 800, 900, 1000, 1500, 2000, 3000, 4000, or 5000 microns. The average pellet diameter of the smaller biochar pellets is often larger than the average particle diameter of the initial carbon-containing particles used to produce the pellets together with the binder.

[0378] When crushing biochar pellets to produce smaller biochar pellets, the crushing (and optionally, sieving) process can be integrated with other process steps, potentially including those in industrial applications. Any process for producing smaller biochar pellets can utilize a crushing device. In some embodiments, the crushing device comprises or essentially consists of a hammer mill, attrition mill, disc mill, pin mill, ball mill, cone crusher, jaw crusher, rock crusher, or a combination thereof. In some embodiments, the crushing device can be selected from the group consisting of a hammer mill, attrition mill, disc mill, pin mill, ball mill, cone crusher, jaw crusher, rock crusher, and combinations thereof.

[0379] The size and geometric shape of biochar pellets can vary considerably. As used herein, “pellets” refers to aggregated material, not loose powder. The geometric shape of pellets is not limited to spherical or nearly spherical. Also, in this disclosure, “pellets” is synonymous with “briquettes.” The geometric shape of pellets may be spherical (round or ball-shaped), cubic (square), octagonal, hexagonal, honeycomb / beehive-shaped, elliptical, egg-shaped, cylindrical, rod-shaped, pillow-shaped, amorphous, or a combination thereof. For convenience of disclosure, the term “pellets” is generally used for any material containing powder aggregated with a binder. It is also emphasized again that the present invention is by no means limited to biochar compositions in the form of pellets.

[0380] Biochar pellets may be characterized by an average pellet diameter, which is the true diameter in the case of a sphere, or the equivalent (or effective) diameter in the case of any other 3D geometric shape. The equivalent diameter of a non-spherical pellet is the diameter of a sphere with an equivalent volume to the actual pellet. In some embodiments, the average pellet diameter is about or at least about 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 20, or 25 millimeters, including all intervening ranges. In some embodiments, the average pellet diameter is about or at least about 500, 1000, 1500, 2000, 2500, 3000, 3500, 4000, 4500, 5000, 5500, 6000, or 6500 microns, including all intervening ranges.

[0381] In some embodiments, the biochar pellets are relatively uniform in size, with standard deviations of less than ±100%, ±50%, ±25%, ±10%, or ±5% of the average pellet diameter. In other embodiments, the biochar pellets are of a wide range of sizes, which may be advantageous in some applications.

[0382] Biochar pellets may contain moisture. Moisture present in biochar pellets may be water chemically bonded to carbon or a binder, water physically bonded (absorbed or adsorbed) to carbon or a binder, free water in the aqueous phase that is not chemically or physically bonded to carbon or a binder, or a combination of these. If moisture is desired during the bonding process, such moisture may be chemically or physically bonded to carbon or a binder rather than free water.

[0383] Various moisture levels are possible. For example, biochar pellets may contain about 1% to about 30% by weight (e.g., 32% by weight) of moisture, for example, about 5% to about 15% by weight, about 2% to about 10% by weight, or about 0.1% to about 1% by weight. In some embodiments, biochar pellets contain about 4 to 8% by weight of moisture. In various embodiments, biochar pellets contain about, at least about, or at most about 0.5, 1, 1.5, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, or 35% by weight of moisture, including all intervening ranges. The moisture content of biochar pellets can be optimized, for example, to alter the densification within the pellets.

[0384] For some market applications, such as agriculture, higher moisture levels are desirable for dust control or other reasons. For other market applications, such as metallurgy, lower moisture levels (e.g., 1% by weight or even less) may be desirable. Note that while water is present during the process of manufacturing biochar pellets, these pellets are then optionally dried, so the final biochar pellets do not necessarily contain moisture.

[0385] In some biochar pellets, the biochar pellet contains about 2% to about 25% by weight of an external binder, about 5% to about 20% by weight of the binder, or about 1% to about 5% by weight of the binder. In various embodiments, the biochar pellet contains about, at least about, or at most about 0.5, 1, 1.5, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 20, 25, or 30% by weight of the binder, including all intermediaries. In some embodiments, there is an inverse correlation between the desired moisture content and the external binder concentration.

[0386] The external binder may be pore-filling within the biogenic reagent of the biochar pellet. Alternatively or additionally, the external binder may be placed on the surface of the biochar pellet.

[0387] The external binder may be an organic binder or an inorganic binder. In some embodiments, the external binder is or contains a renewable material. In some embodiments, the external binder contains or is essentially made from a biodegradable material. In some embodiments, the external binder may be partially oxidized or burned.

[0388] In various embodiments, the external binder includes or is essentially composed of starch, thermoplastic starch, cross-linked starch, starch polymer, cellulose, cellulose ether, hemicellulose, methylcellulose, chitosan, lignin, lactose, sucrose, glucose, maltodextrin, banana flour, wheat flour, wheat starch, soy flour, corn flour, wood flour, coal tar, coal powder, metcoke, asphalt, coal tar pitch, petroleum pitch, bitumen, pyrolysis tar, gilsonite, bentonite clay, borax, limestone, lime, wax, vegetable wax, baking soda, baking powder, sodium hydroxide, potassium hydroxide, iron ore concentrate, silica fume, gypsum, Portland cement, guar gum, xanthan gum, polyvidone, polyacrylamide, polylactide, phenol formaldehyde resin, vegetable resin, recycled single, recycled tire, or derivatives thereof, or combinations thereof. The external binder may contain, or may be essentially composed of, pulverizable plasticizers.

[0389] In various embodiments, the external binder is selected from the group consisting of starch, thermoplastic starch, cross-linked starch, starch polymer, cellulose, cellulose ether, hemicellulose, methylcellulose, chitosan, lignin, lactose, sucrose, glucose, maltodextrin, banana flour, wheat flour, wheat starch, soy flour, corn flour, wood flour, coal tar, coal powder, metcoke, asphalt, coal tar pitch, petroleum pitch, bitumen, pyrolysis tar, gilsonite, bentonite clay, borax, limestone, lime, wax, vegetable wax, baking soda, baking powder, sodium hydroxide, potassium hydroxide, iron ore concentrate, silica fume, gypsum, Portland cement, guar gum, xanthan gum, polyvidone, polyacrylamide, polylactide, phenol formaldehyde resin, vegetable resin, recycled single, recycled tire, or derivatives thereof, and any combination thereof.

[0390] In one embodiment, the external binder includes or is essentially made of starch, thermoplastic starch, crosslinked starch, starch-based polymers (e.g., polymers based on amylose and amylopectin), derivatives thereof, or combinations thereof. In one embodiment, the external binder is selected from the group consisting of starch, thermoplastic starch, crosslinked starch, starch-based polymers (e.g., polymers based on amylose and amylopectin), derivatives thereof, and any combination thereof. The starch may be nonionic starch, anionic starch, cationic starch, or amphoteric starch.

[0391] Starch is one of the most abundant biopolymers. It is completely biodegradable, inexpensive, renewable, and easily chemically modifiable. The cyclic structure of starch molecules, along with strong hydrogen bonding, gives starch a rigid structure, resulting in highly ordered crystalline and granular regions. Granular starch is generally unsuitable for thermoplastic processing. To obtain thermoplastic starch, semi-crystalline starch particles can be broken by thermal and mechanical forces. Since the melting point of pure starch is considerably higher than its decomposition temperature, plasticizers such as water or glycol can be added. The natural crystallinity can then be broken by vigorous mixing (shearing) at high temperatures, thereby obtaining thermoplastic starch. Starch can be plasticized (structurally broken) by relatively low levels of molecules that can hydrogen bond with the hydroxyl groups of starch, such as water, glycerol, or sorbitol.

[0392] Thermoplastic starch can be chemically modified or blended with other biopolymers to produce tougher, more ductile, and resilient bioplastics. For example, starch can be blended with natural and synthetic (biodegradable) polyesters such as polylactic acid, polycaprolactone, or polyhydroxybutyric acid. To improve the compatibility of the starch / polyester blend, suitable compatibilizers such as poly(ethylene-co-vinyl alcohol) or polyvinyl alcohol can be added. The hydrophilic hydroxyl groups (-OH) of starch can be replaced with hydrophobic (reactive) groups, for example, by esterification or etherification.

[0393] In some embodiments, the starch-containing binder is or comprises crosslinked starch. Various methods for crosslinking starch are known in the art. Starch materials can be crosslinked under acidic or alkaline conditions, for example, after being dissolved or dispersed in an aqueous medium. Aldehydes (e.g., glutaraldehyde or formaldehyde) can be used to crosslink starch.

[0394] An example of a crosslinked starch is the reaction product of starch with glycerol or another polyol, such as (but not limited to) ethylene glycol, propylene glycol, glycerol, butanediol, butanetriol, erythritol, xylitol, sorbitol, or a combination thereof. The reaction product may be formed from crosslinking catalyzed by an acid, such as (but not limited to) formic acid, acetic acid, lactic acid, citric acid, oxalic acid, uronic acid, glucuronic acid, or a combination thereof. Inorganic acids, such as sulfuric acid, can also be used to catalyze the crosslinking reaction. In some embodiments, the thermoplasticized or crosslinking reaction product may instead be formed from a crosslinking reaction catalyzed by a base, such as (but not limited to) ammonia or sodium borate.

[0395] In some embodiments, the external binder is designed to be a water-resistant binder. For example, in the case of starch, hydrophilic groups can be replaced with hydrophobic groups that have better water resistance.

[0396] In some embodiments, the external binder serves other purposes, such as (but not limited to) retaining moisture in the biochar pellets or providing a food source for microorganisms.

[0397] In some embodiments, the external binder reduces the reactivity of the biochar pellets compared to biochar pellets without the binder, which are otherwise equivalent. Reactivity can refer to thermal reactivity or chemical reactivity (or both).

[0398] In the case of thermal reactivity, biochar pellets may exhibit lower self-heating compared to binder-free, otherwise equivalent biochar pellets. "Self-heating" refers to the spontaneous exothermic reaction that occurs in biochar pellets at relatively low temperatures and in an oxidizing atmosphere, without external ignition, which raises the internal temperature of the biochar pellet.

[0399] Chemical reactivity may involve reactions with oxygen, water, hydrogen, carbon monoxide, metals (e.g., iron), or combinations thereof. Chemical reactivity may also involve reactions with CO, CO2, H2O, pyrolysis oils, and heat.

[0400] Optionally, the biochar pellets may contain one or more additives (not necessarily binders) such as inorganic bentonite clay, limestone, starch, cellulose, lignin, or acrylamide. When lignin is used as a binder or other additive, it can be obtained from the same biomass raw material used in the pyrolysis process. For example, the starting biomass raw material can be subjected to a lignin extraction process to remove an amount of lignin for use as a binder or additive.

[0401] Other possible additives include fluxing agents such as inorganic chlorides, inorganic fluorides, or lime. In some embodiments, the additive is selected from acids, bases, or salts thereof. In some embodiments, at least one additive comprises or is essentially composed of metals, metal oxides, metal hydroxides, metal halides, or combinations thereof. In some embodiments, at least one additive is selected from the group consisting of metals, metal oxides, metal hydroxides, metal halides, and combinations thereof. For example, the additive may be selected from the group consisting of (but not limited to) sodium hydroxide, potassium hydroxide, magnesium oxide, hydrogen bromide, hydrogen chloride, sodium silicate, potassium permanganate, magnesium, manganese, aluminum, nickel, chromium, silicon, boron, cerium, molybdenum, phosphorus, tungsten, vanadium, iron halides, iron chloride, iron bromide, dolomite, dolomite lime, fluorite, fluorospar, bentonite, calcium oxide, lime, or combinations thereof. Additives may be added before, during, or after any one or more steps in the process, including adding them to the raw materials themselves at any time before or after harvesting.

[0402] The biochar pellets disclosed herein have a wide variety of downstream applications. Biochar pellets can be stored, sold, transported, and converted into other products. Biochar pellets can be pulverized for use in boilers to burn carbon and generate electrical energy or heat. Biochar pellets can be pulverized, crushed, or ground for feed into furnaces such as blast furnaces in steelmaking. Biochar pellets can be fed directly into furnaces such as TechnoRed furnaces in steelmaking. Biochar pellets can be pulverized, crushed, or ground for feed into gasifiers for the purpose of producing synthesis gas from biochar pellets.

[0403] In many embodiments, biochar pellets are fed into the furnace either directly or after a process that reduces the particle size by micronization, crushing, grinding, or other means. The furnace may be a blast furnace, top gas recycling blast furnace, shaft furnace, reverberatory furnace (also known as an air furnace), crucible furnace, muffle furnace, retort furnace, flash furnace, technored furnace, aussmelt furnace, isasmelt furnace, paddle furnace, trolley furnace, continuous chain furnace, pusher furnace, rotary hearth furnace, walking beam furnace, electric furnace, induction furnace, basic oxygen furnace, paddle furnace, Bessemer furnace, direct reducing metal furnace, or a combination or derivative thereof.

[0404] Regardless of the hard-glob pulverability index of biochar pellets, it should be noted that they are not necessarily subjected to subsequent pulverization processes. For example, biochar pellets can be used directly in agricultural applications. As another example, biochar pellets can be directly incorporated into engineering structures such as landscape walls. At the end of the lifespan of a structure containing biochar pellets, the pellets can then be reused or recycled by pulverization, combustion, gasification, or other means.

[0405] (Thermolysis process and system) Preferred processes and systems for pyrolysis of biomass raw materials to produce biogenic reagents are described in further detail here. In this specification, references to “biocal reagents” are understood, depending on the context, in various examples to refer to biogenic carbon or bioocal compositions containing biogenic carbon.

[0406] "Pyrolysis" and "to decompose" usually refer to the thermal decomposition of carbonaceous materials. In pyrolysis, less oxygen is present than is required for the complete combustion of the material, for example, 10%, 5%, 1%, 0.5%, 0.1%, or less than 0.01% of the oxygen required for complete combustion (based on O2 moles). In some embodiments, pyrolysis is carried out in the absence of oxygen.

[0407] Exemplary changes that may occur during pyrolysis include any of the following: (i) heat transfer from the heat source increases the temperature inside the raw material; (ii) the initiation of the primary pyrolysis reaction at this higher temperature releases volatiles and forms char; (iii) the flow of high-temperature volatiles toward the lower-temperature solid results in heat transfer between the high-temperature volatiles and the lower-temperature un-pyrolytic raw material; (iv) condensation of some of the volatiles in the lower-temperature portion of the raw material and subsequent secondary reactions may produce tar; (v) while primary pyrolysis reactions occur simultaneously and competitively, autocatalytic secondary pyrolysis reactions proceed; and (vi) further pyrolysis, reforming, water-gas shift reactions, free radical recombination, or dehydration may also occur as a function of residence time, temperature, and pressure profile.

[0408] Pyrolysis can at least partially dehydrate the starting material (e.g., lignocellulosic biomass). In various embodiments, pyrolysis removes about 50%, 75%, 90%, 95%, more than 99%, or more water from the starting material.

[0409] In some embodiments, the starting biomass raw materials include coniferous wood chips, hardwood wood chips, wood harvest residues, tree branches, tree stumps, leaves, bark, sawdust, corn, corn stover, wheat, wheat straw, rice, rice straw, sugarcane, sugarcane bagasse, sugarcane straw, energy cane, sugar beet, sugar beet pulp, sunflower, sorghum, canola, algae, Japanese pampas grass, alfalfa, switchgrass, fruits, fruit shells, and fruit stems. This includes, or is essentially, fruit peels, fruit seeds, vegetables, vegetable shells, vegetable stems, vegetable peels, vegetable seeds, grape pomace, almond shells, pecan shells, coconut shells, coffee grounds, food waste, commercial waste, grass pellets, hay pellets, wood pellets, cardboard, paper, paper pulp, paper packaging, paper scraps, food packaging, construction or demolition waste, railway sleepers, lignin, animal manure, municipal solid waste, municipal sewage, or combinations thereof.

[0410] In some embodiments, the starting biomass raw materials are selected from coniferous wood chips, hardwood chips, wood harvest residues, tree branches, tree stumps, leaves, bark, sawdust, corn, corn stover, wheat, wheat straw, rice, rice straw, sugarcane, sugarcane bagasse, sugarcane straw, energy cane, sugar beet, sugar beet pulp, sunflower, sorghum, canola, algae, Japanese pampas grass, alfalfa, switchgrass, fruits, fruit shells, fruit stems, fruit peels, fruit seeds, vegetables, vegetable shells, vegetable stems, vegetable peels, vegetable seeds, grape pomace, almond shells, pecan shells, coconut shells, coffee grounds, food waste, commercial waste, grass pellets, hay pellets, wood pellets, cardboard, paper, paper pulp, paper packaging, paper scraps, food packaging, construction or demolition waste, railway sleepers, lignin, animal manure, municipal solid waste, municipal sewage, and combinations thereof. It should be noted that biomass raw materials typically contain at least carbon, hydrogen, and oxygen.

[0411] Biogenic reagents may contain at least about 50% by weight, at least about 75% by weight, or at least about 90% by weight of total carbon. In various embodiments, biogenic reagents contain about, at least about, or at most about 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, or 99% by weight of carbon. Total carbon is fixed carbon plus unfixed carbon present in volatile matter. In some embodiments, component weight percentages are absolute unless otherwise specified. In other embodiments, component weight percentages are based on an anhydrous, ash-free standard.

[0412] The pyrolysis conditions can vary widely depending on the desired composition of the biogenic reagent and pyrolysis off-gas, the starting materials, the reactor configuration, and other factors.

[0413] In some embodiments, multiple reactor zones are designed and operated in a manner that optimizes carbon yield from pyrolysis and product quality while maintaining flexibility and adaptability to variations in raw materials and product requirements.

[0414] In some non-limiting embodiments, temperature and residence time may be selected to achieve a relatively slow pyrolysis chemistry. The potential advantage of this is substantial preservation of the cell walls contained within the biomass structure, meaning that the final product can retain some, most, or all of the shape and strength of the starting biomass. To maximize this potential advantage, apparatus can be used that does not mechanically break down the cell walls or otherwise convert the biomass particles into fine powder. Specific reactor configurations will be discussed after the process description below.

[0415] Furthermore, if the raw material is a crushed or sized material such as wood chips or pellets, it may be desirable that the raw material be carefully crushed or sized. Careful initial processing tends to preserve the strength and cell wall integrity present in the natural raw material source (e.g., trees). This may also be important if the final product should retain some, most, or all of the shape and strength of the starting biomass.

[0416] In some embodiments, the first zone of the pyrolysis reactor is configured to supply biomass (or another carbon-containing feedstock) in a manner that does not "shock" the biomass, thereby disrupting the cell walls and initiating rapid decomposition from the solid phase to vapor and gas. This first zone can be thought of as gentle pyrolysis.

[0417] In some embodiments, the second zone of the pyrolysis reactor is configured as the primary reaction zone, where preheated biomass undergoes a pyrolysis chemical reaction, releasing gas and condensable vapors, leaving behind a considerable amount of solid material, which is a high-carbon reaction intermediate. The biomass components (mainly cellulose, hemicellulose, and lignin) decompose to produce vapors, which escape by penetrating pores or forming new nanopores. The latter effect contributes to the creation of porosity and surface area.

[0418] In some embodiments, a third zone of the pyrolysis reactor is configured to receive high-carbon reaction intermediates and to cool the solid to some extent. Typically, the third zone is at a lower temperature than the second zone. Chemical reactions and mass transfers in the third zone can be surprisingly complex. Secondary reactions are thought to occur in the third zone, although not limited to any particular theory or proposed mechanism. Essentially, carbon-containing components in the gas phase may decompose to form further fixed carbon or be adsorbed onto carbon. Thus, the final carbonaceous material may not merely be the defoliated solid residue of the processing step, but rather may contain further carbon deposited from the gas phase, for example, by the decomposition of organic vapors capable of forming carbon (e.g., tar).

[0419] One embodiment extends the concept of further carbon formation by including a separate unit that exposes cooled carbon to an environment containing carbon-containing species to increase the carbon content of the final product. If the temperature of this unit falls below the thermal decomposition temperature, the further carbon is expected to be in the form of adsorbed carbonaceous species rather than further fixed carbon.

[0420] There are many options regarding intermediate input and output (purge or probe) streams of one or more phases present in any specific zone, various mass and energy recycling schemes, various additives that can be introduced anywhere in the process, and the adjustability of process conditions, including both reaction and separation conditions, to adjust product distribution. Zone-specific input and output streams enable good process monitoring and control, for example, through FTIR sampling and dynamic process adjustment.

[0421] (Thermal decomposition process for manufacturing biogenic reagents) Some embodiments do not utilize rapid thermal decomposition, and some embodiments do not utilize slow thermal decomposition. Remarkably high-quality carbon materials, including compositions with a very high percentage of fixed carbon, can be obtained from the disclosed processes and systems.

[0422] In some embodiments, the pyrolysis process for producing a biogenic reagent consists of the following steps: (a) A process of providing carbon-containing raw materials including biomass; (b) Optionally, a step of drying the raw materials to remove at least some of the moisture contained therein; (c) Optionally, a step of degassing the raw materials to remove at least some of the interstitial oxygen (if any) contained with the raw materials; (d) A step of thermally decomposing a raw material in the presence of a substantially inert gas phase for at least 10 minutes at at least one temperature selected from about 250°C to about 700°C to produce a high-temperature thermally decomposed solid, a condensable vapor, and a non-condensable gas; (e) A step of separating at least a portion of the condensable vapor and at least a portion of the non-condensable gas from the high-temperature pyrolysis solid; (f) A step of cooling a high-temperature pyrolysis solid to produce a cooled pyrolysis solid; and (g) A step of recovering a biogenic reagent containing at least a portion of the cooled pyrolysis solid. Includes.

[0423] For the purposes of this disclosure, “biomass” shall be interpreted as any biogenic raw material, or a mixture of biogenic and non-biogenic raw materials. With respect to elements, biomass includes at least carbon, hydrogen, and oxygen. The methods and apparatus of the present invention can be adapted to a wide range of raw materials of various types, sizes, and moisture content.

[0424] Examples of biomass include plants and plant-derived materials, vegetation, agricultural waste, forestry waste, wood waste, paper waste, animal-derived waste, poultry-derived waste, and municipal solid waste. In various embodiments of the present invention utilizing biomass, biomass raw materials can include one or more materials selected from wood harvest residues, coniferous wood chips, hardwood chips, tree branches, tree stumps, knots, leaves, bark, sawdust, off-grade paper pulp, cellulose, corn, corn stover, wheat straw, rice straw, sugarcane bagasse, switchgrass, pampas grass, animal manure, municipal solid waste, municipal sewage, commercial waste, grape pomace, almond shells, pecan shells, coconut shells, coffee grounds, grass pellets, hay pellets, wood pellets, cardboard, paper, carbohydrates, plastics, and cloth. Those skilled in the art will readily understand that the selection of raw materials is virtually unlimited.

[0425] The present invention can also be used with carbon-containing raw materials other than biomass, such as fossil fuels (e.g., coal or petroleum coke), or any mixture of biomass and fossil fuels (e.g., biomass / coal blends). In some embodiments, the biogenic raw material is or includes coal, oil shale, crude oil, asphalt, or solids from crude oil processing (e.g., petroleum coke). Examples of raw materials include waste tires, recycled plastics, recycled paper, construction waste, demolition waste, and other waste or recycled materials. To avoid misunderstanding, any method, apparatus, or system described herein can be used with any carbonaceous raw material. The carbon-containing raw material may be transported by any known means, such as trucks, trains, ships, barges, tractor trailers, or any other vehicle or means of transport.

[0426] The selection of specific raw materials (one or more) is carried out in a manner that is not considered technically important but tends to be advantageous to the economic process. Typically, regardless of the selected raw materials, screening can be performed (in some embodiments) to remove undesirable materials. The raw materials may optionally be dried before processing.

[0427] The raw materials used can be provided in a wide variety of particle sizes or shapes, or can be processed into such sizes or shapes. For example, the supply material may be a fine powder or a mixture of fine and coarse particles. The supply material may be in the form of larger material pieces, such as wood chips or other forms of wood (e.g., round, cylindrical, square, etc.). In some embodiments, the supply material may include pellets or other aggregated forms of particles that are pressed together or otherwise bound together, for example, with a binder.

[0428] It should be noted that size reduction is a costly and energy-intensive process. Pyrolytically decomposed materials can be sized with significantly less energy input. That is, in some embodiments, the particle size of the product, rather than the raw material, can be reduced. This process does not require fine starting material and does not necessarily result in significant particle size reduction during processing, making it one option in the present invention. The ability to process very large raw material pieces is a significant economic advantage of the present invention. In particular, some market applications of high-carbon products require large sizes (e.g., on the order of centimeters), so in some embodiments, large fragments are supplied, manufactured, and sold.

[0429] For example, if it is desired to produce a cylindrical, structurally intact final carbonaceous biogenic reagent, there are at least two options in the context of the present invention. First, the material produced from the process can be recovered and then further mechanically processed to form the desired shape. For example, the product can be pressed or pelletized with a binder. Second, the option is to utilize a supply material that generally has the desired size or shape for the final product and to utilize a processing step that does not destroy the basic structure of the supply material. In some embodiments, the supply and the product have similar geometric shapes, such as spheres, cylinders, or cubes.

[0430] The ability to maintain the approximate size of the supply material throughout the process is beneficial when product strength is critical. Furthermore, it avoids the difficulties and costs associated with pelletizing high-fixed-carbon materials.

[0431] As can be understood, the starting feed material can be provided at various moisture levels. In some embodiments, the feed material may already be sufficiently dry so that it does not need to be further dried before pyrolysis. Typically, it is desirable to use commercially available biomass sources that mostly contain moisture and to supply the biomass through a drying process before introducing it into the pyrolysis reactor. However, in some embodiments, dried raw materials can be used.

[0432] In a pyrolysis reactor, it is usually desirable to provide a relatively low-oxygen environment, for example, providing about or at most about 10 mol%, 5 mol%, 4 mol%, 3 mol%, 2 mol%, 1.5 mol%, 1 mol%, 0.5 mol%, 0.2 mol%, 0.1 mol%, 0.05 mol%, 0.02 mol%, or 0.01 mol% of O2 in the gas phase. Firstly, for safety reasons, uncontrolled combustion in the pyrolysis reactor should be avoided. Some degree of total carbon oxidation to CO2 may occur, and the heat released from exothermic oxidation can support endothermic pyrolysis chemistry. Large amounts of carbon oxidation, including partial oxidation to synthesis gas, will reduce the carbon yield to solids.

[0433] Realistically, achieving a strictly oxygen-free environment within a reactor can be difficult. However, approaching this limit, in some embodiments, the reactor is substantially free of molecular oxygen in the gas phase. To ensure that little to no oxygen is present in the pyrolysis reactor, it may be desirable to remove air from the feed material before it is introduced into the reactor. Various methods exist for removing or reducing air from the feed material.

[0434] In some embodiments, a degassing unit is used, where the raw material is transported in the presence of another gas before or after drying, which can remove adsorbed oxygen and penetrate the pores of the raw material to remove oxygen from the pores. Essentially any gas having less than 21% by volume of O2 can be used with varying degrees of effectiveness. In some embodiments, nitrogen is used. In some embodiments, CO or CO2 is used. Mixtures such as a mixture of nitrogen and a small amount of oxygen can be used. Water vapor may be present in the degassing gas, but it is important to avoid returning a significant amount of moisture to the feed. The effluent from the degassing unit can be purged (to the atmosphere or into an emissions treatment unit) or recycled.

[0435] In principle, the effluent (or a portion thereof) from the degassing unit can be introduced into the pyrolysis reactor itself because the oxygen removed from the solid is highly diluted at that point. In this embodiment, if the degassed effluent gas is operated in a countercurrent configuration, it may be advantageous to introduce it into the final zone of the reactor.

[0436] Various types of degassing units can be used. When drying, scrubbing dissolved oxygen from the present moisture can be inefficient, so drying and then degassing may be more efficient. In one embodiment, the drying and degassing processes are integrated into a single unit, or some degassing is achieved during drying.

[0437] The optionally dried and optionally degassed feed material is introduced into a pyrolysis reactor or multiple reactors in series or parallel. The feed material can be introduced using any known means, including a screw feeder or a rock hopper. In some embodiments, the material feeding system incorporates an air knife.

[0438] When a single reactor is used, multiple zones may be present. Multiple zones, for example, two, three, four, or more, allow for individual control of temperature, solid residence time, gas residence time, gas composition, flow pattern, or pressure to adjust the overall process performance.

[0439] References to “zones” should be broadly interpreted to include spatial areas within a single physical unit, physically separated units, or any combination thereof. In the case of a continuous reactor, zone boundaries may relate to structural aspects such as the presence of flights within the reactor or the presence of independent heating elements for supplying heat to separate zones. Alternatively or additionally, zone boundaries in a continuous reactor may relate to functional aspects such as independent temperatures, fluid flow patterns, solid flow patterns, or the degree of reaction. In a single batch reactor, a “zone” is a temporal operating area, not a spatial one. Multiple batch reactors can also be used.

[0440] It will be understood that there is not necessarily an abrupt transition from one zone to another. For example, the boundary between the preheating zone and the pyrolysis zone can be arbitrary to some extent; some pyrolysis may occur in part of the preheating zone, and some "preheating" may continue in part of the pyrolysis zone. The temperature profile within the reactor is usually continuous, including the zone boundaries within the reactor.

[0441] Some embodiments utilize a first zone operated under preheating or mild thermal decomposition conditions. The temperature of the first zone can be selected from about 150°C to about 500°C, for example, about 300°C to about 400°C. At certain higher temperatures in the first zone, the biomass material may be shocked, thereby breaking down the cell walls and initiating rapid decomposition from solid phase to vapor and gas.

[0442] All references to zone temperatures in this specification should be interpreted non-restrictively to include temperatures applicable to the bulk solid, gas phase, or reactor walls (on the process side) present. It will be understood that each zone has temperature gradients both axially and radially, and over time (i.e., after startup or due to transient events). Thus, references to zone temperatures may refer to average temperatures or other effective temperatures that may affect the actual dynamics. Temperatures can be measured directly by thermocouples or other temperature probes, or indirectly by other means.

[0443] The second zone, or more generally, the primary pyrolysis zone, is operated under pyrolysis or carbonization conditions. The temperature of the second zone can be selected from approximately 250°C to approximately 700°C, for example, approximately or at least approximately or at most approximately 300°C, 350°C, 400°C, 450°C, 500°C, 550°C, 600°C, or 650°C. Within this zone, the preheated biomass undergoes pyrolysis chemistry, releasing gases and condensable vapors, leaving a considerable amount of solid material as high-carbon reaction intermediates. The biomass components (mainly cellulose, hemicellulose, and lignin) decompose to produce vapors, which escape by penetrating pores or forming new pores. The selected temperature is determined by at least the residence time in the second zone, as well as the properties of the raw materials and the desired product characteristics.

[0444] A third zone, or cooling zone, is operated to cool the high-carbon reaction intermediate to varying degrees. At a minimum, the temperature of the third zone should be lower than the temperature of the second zone. The temperature of the third zone can be selected from approximately 100°C to approximately 550°C, for example, approximately 150°C to approximately 350°C.

[0445] Chemical reactions can continue to occur in the cooling zone. While not limited to any specific theory, it is believed that secondary pyrolysis reactions can be initiated in the third zone. Carbon-containing components in the gas phase can condense (due to the temperature decrease in the third zone). However, the temperature remains high enough to promote reactions (secondary pyrolysis) that can form further fixed carbon from the condensed liquid, or at least to form bonds between the adsorbed species and the fixed carbon. One exemplary reaction that can occur is the Boudouar reaction, which converts carbon monoxide into carbon dioxide and fixed carbon.

[0446] The residence time in a reactor zone can vary. Due to the interaction of time and temperature, a higher temperature can allow for a shorter reaction time for a desired amount of thermal decomposition, and vice versa. In a continuous reactor (zone), the residence time is the volume divided by the volumetric flow rate. In a batch reactor, the residence time is the batch reaction time after heating to the reaction temperature.

[0447] In multiphase reactors, it should be recognized that multiple residence times exist. In this context, each zone will have residence times (and residence time distributions) for both the solid and vapor phases. For a given apparatus that utilizes multiple zones and has a certain processing capacity, the residence times across zones are usually synchronized on the solid side. However, if multiple inlet and outlet ports are used in each zone, the residence times on the vapor side can be independent. The residence times of the solid and vapor phases are independent.

[0448] The solid residence time in the preheating zone can be selected from approximately 5 to 60 minutes, for example, 10, 20, 30, 40, or 50 minutes. Depending on the temperature, a sufficient time is desired to allow the biomass to reach the desired preheating temperature. The type and size of the particles, the physical equipment, and the heat transfer rate, which depends on the heating parameters, will determine the minimum residence time required to allow the solid to reach the desired preheating temperature. Unless some degree of gentle pyrolysis is intended in the preheating zone, additional time may be undesirable as it will contribute to higher capital costs.

[0449] The solid residence time in the pyrolysis zone can be selected from approximately 10 to 120 minutes, for example, 20, 30, 40, 50, 60, 70, 80, 90, or 100 minutes. Depending on the pyrolysis temperature in this zone, there should be sufficient time to allow the carbonization chemical reaction to occur after the necessary heat transfer. To remove a large amount of non-carbon elements in less than approximately 10 minutes, the temperature would need to be considerably higher, such as above 700°C. This temperature would promote rapid pyrolysis and the generation of vapors and gases derived from carbon itself, which should be avoided if the intended product is solid carbon.

[0450] In a static system, there will be an equilibrium conversion rate that can be substantially reached over time. As seen in one embodiment, if the vapor flows continuously over the solid with continuous removal of volatile components, the equilibrium constraint can be removed, allowing thermal decomposition and defoliation to continue until the reaction rate approaches zero. Even over longer periods, there is no tendency to substantially alter the remaining persistent solid.

[0451] The solid residence time in the cooling zone can be selected from approximately 5 to 60 minutes, for example, 10, 20, 30, 40, or 50 minutes. Depending on the cooling temperature in this zone, there should be sufficient time to allow the carbon solid to cool to the desired temperature. The cooling rate and temperature will determine the minimum residence time required to allow the carbon to cool. Additional time may be undesirable unless some degree of secondary pyrolysis is desired.

[0452] As discussed above, the residence time of the vapor phase can be selected and controlled separately. The vapor residence time in the preheating zone can be selected from approximately 0.1 minutes to approximately 15 minutes, for example, from approximately 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 minutes. The vapor residence time in the pyrolysis zone can be selected from approximately 0.1 minutes to approximately 20 minutes, for example, from approximately 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, or 15 minutes. The vapor residence time in the cooling zone can be selected from approximately 0.1 minutes to approximately 15 minutes, for example, from approximately 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 minutes. Shorter vapor residence times promote rapid scavenging of volatile components outside the system, while longer vapor residence times promote the reaction between components in the vapor phase and the solid phase.

[0453] The operating mode of the reactor and the entire system can be continuous, semi-continuous, batch, or any combination or variation thereof. In some embodiments, the reactor is a continuous counterflow reactor in which solids and vapors flow substantially in opposite directions. The reactor can also be operated in batch mode, but with simulated counterflow of vapor, for example, by periodically introducing and removing the gas phase from a batch vessel.

[0454] Various flow patterns may be desired or observed. Due to chemical reactions and simultaneous separations involving multiple phases in multiple reactor zones, the fluid dynamics can become very complex. Typically, solid flows can approach plug flow (well-mixed radially), while vapor flows can approach perfectly mixed flow (high-speed transport in both radial and axial directions). Multiple inlet and outlet ports for vapor can contribute to overall mixing.

[0455] The pressure in each zone can be selected and controlled independently. The pressure in each zone can be independently selected from approximately 1 kPa to approximately 3000 kPa, such as approximately 101.3 kPa (normal atmospheric pressure). Independent zone pressure control is possible when multiple gas inlets and outlets are used, including vacuum ports for extracting gas when zone pressures below atmospheric pressure are desired.

[0456] In some embodiments, the process can be conveniently operated at atmospheric pressure. There are many advantages to operating at atmospheric pressure, ranging from mechanical simplicity to improved safety. In some embodiments, the pyrolysis zone is operated at pressures of approximately 90 kPa, 95 kPa, 100 kPa, 101 kPa, 102 kPa, 105 kPa, or 110 kPa (absolute pressure).

[0457] Vacuum operation (e.g., 10–100 kPa) will facilitate rapid scavenging of volatile components outside the system. Higher pressures (e.g., 100–1000 kPa) may be useful when off-gas is supplied to high-pressure operations. Increased pressure may also be useful to facilitate heat transfer, chemical reactions, or separations.

[0458] The process of separating at least a portion of the condensable vapor and at least a portion of the non-condensable gas from the high-temperature pyrolysis solid can be achieved within the reactor itself or using a separate separation unit. A substantially inert sweep gas can be introduced into one or more zones. The condensable vapor and non-condensable gas are then carried away from the zones to the outside of the reactor by the sweep gas.

[0459] The sweep gas may be, for example, N2, Ar, CO, CO2, H2, H2O, CH4, other light hydrocarbons, or combinations thereof. The sweep gas can be preheated before introduction, or, if obtained from a heat source, may be cooled.

[0460] Sweep gases remove volatile components more completely by evaporating them from the system before they can condense or react further. Sweep gases allow for the removal of volatiles at a higher rate than could be achieved from volatilization alone at a given process temperature. Alternatively, the use of sweep gases allows for the use of milder temperatures to remove a specific amount of volatiles. The reason sweep gases improve volatile removal is that the separation mechanism is not simply specific volatility, but rather liquid / gas disengagement assisted by the sweep gas. Sweep gases can not only lower the mass transfer limit of volatilization, but also lower the thermodynamic limit by continuously depleting a given volatile species, evaporating more of it to reach thermodynamic equilibrium.

[0461] Some embodiments remove gases containing a high amount of volatile organic carbon from subsequent processing steps to produce products with high fixed carbon content. If not removed, the volatile carbon may be adsorbed or absorbed onto the pyrolyzed solid, thereby requiring additional energy (cost) to obtain the desired purer form of carbon. It is also hypothesized that rapid removal of vapors can enhance porosity in the solid during pyrolysis. Higher porosity is desirable for some products.

[0462] In one embodiment, a sweep gas combined with a relatively low process pressure, such as atmospheric pressure, provides rapid vapor removal without requiring a large amount of inert gas.

[0463] In some embodiments, the sweep gas flows countercurrently with respect to the flow direction of the raw materials. In other embodiments, the sweep gas flows parallel to the flow direction of the raw materials. In some embodiments, the solid flow pattern approaches a plug flow, while the sweep gas, and generally the gas phase flow pattern, approaches a fully mixed flow in one or more zones.

[0464] The sweep can be performed in one or more of the reactor zones. In some embodiments, the sweep gas is introduced into the cooling zone and extracted from the cooling zone or the pyrolysis zone (along with the generated volatiles). In some embodiments, the sweep gas is introduced into the pyrolysis zone and extracted from the pyrolysis zone or the preheating zone. In some embodiments, the sweep gas is introduced into the preheating zone and extracted from the pyrolysis zone. In these or other embodiments, the sweep gas can be introduced into and extracted from each of the preheating, pyrolysis, and cooling zones.

[0465] In some embodiments, the zone(s) where separation takes place are units physically separated from the reactor. If desired, the separation unit or zone can be positioned between reactor zones. For example, a separation unit can be positioned between a pyrolysis unit and a cooling unit.

[0466] The sweep gas can be introduced continuously, especially when the solid flow is continuous. When the pyrolysis reaction is operated as a batch process, the sweep gas can be introduced after a certain period of time or periodically to remove volatile components. Even when the pyrolysis reaction is operated continuously, the sweep gas can be introduced semi-continuously or periodically, if desired, using suitable valves and controls.

[0467] The sweep gas containing volatile components can be discharged from one or more reactor zones, and if obtained from multiple zones, it can be combined. The resulting gas stream, containing various vapors, can then be supplied to a thermal oxidation unit for controlling atmospheric discharge. Any known thermal oxidation unit can be utilized. In some embodiments, natural gas and air are supplied to the thermal oxidation unit and heated to a temperature sufficient to substantially destroy the volatile components contained therein.

[0468] The effluent from the thermal oxidation system is a high-temperature gas stream containing water, carbon dioxide, and nitrogen. If desired, this effluent stream can be directly purged into the atmosphere. The energy content of the thermal oxidation system effluent can be recovered, for example, in a waste heat recovery unit. The energy content can also be recovered by heat exchange with another stream (e.g., sweep gas). The energy content can be utilized to directly or indirectly heat, or assist in heating, other units in the process, such as dryers or reactors. In some embodiments, essentially all of the thermal oxidation system effluent is used for indirect heating (utility side) of the dryer. The thermal oxidation system can utilize fuels other than natural gas.

[0469] The yield of carbonaceous materials may vary depending on the above factors, including the type of raw materials and process conditions. In some embodiments, the net yield of solids as a percentage of the starting materials is at least 25%, 30%, 35%, 40%, 45%, 50%, or more on a dry basis. The remainder is divided into condensable vapors such as terpenes, tars, alcohols, acids, aldehydes, or ketones, and non-condensable gases such as carbon monoxide, hydrogen, carbon dioxide, and methane. The relative amount of condensable vapors compared to non-condensable gases also depends on the process conditions, including the presence of water.

[0470] With respect to carbon balance, in some embodiments, the net yield of carbon as a percentage of the starting carbon in the raw materials is at least 25%, 30%, 40%, 50%, 60%, 65%, 70%, 75%, 80%, or more. For example, in some embodiments, the carbonaceous material contains about 40% to about 70% of the carbon contained in the starting materials. The remaining carbon results in the formation of methane, carbon monoxide, carbon dioxide, light hydrocarbons, aromatic compounds, tars, terpenes, alcohols, acids, aldehydes, or ketones to varying degrees.

[0471] In alternative embodiments, some of these compounds are combined with carbon-rich solids to increase the carbon and energy content of the product. In these embodiments, some or all of the gas stream obtained from the reactor, containing various vapors, can be at least partially condensed and then passed over cooled pyrolysis solids obtained from a cooling zone or separate cooling unit. These embodiments are described in more detail below.

[0472] Following the reaction and cooling in the cooling zone (if present), the carbonaceous solid can be introduced into a separate cooling unit. In some embodiments, the solid is recovered and simply allowed to cool at a slow rate. If the carbonaceous solid is reactive or unstable in air, it may be desirable to maintain an inert atmosphere or to rapidly cool the solid to a temperature below 40°C, e.g., ambient temperature. In some embodiments, a water quench is used for rapid cooling. In some embodiments, a fluidized bed cooler is used. The term "cooling unit" should be broadly interpreted to include a container, tank, pipes, or parts thereof.

[0473] In some embodiments, the process further includes operating a cooling unit to cool a warm pyrolysis solid with steam, thereby producing a cold pyrolysis solid and superheated steam; where drying is carried out at least partially using the superheated steam obtained from the cooling unit. Optionally, the cooling unit may be operated to first cool the warm pyrolysis solid with steam to a first cooling unit temperature, and then cool it with air to a second cooling unit temperature, where the second cooling unit temperature is lower than the first cooling unit temperature and relates to reducing the risk of combustion of the warm pyrolysis solid in the presence of air.

[0474] After cooling to ambient conditions, the carbonaceous solid can be recovered and stored, transported to another site, shipped to another site, or otherwise disposed of, traded, or sold. The solid can be fed into a unit for reducing particle size. Various size reduction units, including crushers, shredders, pulverizers, fine grinders, jet mills, pin mills, and ball mills, are known in the art.

[0475] This may include sieving or some other means for separation based on particle size. Grinding, if any, may occur upstream or downstream of grinding. Some of the sieved material (e.g., large lumps) can be returned to the grinding unit. Smaller and larger particles can be recovered for separate downstream use. In some embodiments, the cooled pyrolysis solid is ground into a fine powder, such as pulverized coal or activated carbon products.

[0476] Various additives can be introduced before, during, or after any of the steps disclosed herein, or throughout the entire process. Additives can be broadly classified into process additives selected to improve process performance, such as the time / temperature of decomposition to achieve the carbon yield or desired carbon purity; and product additives selected to improve one or more properties of a biogenic reagent or a downstream product incorporating said reagent. Certain additives can provide enhanced process and product (biogenic reagent or product containing a biogenic reagent) properties.

[0477] Additives may be added before, during, or after any one or more steps in the process, including adding them to the raw material itself at any time before or after harvesting. Additive treatment may be incorporated before, during, or after sizing, drying, or other preparation of the raw material. Additives may be incorporated in or on raw material supply facilities, transport trucks, unloading equipment, storage bins, conveyors (including open or closed conveyors), dryers, process heaters, or any other units. Additives may be added anywhere in the pyrolysis process itself using suitable means for introducing the additives. If desired, additives may also be added after carbonization or after grinding.

[0478] In some embodiments, the additive is selected from metals, metal oxides, metal hydroxides, or combinations thereof. For example, the additive may be selected from, but is not limited to, the group consisting of magnesium, manganese, aluminum, nickel, chromium, silicon, boron, cerium, molybdenum, phosphorus, tungsten, vanadium, iron chloride, iron bromide, magnesium oxide, dolomite, dolomite lime, fluorite, fluorospar, bentonite, calcium oxide, lime, and combinations thereof.

[0479] In some embodiments, the additive is selected from acids, bases, or salts thereof. For example, the additive may be selected from, but is not limited to, sodium hydroxide, potassium hydroxide, magnesium oxide, hydrogen bromide, hydrogen chloride, sodium silicate, potassium permanganate, or combinations thereof.

[0480] In some embodiments, the additive is selected from metal halides. Metal halides are compounds of metals and halogens (fluorine, chlorine, bromine, iodine, and astatine). Halogens can form many compounds with metals. Metal halides are usually obtained by direct combination or, more generally, by neutralization of basic metal salts with hydrohalic acids. In some embodiments, the additive is selected from iron chloride (FeCl2 or FeCl3), iron bromide (FeBr2 or FeBr3), or hydrates thereof, and any combination thereof.

[0481] Additives can result in a final product with a higher energy content (energy density). The increase in energy content may be due to an increase in total carbon, fixed carbon, volatile carbon, or even hydrogen. Alternatively or additionally, the increase in energy content may be due to the removal of non-combustible substances or materials with a lower energy density than carbon. In some embodiments, additives reduce the degree of liquid formation, favoring the formation of solids and gases, or favoring the formation of solids.

[0482] While not limited to any particular hypothesis, additives can chemically modify the starting biomass before pyrolysis or the treated biomass to reduce cell wall breakdown for greater strength / integrity. In some embodiments, additives can increase the fixed carbon content of the biomass raw material before pyrolysis.

[0483] Additives can result in biogenic reagents having improved mechanical properties such as yield strength, compressive strength, tensile strength, fatigue strength, impact strength, modulus of elasticity, bulk modulus, or shear modulus. Additives can improve mechanical properties simply by their presence (e.g., the additive itself imparts strength to the mixture) or due to some transformation occurring within the additive phase or the resulting mixture. For example, reactions such as vitrification may occur in a portion of the biogenic reagent containing the additive, thereby improving the final strength.

[0484] Chemical additives can be applied to wet or dry biomass raw materials. Additives can be applied as solid powders, sprays, mists, liquids, or vapors. In some embodiments, additives can be introduced by spraying a liquid solution (e.g., an aqueous solution or one in a solvent) or by immersion in a tank, bottle, bag, or other container.

[0485] In one embodiment, a pre-immersion treatment is used in which a solid raw material is immersed in a bath containing an additive for a time sufficient to allow the additive to penetrate into the solid supply material, either in a batch or continuous manner.

[0486] In some embodiments, additives applied to the raw materials can reduce the energy required for thermal decomposition or increase the yield of carbonaceous products. In these or other embodiments, additives applied to the raw materials can provide the functionality desired for the intended use of the carbonaceous product.

[0487] Throughput, or process capacity, can vary significantly from small laboratory-scale units to full-scale operations including pilot, demonstration, or semi-commercial scales. In various embodiments, process capacity (for raw materials, products, or both) can be at least about 1 kg / day, 10 kg / day, 100 kg / day, 1 ton / day (all tons are metric tons), 10 tons / day, 100 tons / day, 500 tons / day, 1000 tons / day, 2000 tons / day, or higher.

[0488] In some embodiments, a portion of the generated solid can be recycled to the front end of the process, i.e., a drying or degassing unit, or directly to the reactor. By returning to the front end and passing through the process again, the processed solid may have a higher fixed carbon content. Solids, liquids, and gas streams generated or present in the process can be independently recycled, sent to subsequent processes, or removed / purged from the process at any point.

[0489] In some embodiments, the pyrolyzed material is recovered and then supplied to separate units for further pyrolysis to produce a product with higher carbon purity (e.g., conversion from low fixed carbon material to high fixed carbon material). In some embodiments, the secondary process can be carried out in a simple container, such as a steel drum through which a heated inert gas (e.g., heated N2) is passed. Other containers useful for this purpose include process tanks, barrels, bins, totes, sacks, and roll-offs. This secondary sweep gas, containing volatile components, can be sent, for example, to a thermal oxidation unit or back to the main process reactor. To cool the final product, for example, the solid can be cooled by passing another stream of inert gas, initially at ambient temperature, through it, and then returned to the inert gas preheating system.

[0490] (Biogenic Reagent Manufacturing System) Some variations of the present invention are (a) A feeder configured to introduce carbon-containing raw materials; (b) Any dryer, which is operably connected to the feeder and configured to remove moisture contained in the carbon-containing raw material; (c) A multi-zone reactor configured to be operationally connected to the dryer (wherein the multi-zone reactor includes at least a pyrolysis zone configured to be operationally connected to a spatially separated cooling zone, and the multi-zone reactor is configured to have outlets for removing condensable vapors and non-condensable gases from a solid); (d) Solid coolers arranged in operable communication with multi-zone reactors; and (e) Biogenic reagent recovery unit positioned in operable communication with a solid cooler. Utilize a biogenic reagent manufacturing system equipped with:

[0491] Some variations are (a) A feeder configured to introduce carbon-containing raw materials; (b) Any dryer, which is operably connected to the feeder and configured to remove moisture contained in the carbon-containing raw material; (c) Any preheater, which is operably connected to the dryer and configured to heat or gently thermally decompose the raw material; (d) A pyrolysis reactor configured to be operationally connected to a preheater and to pyrolyze the raw materials; (e) A cooler configured to be operably connected to the pyrolysis reactor and configured to cool the pyrolysis solids; and (f) Biogenic reagent recovery unit positioned in operable communication with the cooler. A biogenic reagent manufacturing system is utilized, wherein the system is configured to include at least one gas outlet for removing condensable vapors and non-condensable gases from a solid.

[0492] The feeder can be physically integrated with a multi-zone reactor, for example, by using a screw feeder or auger mechanism to introduce the supply solid into the first reaction zone.

[0493] In some embodiments, the system further comprises a preheating zone operably connected to the pyrolysis zone. Each of the pyrolysis zone, cooling zone, and preheating zone (if present) may be located within a single unit or in separate units.

[0494] Optionally, a dryer can be configured as a drying zone within a multi-zone reactor. Optionally, a solid cooler can be placed within a multi-zone reactor (i.e., configured as an additional cooling zone or integrated with the main cooling zone).

[0495] The system may include purging means for removing oxygen from the system. For example, the purging means may include one or more inlets for introducing a substantially inert gas, and one or more outlets for removing the substantially inert gas and replaced oxygen from the system. In some embodiments, the purging means is a deaerater operably connected between the dryer and the multi-zone reactor.

[0496] A multi-zone reactor may be configured to include at least a first gas inlet and a first gas outlet. The first gas inlet and the first gas outlet may be in communication with different zones or with the same zone.

[0497] In some embodiments, the multi-zone reactor is configured to include a second gas inlet or a second gas outlet. In some embodiments, the multi-zone reactor is configured to include a third gas inlet or a third gas outlet. In some embodiments, the multi-zone reactor is configured to include a fourth gas inlet or a fourth gas outlet. In some embodiments, each zone within the multi-zone reactor is configured to include a gas inlet and a gas outlet.

[0498] The gas inlet and outlet not only allow for the introduction and extraction of steam, but the gas outlet (probe) in particular enables precise process monitoring and control across various stages of the process, including all stages of the process and potentially all of them. Precise process monitoring is expected to lead to improvements in yield and efficiency over a period during which process conditions can be adjusted dynamically and using operational history.

[0499] In some embodiments, a reaction gas probe is positioned to communicate operably with the pyrolysis zone. Such a reaction gas probe may be useful for extracting and analyzing the gas to determine the degree of reaction, the selectivity of pyrolysis, or other process monitoring. The process can then be controlled or regulated in any number of ways based on the measurements, for example, by adjusting the feed rate, the rate of the inert gas sweep, the temperature (of one or more zones), the pressure (of one or more zones), additives, etc.

[0500] As intended herein, “monitoring and control” via the reaction gas probe should be interpreted as including the extraction of one or more samples via the reaction gas probe, and, where deemed necessary or desirable, the adjustment of the process or equipment based on the measurements using well-known principles of process control (such as feedback, feedforward, proportional, integral, and differential logic).

[0501] A reaction gas probe can be configured to extract a gas sample in several ways. For example, the sampling line may have a pressure lower than the pressure of the pyrolysis reactor, so that a certain amount of gas can be easily extracted from the pyrolysis zone when the sampling line is opened. The sampling line may also be under vacuum, for example, if the pyrolysis zone is near atmospheric pressure. Typically, a reaction gas probe is associated with one gas output or a part of it (e.g., a line branched off from a gas output line).

[0502] In some embodiments, both the gas input and gas output are utilized as reaction gas probes by periodically introducing an inert gas into a zone and withdrawing the inert gas containing the process sample from the gas output ("sample sweep"). Such configurations can be used in zones that otherwise do not have gas inlets / outlets for substantially inert gas for processing, or the reaction gas probes can be associated with separate gas inlets / outlets that are added to the process inlets and outlets. The sampling inert gas periodically introduced and withdrawn for sampling (in embodiments utilizing sample sweeps) may even be different from the process inert gas, if desired, for reasons of analytical accuracy or to introduce analytical tracers.

[0503] For example, the acetic acid concentration in the gas phase of the pyrolysis zone can be measured using a gas probe, and a sample can be extracted. This sample is then analyzed using a suitable technique (e.g., gas chromatography, GC; mass spectrometry, MS; GC-MS, or Fourier transform infrared spectroscopy, FTIR). The CO or CO2 concentration in the gas phase can be measured and used, for example, as an indicator of pyrolysis selectivity for gas / vapor. The terpene concentration in the gas phase can be measured and used, for example, as an indicator of pyrolysis selectivity for liquid.

[0504] In some embodiments, the system further comprises at least one additional gas probe operably connected to a cooling zone or drying zone (if present) or a preheating zone (if present).

[0505] Gas probes for cooling zones can be useful, for example, to determine the extent of any additional chemical reactions occurring within the cooling zone. Gas probes within a cooling zone can also be useful as an independent means of measuring temperature (in addition to thermocouples placed within the cooling zone, for example). This independent measurement can be a correlation between the cooling temperature and a specific type of quantifier. This correlation may be developed individually or established after a period of process operation.

[0506] A gas probe for the drying zone may be useful, for example, for determining the degree of drying by measuring the water content. A gas probe in the preheating zone may be useful, for example, for determining the degree of any mild thermal decomposition that is occurring.

[0507] In one embodiment, to generate a substantial countercurrent flow of the gas phase relative to the solid phase, the cooling zone is configured with a gas inlet, and the pyrolysis zone is configured with a gas outlet. Alternatively or additionally, to generate a substantial countercurrent flow of the gas phase relative to the solid phase, the preheating zone (if present) may be configured with a gas outlet. Alternatively or additionally, to generate a substantial countercurrent flow, the drying zone may be configured with a gas outlet.

[0508] The pyrolysis reactor(s) may be selected from any suitable reactor configuration capable of carrying out the pyrolysis process. Exemplary reactor configurations include, but are not limited to, fixed-bed reactors, fluidized-bed reactors, entrained-flow reactors, augers, ablative reactors, rotating cones, rotating drum kilns, calcination furnaces, roasting furnaces, moving-bed reactors, transport-bed reactors, ablative reactors, rotating cones, or microwave-assisted pyrolysis reactors.

[0509] In some embodiments in which the auger is used, sand or another heat transfer medium can be optionally used. For example, the raw material and sand can be supplied at one end of the screw. The screw mixes the sand and raw material and transports them through the reactor. The screw can provide good control over the residence time of the raw material and does not dilute the pyrolysis product with a carrier gas or fluidizing gas. The sand can be reheated in a separate container.

[0510] In some embodiments where an ablative process is used, the raw material is moved at high speed against a high-temperature metal surface. Ablation of any char formed on the surface can maintain a high heat transfer rate. Such apparatus can prevent dilution of the product. Alternatively, the raw material particles can be suspended in a carrier gas and introduced at high speed through a cyclone whose walls are heated.

[0511] In some embodiments in which a fluidized bed reactor is used, the raw materials can be introduced into a bed of hot sand, which is fluidized by gas (which is usually recycled product gas). The term "sand" as used herein also includes similar substantially inert materials, such as glass particles or recovered ash particles. The high heat transfer rate from the fluidized sand can result in rapid heating of the raw materials. Some ablation may occur due to friction with the sand particles. Heat is typically supplied by heat exchange tubes through which hot combustion gases flow.

[0512] A circulating fluidized bed reactor can be used, in which gas, sand, and raw materials move together. Exemplary transport gases include recycled product gas and combustion gas. The high heat transfer rate from the sand ensures rapid heating of the raw materials, and ablation is expected to be stronger than in a conventional fluidized bed. A separator can be used to separate the product gas from the sand and char particles. The sand particles can be reheated in a fluidized combustor vessel and recycled to the reactor.

[0513] In some embodiments, a multi-zone reactor is a continuous reactor comprising a raw material inlet, a plurality of spatially separated reaction zones configured to individually control the temperature and mixing within each reaction zone, and a carbonaceous solid outlet, wherein one of the reaction zones is configured to have a first gas inlet for introducing a substantially inert gas into the reactor, and another reaction zone is configured to have a first gas outlet.

[0514] In various embodiments, the reactor comprises at least two, three, four, or more reaction zones. Each reaction zone is arranged in communication with individually adjustable heating means. The heating means may be independently selected from electric heat transfer, steam heat transfer, hot oil heat transfer, phase change heat transfer, waste heat transfer, or a combination thereof. In some embodiments, at least one reactor zone is heated by an outflow stream from a thermal oxidation unit, if present.

[0515] The reactor may be configured to individually adjust the gas phase composition and gas phase residence time of at least two reaction zones, including all reaction zones present within the reactor.

[0516] The reactor may have a second gas inlet or a second gas outlet. In some embodiments, the reactor is configured with a gas inlet in each reaction zone. In these or other embodiments, the reactor is configured with a gas outlet in each reaction zone. The reactor may be a parallel-flow or counter-flow reactor.

[0517] In some embodiments, the raw material inlet is provided with a screw or auger feeding mechanism. In some embodiments, the carbonaceous solid outlet is provided with a screw or auger output mechanism.

[0518] One embodiment utilizes a rotary or calcining furnace equipped with a screw feeder. In these embodiments, the reactor is axially rotatable, i.e., rotates around its central axis. The rotational speed affects the solid flow pattern, as well as heat and mass transfer. Each reaction zone may be configured with flights positioned on its inner wall to provide agitation of the solid. The flights may be individually adjustable in each reaction zone.

[0519] Other means of stirring the solid, such as augers, screws, or paddle conveyors, can be used. In some embodiments, the reactor comprises a single continuous auger positioned across each reaction zone. In other embodiments, the reactor comprises twin screws positioned across each reaction zone.

[0520] Some systems are specifically designed to process biomass raw materials with the ability to maintain the approximate size of the feed material throughout the process, i.e., without destroying or significantly damaging its structure. In some embodiments, the pyrolysis zone does not contain augers, screws, or rakes, which tend to significantly reduce the size of the feed material being pyrolyzed.

[0521] In some embodiments of the present invention, the system further comprises a thermal oxidizer operably connected to an outlet from which condensable vapors and non-condensables are removed. The thermal oxidizer may be configured to receive a specific fuel (e.g., natural gas) and an oxidizer (e.g., air) and introduce them into a combustion chamber adapted to the combustion of at least a portion of the fuel and condensable vapors. Certain non-condensable gases, such as CO or CH4, can also be oxidized to CO2.

[0522] When a thermal oxidation device is used, the system may include a heat exchanger positioned between the thermal oxidation device and the dryer, configured to utilize at least a portion of the heat of combustion for the dryer. This embodiment can significantly contribute to the overall energy efficiency of the process.

[0523] In some embodiments, the system further comprises a carbon enhancement unit, which is operably connected to a solid cooler and configured to combine condensable vapor in at least a partially condensed form with a solid. The carbon enhancement unit can increase the carbon content of the biogenic reagent obtained from the recovery unit.

[0524] The system may further comprise separate pyrolysis units adapted to further pyrolyze biogenic reagents to increase their carbon content. These separate pyrolysis units may be relatively simple containers, units, or devices, such as tanks, barrels, bottles, drums, totes, sacks, or roll-offs.

[0525] The entire system may be located in a fixed location or distributed across several locations. The system can be constructed using modules that can be simply replicated for practical scaling up. The system can also be constructed using the principles of economies of scale, as is well known in process industries.

[0526] (Solid carbon enhancement) Next, we will describe some variations of solid carbon enhancement. In some embodiments, a method for producing a biogenic reagent is (a) To provide carbon-containing raw materials including biomass; (b) Optionally, drying the raw materials to remove at least some of the moisture contained within them; (c) Optionally, degas the raw materials to remove at least some of the interstitial oxygen (if any) contained with the raw materials; (d) In a pyrolysis zone, in the presence of a substantially inert gas, the raw material is pyrolyzed for at least 10 minutes at a pyrolysis temperature selected from about 250°C to about 700°C to produce a high-temperature pyrolysis solid, condensable vapor, and non-condensable gas; (e) Separating at least a portion of condensable vapor and at least a portion of non-condensable gas from a high-temperature pyrolysis solid; (f) In a cooling zone, in the presence of a substantially inert gas, cool the high-temperature pyrolysis solid for at least 5 minutes at a cooling temperature below the pyrolysis temperature to produce a warm pyrolysis solid; (g) Optionally, cooling a warm pyrolysis solid to produce a cold pyrolysis solid; (h) Thereafter, pass at least a portion of the condensable vapor or at least a portion of the non-condensable gas from step (e) through a hot pyrolysis solid or a cold pyrolysis solid to form an enhanced pyrolysis solid having an increased carbon content; and (i) Recover the biogenic reagent, which contains at least a portion of the enhanced pyrolysis solid. Includes:

[0527] In some embodiments, step (h) includes passing at least a portion of the condensable vapor from step (e) through a warm pyrolysis solid in vapor or condensed form to produce an enhanced pyrolysis solid having an increased carbon content. In some embodiments, step (h) includes passing at least a portion of the non-condensable gas from step (e) through a warm pyrolysis solid to produce an enhanced pyrolysis solid having an increased carbon content.

[0528] Alternatively or additionally, vapor or gas can be brought into contact with the cold pyrolysis solid. In some embodiments, step (h) includes passing at least a portion of the condensable vapor from step (e) through the cold pyrolysis solid in vapor or condensed form to produce an enhanced pyrolysis solid having an increased carbon content. In some embodiments, step (h) includes passing at least a portion of the non-condensable gas from step (e) through the cold pyrolysis solid to produce an enhanced pyrolysis solid having an increased carbon content.

[0529] In one embodiment, step (h) includes passing substantially all of the condensable vapor from step (e) through a cold pyrolysis solid, either in vapor or condensed form, to produce an enhanced pyrolysis solid having an increased carbon content. In another embodiment, step (h) includes passing substantially all of the non-condensable gas from step (e) through a cold pyrolysis solid to produce an enhanced pyrolysis solid having an increased carbon content.

[0530] The process may include various methods for treating or separating steam or gas before using them for carbon enhancement. For example, an intermediate feed stream obtained from step (e), which contains, or is essentially composed of, at least a portion of condensable steam and at least a portion of non-condensable gas, can be supplied to a separation unit configured to produce at least first and second output streams. In one embodiment, the intermediate feed stream contains, or is essentially composed of, all condensable steam, all non-condensable gas, or both.

[0531] Separation techniques include, or can utilize, distillation columns, flash vessels, centrifuges, cyclones, membranes, filters, packed beds, capillary columns, etc. Separation can be based primarily on, for example, distillation, absorption, adsorption, or diffusion, and can utilize differences in vapor pressure, activity, molecular weight, density, viscosity, polarity, chemical functionality, affinity to the stationary phase, and any combination thereof.

[0532] In some embodiments, the first and second output streams are separated from the intermediate feed stream based on their relative volatility. For example, the separation unit may be a distillation column, a flash tank, or a condenser.

[0533] Therefore, in some embodiments, the first output stream contains condensable vapor, and the second output stream contains non-condensable gas. The condensable vapor may contain at least one carbon-containing compound selected from terpenes, alcohols, acids, aldehydes, or ketones. The vapor from pyrolysis may contain aromatic compounds such as benzene, toluene, ethylbenzene, and xylene. Heavier aromatic compounds, such as persistent tar, may be present in the vapor. The non-condensable gas may contain, or essentially consist of, at least one carbon-containing molecule selected from the group consisting of carbon monoxide, carbon dioxide, and methane.

[0534] In some embodiments, the first and second output streams are intermediate feed streams separated based on relative polarity. For example, the separation unit may be a diffusion column, a packed bed, a chromatography column, or a membrane.

[0535] Accordingly, in some embodiments, the first output stream contains a polar compound, and the second output stream contains a nonpolar compound. The polar compound may contain, or essentially consist of, at least one carbon-containing molecule selected from the group consisting of methanol, furfural, and acetic acid. The nonpolar compound may contain, or essentially consist of, at least one carbon-containing molecule selected from the group consisting of carbon monoxide, carbon dioxide, methane, terpenes, and terpene derivatives.

[0536] Step (h) can increase the total carbon content of the biogenic reagent compared to a process that is identical except for the absence of step (h). In various embodiments, the degree of increase in carbon content may be, for example, about 1%, 2%, 5%, 10%, 15%, 25%, or more.

[0537] In some embodiments, step (h) increases the fixed carbon content of the biogenic reagent. In these or other embodiments, step (h) increases the volatile carbon content of the biogenic reagent. The volatile carbon content is the carbon resulting from volatile components in the reagent. Volatile components may be, but are not limited to, hydrocarbons containing aliphatic or aromatic compounds (e.g., terpenes); oxygen-containing substances containing alcohols, aldehydes, or ketones; and various tars. Volatile carbon usually remains bound to or adsorbed on the solid under ambient conditions, but is released upon heating before the fixed carbon is released as vapor by oxidation, gasification, or other means.

[0538] Depending on the conditions associated with process (h), a certain amount of volatile carbon can become fixed carbon (e.g., via Boodor carbon formation from CO). Typically, the volatile components enter the micropores of the fixed carbon and exist as condensed / adsorbed species, but remain relatively volatile. This residual volatility may be more advantageous for fuel applications compared to product applications requiring high surface area and porosity.

[0539] Step (h) can increase the energy content (i.e., energy density) of the biogenic reagent. The increase in energy content may result from an increase in total carbon, fixed carbon, volatile carbon, or even hydrogen. In various embodiments, the degree of increase in energy content may be, for example, about 1%, 2%, 5%, 10%, 15%, 25%, or even higher.

[0540] For use within the process or for further processing, one or more non-condensable gases or condensable vapors can be recovered by utilizing further separation. For example, further processing may be included to produce purified carbon monoxide or hydrogen.

[0541] As another example, acetic acid can be separated and then reduced to ethanol. The reduction of acetic acid can be achieved, at least partially, using hydrogen obtained from the resulting non-condensable gas.

[0542] Condensible vapors can be used either for energy in a process (e.g., by thermal oxidation) or in carbon enrichment to increase the carbon content of biogenic reagents. Certain non-condensable gases, such as CO or CH4, can be used either for energy in a process or as part of a substantially inert gas for a pyrolysis step. Any combination of the above is also possible.

[0543] A potential benefit of including step (h) is that the gas stream is scrubbed and the resulting gas stream is enriched with CO and CO2. The resulting gas stream can be used for energy recovery, recycled for solid carbon enrichment, or used as an inert gas in the reactor. Similarly, by separating the non-condensable gas from the condensable vapor, for example, the CO / CO2 stream can be prepared for use as an inert gas in a reactor system or cooling system.

[0544] Other variations are based on the understanding that the principles of the carbon enhancement process can be applied to any raw material to which carbon is desired.

[0545] In some embodiments, batch or continuous processes for producing biogenic reagents are described as follows: (a) To provide a solid stream containing carbon-containing material; (b) to provide a gas stream containing condensable carbon-containing vapor, non-condensable carbon-containing gas, or a mixture of condensable carbon-containing vapor and non-condensable carbon-containing gas; and (c) Passing a gas stream through a solid stream under suitable conditions to form a carbon-containing product having an increased carbon content compared to a carbon-containing material. Includes:

[0546] In some embodiments, the starting carbon-containing material is pyrolysis biomass or semi-carbonized biomass. The gas stream can be obtained during an integrated process that provides the carbon-containing material. Alternatively, the gas stream can be obtained from the individual processing of the carbon-containing material. The gas stream or a portion thereof can be obtained from an external source (e.g., a sawmill oven). Mixtures of gas streams and carbon-containing materials from various sources are also possible.

[0547] In some embodiments, the process further includes recycling or reusing the gas stream to repeat the process to further increase the carbon or energy content of the carbon-containing product. In some embodiments, the process further includes recycling or reusing the gas stream to run the process to increase the carbon or energy content of a different raw material than the carbon-containing material.

[0548] In some embodiments, the process further includes introducing a gas stream into a separation unit configured to produce at least first and second output streams, wherein the gas stream comprises a mixture of condensable carbon-containing vapor and non-condensable carbon-containing gas. The first and second output streams can be separated based on specific volatility, relative polarity, or any other property. The gas streams can be obtained from separate processing of carbon-containing materials.

[0549] In some embodiments, the process further includes recycling or reusing the gas stream to repeat the process to further increase the carbon content of the carbon-containing product. In some embodiments, the process further includes recycling or reusing the gas stream to run the process to increase the carbon content of another raw material.

[0550] Carbon-containing products may have an increased total carbon content, a higher fixed carbon content, a higher volatile carbon content, a higher energy content, or any combination thereof, compared to the starting carbon-containing material.

[0551] (Biogenic Reagent Manufacturing System) In related modifications, the biogenic reagent manufacturing system is (a) A feeder configured to introduce carbon-containing raw materials; (b) Any dryer, which is operably connected to the feeder and configured to remove moisture contained in the carbon-containing raw material; (c) A multi-zone reactor configured to be operationally connected to a dryer (the multi-zone reactor comprising at least a pyrolysis zone configured to be operationally connected to a spatially separated cooling zone, and wherein the multi-zone reactor is configured to be configured to have outlets for removing condensable vapors and non-condensable gases from a solid); (d) Solid coolers arranged in operational communication with multi-zone reactors; (e) a material enhancement unit, which is operably connected to a solid cooler and configured to pass condensable vapor or non-condensable gas through a solid to form an enhanced solid having an increased carbon content; and (f) Biogenic reagent recovery unit positioned in operable communication with the material enhancement unit. It is equipped with:

[0552] The system may further include a preheating zone that is operationally connected to the pyrolysis zone. In some embodiments, the dryer is configured as a drying zone within a multi-zone reactor. Each zone may be located within a single unit or in separate units. A solid cooler may also be located within the multi-zone reactor.

[0553] In some embodiments, to generate a substantial countercurrent flow of the gas phase relative to the solid phase, the cooling zone is configured with a gas inlet and the pyrolysis zone is configured with a gas outlet. In these or other embodiments, to generate a substantial countercurrent flow of the gas phase relative to the solid phase, the preheating zone or drying zone (or dryer) is configured with a gas outlet.

[0554] In a particular embodiment, the system (i) A housing having an upper and lower part; (ii) an inlet located at the bottom of the housing, configured to carry condensable vapors and non-condensable gases; (iii) An outlet located at the top of the housing, configured to carry a concentrated gas stream consisting of condensable vapor and non-condensable gas; (iv) the path defined between the upper and lower parts of the housing; and (v) A transport system along a route, configured to transport solids. It incorporates a material-enhancing unit, wherein the housing is shaped such that the solid adsorbs at least a portion of the condensable vapor or at least a portion of the non-condensable gas.

[0555] The present invention enables the production of various compositions useful as biogenic reagents, and products incorporating such reagents. In some modifications, the biogenic reagent is produced by any of the processes disclosed herein, for example, (a) A process of providing carbon-containing raw materials including biomass; (b) Optionally, a step of drying the raw materials to remove at least some of the moisture contained therein; (c) Optionally, a step of degassing the raw materials to remove at least some of the interstitial oxygen (if any) contained with the raw materials; (d) A step of pyrolysis in a pyrolysis zone in the presence of a substantially inert gas for at least 10 minutes at a pyrolysis temperature selected from about 250°C to about 700°C to produce a high-temperature pyrolysis solid, condensable vapor, and non-condensable gas; (e) A step of separating at least a portion of condensable vapor and at least a portion of non-condensable gas from a high-temperature pyrolysis solid; (f) A step of generating a warm pyrolysis solid by cooling a high-temperature pyrolysis solid in a cooling zone in the presence of a substantially inert gas for at least 5 minutes at a cooling temperature below the pyrolysis temperature; (g) A step of cooling a warm pyrolysis solid to produce a cold pyrolysis solid; and (h) A step of recovering a biogenic reagent containing at least a portion of the cold pyrolysis solid. It is manufactured by a process that includes:

[0556] In some embodiments, the reagent contains, on a dry basis, at least 70% by weight, at least 80% by weight, at least 90% by weight, or at least 95% by weight of total carbon. The total carbon includes at least fixed carbon and may further include carbon from volatile matter. In some embodiments, the carbon from volatile matter accounts for at least 5%, at least 10%, at least 25%, or at least 50% of the total carbon present in the biogenic reagent. For example, fixed carbon can be measured using ASTM D3172, while volatile carbon can be measured using ASTM D3175.

[0557] Biogenic reagents may contain approximately 10% by weight or less of hydrogen on a dry basis, for example, approximately 5% by weight or less. Biogenic reagents may contain approximately 1% by weight or less of nitrogen on a dry basis, for example, approximately 0.5% by weight or less. Biogenic reagents may contain approximately 0.5% by weight or less of phosphorus on a dry basis, for example, approximately 0.2% by weight or less. Biogenic reagents may contain approximately 0.2% by weight or less of sulfur on a dry basis, for example, approximately 0.1% by weight or less.

[0558] Carbon, hydrogen, and nitrogen can be measured, for example, using ASTM D5373 for elemental analysis. Oxygen can be measured, for example, using ASTM D3176. Sulfur can be measured, for example, using ASTM D3177.

[0559] One embodiment provides a reagent that contains little to no hydrogen (except from any moisture present), nitrogen, phosphorus, or sulfur, and is substantially composed of carbon and any ash and moisture. Accordingly, some embodiments provide biogenic reagents containing up to 100% carbon, including 100%, on a dry ash (DAF) basis.

[0560] Generally speaking, raw materials such as biomass contain non-volatile species including silica and various metals, which are not easily released during thermal decomposition. Of course, it is also possible to use ashless raw materials, in which case there should be virtually no ash content in the thermally decomposed solid. Ash content can be measured using, for example, ASTM D3174.

[0561] Various amounts of non-combustible materials, such as ash, may be present. Biogenic reagents may contain about 10% by weight or less of non-combustible materials on a dry basis, for example, about 5% by weight, about 2% by weight, or about 1% by weight or less. In some embodiments, the reagent contains little to no ash, or even essentially no ash or other non-combustible materials at all. Thus, some embodiments provide essentially pure carbon, containing 100% carbon on a dry basis.

[0562] Various amounts of water may be present. On a total mass basis, biogenic reagents may contain at least 1% by weight, 2% by weight, 5% by weight, 10% by weight, 15% by weight, 25% by weight, 35% by weight, 50% by weight, or more water. As intended herein, “water” should be interpreted to include any form of water present in the biogenic reagent, including absorbed water, adsorbed water molecules, chemical hydrates, and physical hydrates. Equilibrium water content may change depending on local environmental factors, at least relative humidity. Furthermore, water may change during transport, preparation for use, and other logistics. Water can be measured, for example, using ASTM D3173.

[0563] Biogenic reagents can have varying energy content, which for this purpose refers to the energy density based on the higher heating value associated with the total combustion of the oven-dry reagent. For example, a biogenic reagent may have an energy content of at least 11,000 Btu / lb, at least 12,000 Btu / lb, at least 13,000 Btu / lb, at least 14,000 Btu / lb, or at least 15,000 Btu / lb. In one embodiment, the energy content is about 14,000–15,000 Btu / lb. The energy content can be measured, for example, using ASTM D5865.

[0564] Biogenic reagents can be formed in powder form, such as coarse or fine powder. For example, in this embodiment, the reagent can be formed in powder form having an average mesh size of about 200 mesh, about 100 mesh, about 50 mesh, about 10 mesh, about 6 mesh, about 4 mesh, or about 2 mesh.

[0565] In some embodiments, the biogenic reagent is formed into a structural object comprising pressed, bound, or aggregated particles. The starting material for forming these objects may be a reagent in powder form, such as an intermediate obtained by particle size reduction. The objects may be formed by mechanical pressing or other forces, optionally using a binder or other means to aggregate the particles together.

[0566] In some embodiments, biogenic reagents are manufactured in the form of structural objects whose structure is substantially derived from the raw materials. For example, product chips of biogenic reagents can be manufactured from raw material chips. Alternatively, cylinders of biogenic reagents can be manufactured from raw material cylinders, which are somewhat smaller but otherwise retain the basic structure and geometry of the starting materials.

[0567] The biogenic reagents according to the present invention are manufactured or formed into objects having a minimum dimension of at least about 1 cm, 2 cm, 3 cm, 4 cm, 5 cm, 6 cm, 7 cm, 8 cm, 9 cm, 10 cm, or larger. In various embodiments, the minimum or maximum dimension may be length, width, or diameter.

[0568] Other modifications of the present invention relate to the incorporation of additives into a process, a product, or both. In some embodiments, the biogenic reagent includes at least one process additive incorporated during the process. In these or other embodiments, the reagent includes at least one product additive introduced into the reagent after the process.

[0569] In some embodiments, the biogenic reagent is measured on a dry basis. 70% by weight or more of total carbon; Hydrogen at a concentration of 5% by weight or less; 1% by weight or less of nitrogen; Phosphorus content of 0.5% by weight or less; Sulfur at a rate of 0.2% by weight or less; and Additives selected from metals, metal oxides, metal hydroxides, metal halides, or combinations thereof. Includes:

[0570] The additives may be selected from, but are not limited to, magnesium, manganese, aluminum, nickel, chromium, silicon, boron, cerium, molybdenum, phosphorus, tungsten, vanadium, iron chloride, iron bromide, magnesium oxide, dolomite, dolomite lime, fluorite, fluorospar, bentonite, calcium oxide, lime, and combinations thereof.

[0571] In some embodiments, the biogenic reagent is measured on a dry basis. 70% by weight or more of total carbon; Hydrogen at a concentration of 5% by weight or less; 1% by weight or less of nitrogen; Phosphorus content of 0.5% by weight or less; Sulfur at a rate of 0.2% by weight or less; and Additives selected from acids, bases, or salts thereof Includes:

[0572] The additives may be selected from, but are not limited to, sodium hydroxide, potassium hydroxide, magnesium oxide, hydrogen bromide, hydrogen chloride, sodium silicate, potassium permanganate, or combinations thereof.

[0573] In one embodiment, biogenic reagents are measured on a dry basis. 70% by weight or more of total carbon; Hydrogen at a concentration of 5% by weight or less; 1% by weight or less of nitrogen; Phosphorus content of 0.5% by weight or less; Sulfur at a rate of 0.2% by weight or less; A first additive selected from metals, metal oxides, metal hydroxides, metal halides, or combinations thereof; and A second additive selected from acids, bases, or salts thereof. This includes, where the first additive is different from the second additive.

[0574] The first additive may be selected from magnesium, manganese, aluminum, nickel, chromium, silicon, boron, cerium, molybdenum, phosphorus, tungsten, vanadium, iron chloride, iron bromide, magnesium oxide, dolomite, dolomite lime, fluorite, fluorospar, bentonite, calcium oxide, lime, and combinations thereof. The second additive may be independently selected from sodium hydroxide, potassium hydroxide, magnesium oxide, hydrogen bromide, hydrogen chloride, sodium silicate, potassium permanganate, or combinations thereof.

[0575] A certain biogenic reagent contains, on a dry basis, carbon, hydrogen, nitrogen, phosphorus, sulfur, non-combustible substances, and additives selected from the group consisting of magnesium, manganese, aluminum, nickel, chromium, silicon, boron, cerium, molybdenum, phosphorus, tungsten, vanadium, iron chloride, iron bromide, magnesium oxide, dolomite, dolomite lime, fluorite, fluorospar, bentonite, calcium oxide, lime, and combinations thereof, or is essentially composed of these.

[0576] A certain biogenic reagent, on a dry basis, contains or is essentially composed of carbon, hydrogen, nitrogen, phosphorus, sulfur, non-combustible substances, and additives selected from the group consisting of sodium hydroxide, potassium hydroxide, magnesium oxide, hydrogen bromide, hydrogen chloride, sodium silicate, and combinations thereof.

[0577] The amount of additive (or total additive) can vary widely from about 0.01% to about 25% by weight, including about 0.1% by weight, about 1% by weight, about 5% by weight, about 10% by weight, or about 20% by weight. For example, it will be understood that if a relatively large amount of additive, higher than about 1% by weight, is incorporated, the energy content calculated based on the total reagent weight (including the additive) will decrease. Nevertheless, in various embodiments, the biogenic reagent including the additive may have an energy content of at least about 11,000 Btu / lb, at least 12,000 Btu / lb, at least 13,000 Btu / lb, at least 14,000 Btu / lb, or at least 15,000 Btu / lb.

[0578] The above discussion regarding product form also applies to embodiments incorporating additives. In fact, some embodiments incorporate additives as binders, fluxes, or other modifiers to enhance the final properties for a particular application.

[0579] In some embodiments, the majority of the carbon in a biogenic reagent is classified as renewable carbon. In some embodiments, substantially all of the carbon is classified as renewable carbon. Certain market mechanisms (e.g., renewable identification numbers, tax credits, etc.) may exist in which value is attributed to the renewable carbon content in a biogenic reagent.

[0580] In one embodiment, fixed carbon may be classified as non-renewable carbon (e.g., coal-derived), while volatile carbon, which may be added separately, may be renewable carbon to increase not only the energy content but also the renewable carbon value.

[0581] The biogenic reagents manufactured as described herein are useful for a wide variety of carbonaceous products. Biogenic reagents can themselves become desirable market products. The biogenic reagents provided herein offer lower impurity levels, reduced process emissions, and improved sustainability (including higher renewable carbon content) compared to state-of-the-art products.

[0582] In a modified example, the product comprises any of the biogenic reagents that can be obtained by the disclosed process or that are described in the compositions described herein, or any part, combination, or derivative thereof.

[0583] Generally speaking, biogenic reagents can be burned to generate energy (including electricity and heat); partially oxidized, gasified, or steam reformed to produce synthesis gas; utilized for their adsorption or absorption properties; utilized for their reaction properties in metal refining (e.g., reduction of metal oxides) or other industrial processes; or utilized for their material properties in carbon steel and various other metal alloys. Essentially, biogenic reagents can be used in any market application of carbon-based commodities or advanced materials, including special applications that will be developed.

[0584] Prior to suitability for any product application or actual use, the disclosed biogenic reagents can be analyzed, measured, and optionally modified (e.g., through additives) in various ways. Some properties of potential interest other than chemical composition and energy content include, but are not limited to, density, particle size, surface area, microporosity, absorbency, adsorption, binding capacity, reactivity, desulfurization activity, and basicity.

[0585] Products or materials that may incorporate these biogenic reagents include, but are not limited to, carbon-based blast furnace additives, carbon-based taconite pellet additives, ladle-added carbon-based products, metcoke carbon-based products, coal substitutes, carbon-based coking products, coke breeze products, fluidized bed carbon-based raw materials, carbon-based furnace additives, blown carbon-based products, pulverized coal-based products, stoker carbon-based products, carbon electrodes, or activated carbon products.

[0586] The use of the disclosed biogenic reagents in metal production can reduce slag, increase overall efficiency, and mitigate the environmental impact throughout the lifecycle. Therefore, embodiments of the present invention are particularly well suited to the processing and manufacture of metals.

[0587] Some variations of the present invention utilize biogenic reagents as carbon-based blast furnace additives. A blast furnace is a type of metallurgical furnace used for smelting to produce industrial metals, such as (but not limited to) iron. Smelting is a form of extractive metallurgy; its primary use is to produce metals from their ore. Smelting uses heat and chemical reducing agents to decompose the ore. Carbon, or carbon monoxide derived from carbon, removes oxygen from the ore, leaving the elemental metal.

[0588] The reducing agent may contain or be essentially composed of a biogenic reagent. In a blast furnace, the biogenic reagent, ore, and typically limestone are continuously supplied from the top of the furnace, while air (optionally oxygen-enriched) is blown into the bottom of the furnace chamber, so that chemical reactions occur throughout the furnace as the material descends. The final product is typically the molten metal and slag phases flowing out from the bottom, as well as the flue gases exiting from the top of the furnace. The descending flow of ore in contact with the rising flow of hot, carbon monoxide-rich gas is a countercurrent process.

[0589] The quality of carbon in a blast furnace is measured by its resistance to degradation. The role of carbon as a permeable medium is crucial for economical blast furnace operation. Carbon degradation varies considerably depending on its location within the blast furnace and involves a combination of reactions with CO2, H2O, or O2, and abrasion between carbon particles and with other components of the charged material. Degraded carbon particles can cause clogging and performance degradation.

[0590] The coke reactivity test is a highly valued measure of the performance of carbon in blast furnaces. This test has two components: the coke reactivity index (CRI) and the post-reaction coke strength (CSR). For use in blast furnaces, carbon-based materials with low CRI values ​​(high reactivity) and high CSR values ​​are often obtained. The CRI can be determined according to any suitable method known in the art, for example, by the acceptance-based ASTM method DS341.

[0591] In some embodiments, the biogenic reagent provides a carbon product having properties suitable for direct introduction into a blast furnace.

[0592] The strength of the biogenic reagent can be determined by any suitable method known in the art, for example, by a drop shutter test or a CSR test. In some embodiments, the biogenic reagent, when optionally blended with another carbon source, provides a final carbon product having at least about 50%, 60%, or 70% CSR. The combined product can also provide a final coke product having suitable reactivity for combustion in a blast furnace. In some embodiments, the product has a CRI such that the biogenic reagent is suitable for use as an additive or substitute for met coal, met coke, coke breeze, foundry coke, or blown coal.

[0593] Some embodiments utilize one or more additives in sufficient quantities to provide a biogenic reagent that, when added to another carbon source (e.g., coke) having a CRI or CSR insufficient for use as a blast furnace product, provides a composite product having a CRI or CSR sufficient for use in a blast furnace. In some embodiments, one or more additives are present in sufficient quantities to provide a biogenic reagent having a CRI of about 40%, 30%, or 20% or less.

[0594] In some embodiments, one or more additives selected from alkaline earth metals, or their oxides or carbonates, are introduced during or after the process of producing the biogenic reagent. For example, calcium, calcium oxide, calcium carbonate, magnesium oxide, or magnesium carbonate can be introduced as additives. The addition of these compounds before, during, or after pyrolysis can increase the reactivity of the biogenic reagent in the blast furnace. These compounds result in stronger material, i.e., higher CSR, which can improve the efficiency of the blast furnace. Furthermore, additives such as those selected from alkaline earth metals, or their oxides or carbonates, can result in lower emissions (e.g., SO2).

[0595] In some embodiments, the blast furnace substitute is a biogenic reagent according to the present invention comprising at least about 55 wt% carbon, less than or equal to about 0.5 wt% sulfur, less than or equal to about 8 wt% non-combustible material, and a calorific value of at least about 11,000 Btu / pound. In some embodiments, the blast furnace substitute further comprises about 0.035 wt% or less phosphorus, about 0.5 wt% to about 50 wt% volatile matter, and optionally one or more additives. In some embodiments, the blast furnace substitute comprises about 2 wt% to about 15 wt% dolomite, about 2 wt% to about 15 wt% dolomite lime, about 2 wt% to about 15 wt% bentonite, or about 2 wt% to about 15 wt% calcium oxide. In some embodiments, the blast furnace substitute has dimensions substantially in the range of about 1 cm to about 10 cm.

[0596] In some embodiments, the biogenic reagents according to the present invention are useful as a substitute for foundry coke. Foundry coke is typically characterized by having a carbon content of at least about 85% by weight, a sulfur content of about 0.6% by weight, volatile matter of about 1.5% by weight or less, ash content of about 13% by weight or less, moisture of about 8% by weight or less, phosphorus of about 0.035% by weight, a CRI value of about 30, and dimensions ranging from about 5 cm to about 25 cm.

[0597] Some variations of the present invention utilize biogenic reagents as carbon-based taconite pellet additive products. The ore used in the production of iron and steel is iron oxide. Major iron oxide ores include hematite, limonite (also known as brown iron ore), taconite, and black magnetite. Taconite is an important but low-quality ore, containing both magnetite and hematite. The iron content of taconite is typically 25% to 30% by weight. Blast furnaces usually require ore with an iron content of at least 50% by weight for efficient operation. Iron ore can undergo beneficiation, including crushing, sieving, tumbling, flotation, and magnetic separation. The refined ore is concentrated to over 60% iron and is often formed into pellets before shipment.

[0598] For example, taconite can be crushed into a fine powder and combined with binders such as bentonite clay and limestone. For instance, pellets approximately 1 centimeter in diameter containing about 65% by weight of iron can be formed. The pellets are then calcined to oxidize the magnetite to hematite. The pellets are durable, thereby ensuring that they maintain sufficient porosity to allow the blast furnace charging material to pass through and react with the pelletized ore as heated gases pass through.

[0599] Taconite pellets can be supplied to a blast furnace for iron production, as described above with respect to blast furnace additive products. In some embodiments, biogenic reagents are introduced into the blast furnace. In these or other embodiments, the biogenic reagents are incorporated into the taconite pellets themselves. For example, taconite ore powder can be mixed with a biogenic reagent and a binder after beneficiation, rolled into small objects, and then fired until hardened. In such embodiments, taconite-carbon pellets with a suitable composition can be conveniently introduced into the blast furnace without requiring a separate carbon source.

[0600] Some variations of the present invention utilize biogenic reagents as ladle-added carbon-based products. A ladle is a container used to transport and pour molten metal. Casting ladles are used to pour molten metal into molds to produce castings. Transfer ladles are used to transfer large quantities of molten metal from one process to another. Processing ladles are used for processes carried out in the ladle to alter some aspect of the molten metal, such as the conversion of cast iron to ductile cast iron by adding various elements to the ladle.

[0601] Biogenic reagents can be introduced into any type of ladle, but typically carbon is added to the processing ladle in a suitable amount based on the target carbon content. The carbon blown into the ladle may be in the form of a fine powder for good mass transfer of carbon to the final composition. In some embodiments, when used as a ladle additive product, the biogenic reagent according to the present invention has a minimum dimension of about 0.5 cm, for example, about 0.75 cm, about 1 cm, about 1.5 cm, or larger.

[0602] In some embodiments, the high-carbon biogenic reagents according to the present invention are useful as ladle additive carbon additives in basic oxygen furnaces or electric furnace facilities, for example, wherever ladle addition of carbon is used (e.g., added to ladle carbon during steelmaking).

[0603] In some embodiments, the carbon additive for ladle addition further comprises up to about 5% by weight of manganese, up to about 5% by weight of calcium oxide, or up to about 5% by weight of dolomite lime.

[0604] Directly reduced iron (DRI), also known as sponge iron, is produced by the direct reduction of iron ore (in the form of lumps, pellets, or powder) with a reducing gas conventionally produced from natural gas or coal. The reducing gas is typically synthesis gas, which is a mixture of hydrogen and carbon monoxide that acts as a reducing agent. The biogenic reagents provided herein can be converted into a CO-containing gas stream to act as a reducing agent for producing directly reduced iron.

[0605] Iron nuggets are a high-quality raw material for steelmaking and iron casting. Iron nuggets are essentially all iron and carbon, with minimal gangue (slag) and low levels of metal residue. They are a premium grade pig iron product with excellent transport and handling properties. The carbon in the iron nuggets, or any portion thereof, may be a biogenic reagent provided herein. Iron nuggets can be produced by the reduction of iron ore in a rotary hearth furnace, using the biogenic reagent as a reducing agent and energy source.

[0606] Some variations of the present invention utilize biogenic reagents as metallurgical coke carbon-based products. Metallurgical coke, also known as "met" coke, is a carbon material typically produced by destructive distillation of various blends of bituminous coal. The final solid is an unmolten carbon called metallurgical coke. As a result of the loss of volatile gases and partial melting, met coke has an open, porous form. Met coke has a very low volatile content. However, the ash components that were part of the original bituminous coal raw material remain trapped in the resulting coke. Met coke raw materials are available in a wide range of sizes, from fine powder to basketball-sized chunks. Typical purity ranges from 86–92% by weight of fixed carbon.

[0607] Metallurgical coke is used when high-quality, tough, resilient, and wear-resistant carbon is required. Applications include, but are not limited to, conductive flooring, friction materials (e.g., carbon linings), casting coatings, casting carburizers, corrosive materials, drilling applications, reducing agents, heat treatment agents, ceramic packing media, electrolytic processes, and oxygen elimination.

[0608] Metcoke is characterized by having a calorific value of about 10,000 to 14,000 Btu / pound and an ash content of about 10% by weight or more. Accordingly, in some embodiments, a metcoke substitute product comprises a biogenic reagent according to the present invention containing at least about 80% by weight, 85% by weight, or 90% by weight of carbon, about 0.8% by weight or less of sulfur, about 3% by weight or less of volatile matter, about 15% by weight or less of ash, about 13% by weight or less of moisture, and about 0.035% by weight or less of phosphorus. When used as a metcoke substitute product, the biogenic reagent according to the present invention may have a size range of, for example, about 2 cm to about 15 cm.

[0609] In some embodiments, the metcoke substitute product further includes additives such as chromium, nickel, manganese, magnesium oxide, silicon, aluminum, dolomite, fluorospar, calcium oxide, lime, dolomite lime, bentonite, and combinations thereof.

[0610] Some modifications of the present invention utilize biogenic reagents as coal substitutes. Any process or system that uses coal can, in principle, be adapted to use biogenic reagents.

[0611] In some embodiments, a biogenic reagent is combined with one or more coal-based products to form a composite product that has a higher rank than the coal-based products or emits fewer emissions during combustion than the pure coal-based products.

[0612] For example, lower-grade coals, such as subvital coal, can be used in applications that typically require higher-grade coal products, such as bituminous coal, by combining them with a selected amount of the biogenic reagent according to the present invention. In other embodiments, the grade of a mixed coal product (e.g., a combination of several coals of different grades) can be improved by combining the mixed coal with a certain amount of the biogenic reagent. The amount of the biogenic reagent to be mixed with the coal product may vary depending on the grade of the coal product, the properties of the biogenic reagent (e.g., carbon content, calorific value, etc.), and the desired grade of the final combined product.

[0613] For example, anthracite typically contains at least about 80% by weight of carbon, about 0.6% by weight of sulfur, about 5% by weight of volatile matter, up to about 15% by weight of ash, up to about 10% by weight of water, and a calorific value of about 12,494 Btu / lb. In some embodiments, anthracite substitutes are biogenic reagents containing at least about 80% by weight of carbon, about 0.6% by weight or less of sulfur, about 15% by weight or less of ash, and a calorific value of at least about 12,000 Btu / lb.

[0614] In some embodiments, biogenic reagents are useful as alternatives to conventional coal. Conventional coal products are typically characterized by high sulfur levels, high phosphorus levels, high ash content, and a calorific value of up to approximately 15,000 Btu / lb. In some embodiments, the conventional coal alternative is a biogenic reagent containing approximately 0.5% by weight or less of sulfur, approximately 4% by weight or less of ash, and a calorific value of at least approximately 12,000 Btu / lb.

[0615] Some variations of the present invention utilize the biogenic reagent as a carbon-based coking product. Any coking process or system can be adapted to use the biogenic reagent to produce coke, or to use it as a coking raw material.

[0616] In some embodiments, the biogenic reagent is useful as a general coal or coke substitute. For example, the general coal or coke substitute may contain, or be essentially, a biogenic reagent containing at least about 50% by weight of carbon, about 8% by weight or less of ash, about 0.5% by weight or less of sulfur, and at least about 11,000 Btu / lb of calorific value. In other embodiments, the general coke substitute further contains about 0.5% to about 50% by weight of volatile matter. The general coal or coke substitute may contain about 0.4% to about 15% by weight of moisture.

[0617] In some embodiments, the biogenic reagent is useful as a substitute for petroleum (PET) coke or calcined PET coke. Calcined PET coke is typically characterized by having at least about 66% by weight of carbon, up to 4.6% by weight of sulfur, up to about 5.5% by weight of volatile matter, up to about 19.5% by weight of ash, and up to about 2% by weight of moisture, and is typically sized to about 3 mesh or less. In some embodiments, the calcined PET coke substitute is a biogenic reagent containing at least about 66% by weight of carbon, up to about 4.6% by weight of sulfur, up to about 19.5% by weight of ash, up to about 2% by weight of moisture, and sized to about 3 mesh or less.

[0618] In some embodiments, the biogenic reagent is useful as a carbon substitute for coke (for example, co-fired with metallurgical coal in a coke oven). In one embodiment, the carbon substitute for coke is a biogenic reagent containing at least about 55% by weight of carbon, less than or equal to about 0.5% by weight of sulfur, less than or equal to about 8% by weight of non-combustible material, and a calorific value of at least about 11,000 Btu / pound. In some embodiments, the carbon substitute for coke contains about 0.5% to about 50% by weight of volatile matter or one or more additives.

[0619] Some modifications of the present invention utilize the biogenic reagent as a carbon breeze product having very fine particle sizes, typically, for example, 6 mm, 3 mm, 2 mm, 1 mm, or smaller. In some embodiments, the biogenic reagent according to the present invention is useful as a coke breeze substitute. Coke breeze is typically characterized by having a maximum dimension of about 6 mm or less, a carbon content of at least about 80% by weight, 0.6 to 0.8% by weight of sulfur, 1% to 20% by weight of volatile matter, a maximum of about 13% by weight of ash, and a maximum of about 13% by weight of moisture. In some embodiments, the coke breeze substitute is a biogenic reagent according to the present invention, comprising at least about 80% by weight of carbon, about 0.8% by weight or less of sulfur, about 20% by weight or less of volatile matter, about 13% by weight or less of ash, about 13% by weight or less of moisture, and a maximum dimension of about 6 mm.

[0620] In some embodiments, biogenic reagents are useful, for example, as carbon breeze substitutes during taconite pellet production or in steelmaking processes.

[0621] Several modifications utilize biogenic reagents as raw materials for various fluidized beds or as carbon-based raw material substitutes for fluidized beds. Carbon can be used in fluidized beds for complete combustion, partial oxidation, gasification, steam reforming, etc. Carbon can be converted into synthesis gas for various downstream applications, primarily including the production of energy (e.g., combined heat and power) or liquid fuels (e.g., methanol or Fischer-Tropsch diesel fuel).

[0622] In some embodiments, the biogenic reagents according to the present invention are useful as fluidized bed coal substitutes in fluidized bed furnaces, for example, wherever coal is used (e.g., for process heat or energy production).

[0623] Some variations utilize biogenic reagents as carbon-based furnace additives. Coal-based carbon furnace additives are typically characterized by high sulfur levels, high phosphorus levels, and high ash content, which contribute to the degradation of metal products and cause air pollution. In some embodiments, carbon furnace additive alternatives containing biogenic reagents contain about 0.5% by weight or less of sulfur, about 4% by weight or less of ash, about 0.03% by weight or less of phosphorus, and a maximum dimension of about 7.5 cm. In some embodiments, carbon furnace additive alternatives contain about 0.5% to about 50% by weight of volatile matter and about 0.4% to about 15% by weight of water.

[0624] In some embodiments, biogenic reagents are useful as furnace-added carbon additives in basic oxygen furnaces or electric furnace facilities, for example, wherever furnace-added carbon is used. For example, furnace-added carbon can be added to scrap steel during steelmaking in electric furnace facilities. In electric furnace applications, high-purity carbon is desired to prevent impurities from being returned to the process after early removal of impurities.

[0625] In some embodiments, the furnace-added carbon additive is a biogenic reagent containing at least about 80 wt% carbon, less than or equal to about 0.5 wt% sulfur, less than or equal to about 8 wt% non-combustible material, and at least about 11,000 Btu / pound in calorific value. In some embodiments, the furnace-added carbon additive further contains up to about 5 wt% manganese, up to about 5 wt% fluorospar, about 5 wt% to about 10 wt% dolomite, about 5 wt% to about 10 wt% dolomite lime, or about 5 wt% to about 10 wt% calcium oxide.

[0626] Some modifications utilize the biogenic reagent as a stoker furnace carbon-based product. In some embodiments, the biogenic reagent according to the present invention is useful as a stoker coal substitute in stoker furnace facilities, for example, wherever coal is used (e.g., for process heat or energy production).

[0627] Some variations utilize the biogenic reagent as a blown-in (e.g., pulverized) carbon-based material. In some embodiments, the biogenic reagent is useful as a blown-in grade calcined PET coke substitute. Blown-in grade calcined PET coke is typically characterized by having at least about 66 wt% carbon, about 0.55 to about 3 wt% sulfur, up to about 5.5 wt% volatile matter, up to about 10 wt% ash, and up to about 2 wt% moisture, and is sized to about 6 mesh or less. In some embodiments, the calcined PET coke substitute is a biogenic reagent containing at least about 66 wt% carbon, about 3 wt% or less sulfur, about 10 wt% or less ash, and about 2 wt% or less moisture, and is sized to about 6 mesh or less.

[0628] In some embodiments, biogenic reagents are useful as a substitute for blown carbon in basic oxygen furnaces or electric furnace facilities in any application where blown carbon is used (e.g., blown into slag or ladles during steelmaking).

[0629] In some embodiments, the biogenic reagent is useful as a pulverized coal substitute wherever pulverized coal is used (for example, for process heat or energy production). In some embodiments, the pulverized coal substitute contains up to about 10% calcium oxide.

[0630] Some variations utilize the biogenic reagent as a carbon-added product for metal production. In some embodiments, the biogenic reagent according to the present invention is useful as a carbon-added product for the production of carbon steel or another metal alloy containing carbon. Coal-based downstream carbon-added products are typically characterized by high sulfur levels, high phosphorus levels, high ash content, and high mercury levels, which degrade the quality of the metal and cause air pollution. In some embodiments of the present invention, the carbon-added product contains about 0.5% by weight or less of sulfur, about 4% by weight or less of ash, about 0.03% by weight or less of phosphorus, a minimum dimension of about 1 to 5 mm, and a maximum dimension of about 8 to 12 mm.

[0631] Some modifications utilize biogenic reagents within carbon electrodes. In some embodiments, biogenic reagents are useful as electrode (e.g., anode) materials suitable for use, for example, in aluminum production.

[0632] Other applications of biogenic reagents in carbon electrodes include batteries, fuel cells, capacitors, and other energy storage or supply devices. For example, in lithium-ion batteries, biogenic reagents can be used on the anode side to intercalate lithium. In these applications, carbon purity and low ash content can be very important.

[0633] Some variations of the present invention utilize biogenic reagents as catalyst supports. Carbon is a known catalyst support in a wide range of catalytic chemical reactions, such as the synthesis of mixed alcohols from synthesis gas using a cobalt-molybdenum sulfide metal catalyst supported on a carbon phase, or an iron-based catalyst supported on carbon for the Fischer-Tropsch synthesis of higher hydrocarbons from synthesis gas.

[0634] Several modifications utilize biogenic reagents as activated carbon products. Activated carbon is used in a wide range of liquid and gas phase applications, including water treatment, air purification, solvent vapor recovery, food and beverage processing, and pharmaceuticals. For activated carbon, the porosity and surface area of ​​the material are generally important. The biogenic reagents provided herein can provide superior activated carbon products in various embodiments by (i) having a larger surface area than fossil fuel-based activated carbon; (ii) being renewable carbon; (iii) the vascularity of the biomass raw material allowing for better penetration / distribution of additives, which in combination with the additives enhances pollutant control; and (iv) having less inert material (ash) resulting in greater reactivity.

[0635] It should be recognized that the applications described above regarding the market uses of biogenic reagents are neither exclusive nor exhaustive. Therefore, a biogenic reagent described as suitable for one type of carbon product may be suitable for any other application described in various embodiments. These applications are illustrative only, and other applications of biogenic reagents exist.

[0636] Furthermore, in some embodiments, the same physical material can be used in multiple market processes in an integrated or sequential manner. Therefore, for example, a biogenic reagent used as a carbon electrode or activated carbon can, upon reaching the end of its service life as a high-performance material, then be introduced into a combustion process for energy value, or a metal production process (e.g., metal ore reduction), etc.

[0637] In some embodiments, biogenic reagents can be used both for their reaction / adsorption properties and as fuel. For example, biogenic reagents injected into an emissions stream are suitable for removing contaminants, which can then be combusted by the biogenic reagent particles and possibly the contaminants to generate energy that can thermally destroy or chemically oxidize the contaminants.

[0638] Compared to conventional fossil fuel-based products, biogenic reagents can offer significant environmental and product usage advantages. Biogenic reagents may not only be environmentally superior, but also functionally superior from a process perspective, for example, due to their higher purity.

[0639] Regarding some embodiments of metal production, the production of biogenic reagents by the disclosed process is compared to the coking of coal-based products required to prepare them for use in metal production, which involves the production of CO, CO2, NO x This can significantly reduce emissions of SO2 and hazardous air pollutants.

[0640] By using biogenic reagents instead of coal or coke, environmental emissions of SO2, hazardous air pollutants, and mercury are also significantly reduced.

[0641] Furthermore, due to the purity of these biogenic reagents (including low ash content), the disclosed biogenic reagents have the potential to reduce slag and increase production capacity in batch-type metal production processes.

[0642] In some embodiments, the biogenic reagent functions as activated carbon. For example, it can activate a low-fixed-carbon material, activate a high-fixed-carbon material, or activate both materials so that the biochar composition (blend) functions as activated carbon.

[0643] In one embodiment, a portion of the biogenic reagent is recovered as an activated carbon product, while another portion of the biogenic reagent (e.g., the remainder) is pelletized with a binder to produce biochar pellets. In another embodiment, the biogenic reagent is pelletized with a binder to produce biochar pellets, which are then shipped for conversion to an activated carbon product. This conversion may include pulverization into a powder, or it may include chemical treatment with, for example, steam, acid, or base. In these embodiments, the biochar pellets can be considered as activated carbon precursor pellets.

[0644] In one embodiment, the fixed carbon in the biogenic reagent can be used primarily to produce activated carbon, while the volatile carbon in the biogenic reagent can be used primarily to produce a reducing gas. For example, at least 50% by weight, at least 90% by weight, or essentially all, of the fixed carbon in the biogenic reagent produced in step (b) can be recovered as activated carbon in step (f), while at least 50% by weight, at least 90% by weight, or essentially all, of the volatile carbon in the biogenic reagent produced in step (b) can be directed towards a reducing gas (for example, via a steam reforming reaction of volatile carbon to CO).

[0645] Activated carbon, when manufactured, may be characterized by an iodine value of, for example, at least about 500, 750, 800, 1000, 1500, or 2000. Activated carbon is... 14 C / 12 The activated carbon may be characterized by a renewable carbon content of at least 50%, 60%, 70%, 80%, 90%, or 95%, as determined by the measurement of the 1C isotope ratio. In some embodiments, the activated carbon is 14 C / 12 It is characterized as a (fully) renewable activated carbon, as determined by the measurement of its 1C isotope ratio.

[0646] In some embodiments, the pyrolysis reactor is configured to optimize the production of different types of activated carbon. For example, reaction conditions (e.g., time, temperature, and steam concentration) may be selected to obtain activated carbon products having specific attributes, such as iodine value. Different reaction conditions may be selected to obtain different activated carbon products, for example, those with a higher iodine value. The pyrolysis reactor can be operated in campaign mode to produce one product and then switched to another mode for another product. The first product can be removed continuously or periodically during the first campaign, or before switching the reaction conditions of the pyrolysis reactor.

[0647] Activated carbon may be characterized by an iodine value of, for example, at least about 500, 750, 1000, 1500, or 2000. Activated carbon is... 14 C / 12 It may be characterized by a renewable carbon content of at least 90%, as determined by the measurement of the 1C isotope ratio. In some embodiments, the activated carbon is 14 C / 12 It is characterized as a (fully) renewable activated carbon, as determined by the measurement of its 1C isotope ratio.

[0648] Activated carbon produced by the processes disclosed herein can be used in many ways.

[0649] In some embodiments, activated carbon is used internally at the process site to purify one or more major products. In some embodiments, activated carbon is used at site to purify water. In these or other embodiments, activated carbon is used at site to treat liquid waste streams to reduce liquid phase emissions or to treat steam waste streams to reduce atmospheric emissions. In some embodiments, activated carbon is used as a soil conditioner to support the generation of new biomass, which may be the same type of biomass used as local raw materials at the site.

[0650] Activated carbon prepared according to the processes disclosed herein may have properties equal to or better than conventional fossil fuel-based activated carbon. In some embodiments, the activated carbon has a surface area comparable to, equal to, or greater than that associated with fossil fuel-based activated carbon. In some embodiments, the activated carbon can control contaminants as well as or better than conventional activated carbon products.

[0651] In some embodiments, the activated carbon has an inert material (e.g., ash) level that is comparable to, equal to, or lower than, that associated with conventional activated carbon products. In some embodiments, the activated carbon has a particle size or particle size distribution that is comparable to, equal to, greater than, or smaller than, that associated with conventional activated carbon products. In some embodiments, the activated carbon has a particle shape that is comparable to, substantially similar to, or identical to, that associated with conventional activated carbon products. In some embodiments, the activated carbon has a particle shape that is substantially different from the particle shape associated with conventional activated carbon products.

[0652] In some embodiments, the activated carbon has a pore volume that is comparable to, equal to, or greater than, that of conventional activated carbon products. In some embodiments, the activated carbon has pore dimensions that are comparable to, substantially similar to, or the same as, that of conventional activated carbon products. In some embodiments, the activated carbon has particle abrasion resistance that is comparable to, substantially similar to, or the same as, that of conventional activated carbon products. In some embodiments, the activated carbon has a hardness value that is comparable to, substantially similar to, or the same as, that of conventional activated carbon products.

[0653] In some embodiments, the activated carbon has a bulk density that is comparable to, substantially comparable to, or the same as, the bulk density associated with conventional activated carbon products. In some embodiments, the activated carbon product has an adsorption capacity that is comparable to, substantially comparable to, or the same as, the adsorption capacity associated with conventional activated carbon products.

[0654] Prior to suitability or practical application for any particular product use, the disclosed activated carbon can be analyzed, measured, and optionally modified (e.g., by additives) in various ways. Some properties of potential interest include density, particle size, surface area, microporosity, absorbency, adsorption, binding capacity, reactivity, desulfurization activity, basicity, hardness, and iodine value.

[0655] Activated carbon is commercially used in a wide range of liquid and gas phase applications, including water treatment, air purification, solvent vapor recovery, food and beverage processing, sugar and sweetener refining, automotive applications, and pharmaceuticals. Key product attributes of activated carbon include particle size, shape, composition, surface area, pore volume, pore dimensions, particle size distribution, chemical properties of the carbon surface and interior, particle abrasion resistance, hardness, bulk density, and adsorption capacity.

[0656] The bulk density of biogenic activated carbon can range from approximately 50 g / liter to approximately 650 g / liter.

[0657] The surface area of ​​biogenic activated carbon can vary widely. An exemplary surface area (e.g., BET surface area) is approximately 400 m². 2 / g~about 2000m 2 / g or more, for example, about 500m 2 / g, 600m 2 / g, 800m 2 / g, 1000m 2 / g, 1200m 2 / g, 1400m 2 / g, 1600m 2 / g, or 1800m 2 The range is / g. Surface area usually correlates with adsorption capacity.

[0658] Pore ​​size distribution can be important in determining the final performance of activated carbon. Pore size measurements may include micropore content, mesopore content, and macropore content.

[0659] The iodine value is a parameter used to characterize the performance of activated carbon. The iodine value measures the degree of carbon activation and is a measure of micropore (e.g., 0–20 Å) content. This is an important measurement for liquid-phase applications. Exemplary iodine values ​​of activated carbon products manufactured by embodiments of this disclosure include approximately 500, 600, 750, 900, 1000, 1100, 1200, 1300, 1500, 1600, 1750, 1900, 2000, 2100, and 2200, including all intervening ranges. The unit of iodine value is milligrams of iodine per gram of carbon.

[0660] Another pore-related measurement is the methylene blue value, which measures the mesopore content (e.g., 20–500 Å). Exemplary methylene blue values ​​of activated carbon products produced by embodiments of this disclosure include approximately 100, 150, 200, 250, 300, 350, 400, 450, and 500, including all intervening ranges. The unit of the methylene blue value is milligrams of methylene blue (methylthioninium chloride) per gram of carbon.

[0661] Another pore-related measurement is the molasses number, which measures the macropore content (e.g., >500 Å). Exemplary molasses numbers for activated carbon products produced by embodiments of this disclosure include approximately 100, 150, 200, 250, 300, 350, and 400, including all intervening ranges. The unit of molasses number is milligrams of molasses per gram of carbon.

[0662] In some embodiments, the activated carbon is, for example, at least about 0.5 cm 3 / g, for example, at least about 1cm 3It is characterized by a mesopore volume of / g.

[0663] Activated carbon may be characterized by its water retention capacity. In various embodiments, the activated carbon products produced by embodiments of this disclosure have a water retention capacity of about 10% to about 300% (weight of water divided by the weight of dry activated carbon) at 25°C, for example, about 50% to about 100%, for example, about 60% to 80%.

[0664] Hardness, or abrasion number, is a measure of the abrasion resistance of activated carbon. It is an indicator of the physical integrity of the activated carbon to withstand frictional forces and mechanical stress during handling or use. A certain degree of hardness is desirable, but excessive hardness can lead to excessive equipment abrasion. Exemplary abrasion numbers measured according to ASTM D3802 range from about 1% to over 99%, for example, about 1%, about 5%, about 10%, about 15%, about 20%, about 25%, about 30%, about 35%, about 40%, about 45%, about 50%, about 55%, 60%, about 65%, about 70%, about 75%, about 80%, about 85%, about 90%, about 95%, about 96%, about 97%, about 98%, about 99%, or over 99%.

[0665] In some embodiments, activated carbon is considerably resistant to abrasion, but an optimal range of hardness can be achieved that does not cause abrasion and wear in capital facilities that process the activated carbon. This optimal value is made possible in some embodiments of the present disclosure by the selection of raw materials and processing conditions. In some embodiments where downstream applications can cope with high hardness, the processes of the present disclosure can be operated to increase or maximize hardness in order to produce biogenic activated carbon products having abrasion numbers of about 75%, about 80%, about 85%, about 90%, about 95%, about 96%, about 97%, about 98%, about 99%, or more than about 99%.

[0666] The biogenic activated carbon provided by this disclosure has a wide range of commercial applications. For example, but not limited to, biogenic activated carbon can be used in emission control, water purification, groundwater treatment, wastewater treatment, air stripping applications, PCB removal applications, odor removal applications, soil vapor extraction, gas production plants, industrial water filtration, industrial fumigation, tanks and process vents, pumps, blowers, filters, prefilters, mist filters, ductwork, piping modules, adsorbers, absorbers, and columns.

[0667] In one embodiment, a method of using activated carbon to reduce emissions is: (a) To provide activated carbon particles comprising a biogenic activated carbon composition recovered from a second reactor disclosed herein; (b) Provide a gas phase discharge stream containing at least one selected contaminant; (c) To provide additives selected to assist in the removal of selected contaminants from the gas phase exhaust stream; (d) Introducing activated carbon particles and additives into the gas phase discharge stream to adsorb at least a portion of the selected contaminants onto the activated carbon particles, thereby generating carbon particles with adsorbed contaminants within the gas phase discharge stream; and (e) Separating at least a portion of the carbon particles with adsorbed contaminants from the gas phase emission stream to create a gas phase emission stream with reduced contaminants. Includes:

[0668] Additives for biogenic activated carbon compositions can be provided as part of activated carbon particles. Alternatively or additionally, additives can be introduced directly into the gas phase emission stream, the fuel bed, or the combustion zone. As will be understood by those skilled in the art, other methods are possible for introducing additives directly or indirectly into the gas phase emission stream for the removal of selected contaminants.

[0669] The selected contaminants (in the gas phase emission stream) may be metals. The metals may include, or essentially consist of, mercury, boron, selenium, arsenic, or compounds, salts, or mixtures thereof. In some embodiments, the metals are selected from the group consisting of mercury, boron, selenium, arsenic, and any compounds, salts, and mixtures thereof. The selected contaminants may be, for example, hazardous air pollutants, organic compounds (e.g., VOCs), or non-condensable gases. In some embodiments, the biogenic activated carbon product adsorbs, absorbs, or chemically adsorbs the selected contaminants in greater quantities than an equivalent amount of the non-biogenic activated carbon product. In some such embodiments, the selected contaminants are metals, hazardous air pollutants, organic compounds (e.g., VOCs), non-condensable gases, or any combination thereof. In some embodiments, the selected contaminants include mercury. In some embodiments, the selected contaminants include one or more VOCs. In some embodiments, the biogenic activated carbon contains at least about 1% by weight of hydrogen or at least about 10% by weight of oxygen.

[0670] Hazardous air pollutants are pollutants that cause or may cause cancer or other serious health effects, such as reproductive effects or birth defects, or adverse effects on the environment and ecosystems. Section 112 of the Amended Clean Air Act is incorporated herein by reference in its entirety. Under Section 112 of the Clean Air Act, the U.S. Environmental Protection Agency (EPA) is required to control 189 hazardous air pollutants. Current or future compounds classified as hazardous air pollutants by the EPA are included in the possible selected pollutants in this context.

[0671] Volatile organic compounds (VOCs), some of which are hazardous air pollutants, are organic chemicals that have a high vapor pressure under normal room temperature conditions. Examples include short-chain alkanes, olefins, alcohols, ketones, and aldehydes. Many VOCs are hazardous to human health or harmful to the environment. The EPA regulates VOCs in air, water, and land. The EPA's definition of VOCs is found in 40, Section 51.100 of the Code of Federal Regulations (CFR), which is incorporated herein by reference in its entirety.

[0672] Non-condensable gases are gases that do not condense under normal room temperature conditions. Examples of non-condensable gases include, but are not limited to, nitrogen oxides, carbon monoxide, carbon dioxide, hydrogen sulfide, sulfur dioxide, sulfur trioxide, methane, ethane, ethylene, ozone, ammonia, or combinations thereof.

[0673] Multiple contaminants can be removed by the disclosed activated carbon particles. In some embodiments, the carbon particles with adsorbed contaminants contain at least two contaminants, at least three contaminants, or more. The activated carbon disclosed herein can enable not only multi-contaminant control but also control of specific target contaminants (e.g., selenium).

[0674] In some embodiments, carbon particles with adsorbed contaminants are treated to regenerate activated carbon particles. In some embodiments, the method includes thermal oxidation of the carbon particles with adsorbed contaminants. The carbon particles with adsorbed contaminants, or their regenerated form, can be burned to provide energy.

[0675] In some embodiments, additives for activated carbon include or are essentially composed of acids, bases, salts, metals, metal oxides, metal hydroxides, metal halides, or combinations thereof. In some embodiments, the additives are selected from the group consisting of magnesium, manganese, aluminum, nickel, iron, chromium, silicon, boron, cerium, molybdenum, phosphorus, tungsten, vanadium, iron chloride, iron bromide, magnesium oxide, dolomite, dolomite lime, fluorite, fluorospar, bentonite, calcium oxide, lime, sodium hydroxide, potassium hydroxide, hydrogen bromide, hydrogen chloride, sodium silicate, potassium permanganate, organic acids (e.g., citric acid), and combinations thereof.

[0676] In some embodiments, the gas phase exhaust stream is obtained from metal processing, such as the processing of high-sulfur-content metal ores.

[0677] In an exemplary embodiment of mercury control, activated carbon can be blown upstream (e.g., into ductwork) of a particulate matter control device such as an electrostatic precipitator or fabric filter. Depending on the circumstances, a flue gas desulfurization (dry or wet) system may be located downstream of the activated carbon injection point. The activated carbon can be blown in as a powder under pneumatic pressure. The injection location is typically determined by the existing plant configuration (unless it is a new site) and whether additional downstream particulate matter control equipment will be modified.

[0678] For boilers currently equipped with particulate matter control devices, the implementation of biogenic activated carbon injection for mercury control may involve (i) injection of powdered activated carbon upstream of the existing particulate matter control device (electrostatic precipitator or fabric filter); (ii) injection of powdered activated carbon downstream of the existing electrostatic precipitator and upstream of the installed fabric filter; or (iii) injection of powdered activated carbon into the electric field of the electrostatic precipitator. The incorporation of iron or iron-containing compounds can dramatically improve the performance of the electrostatic precipitator for mercury control. Furthermore, the incorporation of iron or iron-containing compounds can dramatically change the options at the end of its lifespan because it allows for the separation of spent activated carbon solids from other ash.

[0679] In some embodiments, the powdered activated carbon blowing approach can be used in combination with existing SO2 control devices. Provided that means for recovering the activated carbon adsorbent downstream of the blowing point are available, the activated carbon can be blown before or after the SO2 control device.

[0680] In some embodiments, the same physical material can be used in multiple processes in an integrated or sequential manner. For example, activated carbon can be introduced at the end of its service life as a high-performance material into combustion processes for energy value, or into metal production processes that require carbon but do not require the properties of activated carbon.

[0681] Biogenic activated carbon and the principles of this disclosure can be applied to liquid-phase applications, for example, including the processing of water, aqueous streams of varying purities, solvents, liquid fuels, polymers, molten salts, and molten metals. As intended herein, “liquid phase” includes slurries, suspensions, emulsions, multiphase systems, or any other material in which at least some amount of liquid is present (or can be conditioned to be present).

[0682] In one embodiment, the present disclosure provi...

Claims

1. A method for producing biochar pellets, (a) to thermally decompose a biomass-containing raw material in a thermal decomposition reactor, thereby generating thermal decomposition steam containing solid biochar-containing material and polyphenol material; (b) Introducing the pyrolysis vapor into a thermally controlled multistage separation system configured to separate the pyrolysis condensate in liquid form from a non-condensable gas (where the pyrolysis condensate contains the polyphenol material); (c) Contacting the solid biochar-containing material with the polyphenol material to produce an intermediate mixture; (d) Introducing the intermediate mixture into a densification unit to generate a biochar pellet precursor; and (e) to at least partially dry the biochar pellet precursor, thereby producing biochar pellets. : includes, The method wherein the biochar pellets are characterized by a 24-hour water absorption rate of approximately 20% by weight or less, as measured at 25°C and 1 bar.

2. The biomass-containing raw materials include coniferous tree chips, hardwood chips, wood harvesting residues, tree branches, tree stumps, leaves, bark, sawdust, corn, corn stover, wheat, wheat straw, rice, rice straw, sugarcane, sugarcane bagasse, sugarcane straw, energy cane, sugar beet, sugar beet pulp, sunflower, sorghum, canola, algae, Japanese pampas grass, alfalfa, switchgrass, fruit, fruit shells, fruit stems, fruit peels, The method according to claim 1, comprising fruit seeds, vegetables, vegetable shells, vegetable stems, vegetable peels, vegetable seeds, grape pomace, almond shells, pecan shells, coconut shells, coffee grounds, food waste, commercial waste, grass pellets, hay pellets, wood pellets, cardboard, paper, paper pulp, paper packaging, paper scraps, food packaging, construction or demolition waste, railway sleepers, lignin, animal manure, municipal solid waste, municipal sewage, or a combination thereof, selected from these.

3. The method according to claim 1, wherein the solid biochar-containing material contains about 65% to about 95% by weight of fixed carbon.

4. The method according to any one of claims 1 to 3, wherein the thermally controlled multistage separation system comprises one or more filters, an absorption bed having a solid medium, an absorption bed having a liquid medium, an adsorption bed having a solid medium, a dry scrubber, a wet scrubber, a venturi scrubber, a centrifuge, a cyclone, a quench unit, a reactive condenser, a distillation column, a reactive distillation column, an evaporator, a reactive evaporator, a heat exchanger, a fan separator, an electrostatic precipitator, a demister, or a combination thereof, configured to produce the pyrolysis condensate and a gas stream from the pyrolysis vapor.

5. The method according to any one of claims 1 to 3, wherein the thermally controlled multi-stage separation system comprises a cyclone unit configured to separate the solid biochar-containing material from the pyrolysis steam.

6. The method according to any one of claims 1 to 3, wherein the quench unit is configured to expose the pyrolysis vapor to water to produce the pyrolysis condensate.

7. The method according to claim 4, further comprising a demister unit configured to recover residual liquid from the gas stream, wherein the thermally controlled multistage separation system is further a demister unit.

8. The method according to claim 7, wherein the residual liquid is combined with the thermal decomposition condensate.

9. The method according to any one of claims 1 to 8, wherein the thermally controlled multi-stage separation system is configured to capture a plurality of liquid fractions.

10. The method according to claim 9, wherein the thermally controlled multi-stage separation system is configured to capture the plurality of liquid fractions according to molecular weight, boiling point, polarity, or a combination thereof.

11. The method according to any one of claims 1 to 10, wherein the polyphenol material contains about 20% to about 80% by weight of fixed carbon.

12. The method according to any one of claims 1 to 11, wherein the polyphenol material has a weight-average molecular weight of about 75 g / mol to about 50,000 g / mol.

13. The method according to any one of claims 1 to 12, wherein the polyphenol material has a viscosity of about 1 cP to about 1000 cP at 25°C.

14. The method according to any one of claims 1 to 13, wherein the polyphenol material contains about 1% to about 60% by weight of water.

15. The method according to any one of claims 1 to 14, wherein the intermediate mixture has a weight ratio of the polyphenol material to the solid biochar-containing material selected from about 0.01 to about 5.

16. The method according to any one of claims 1 to 15, wherein the polyphenol material is heated before it comes into contact with the solid biochar-containing material.

17. The method according to claim 16, wherein the polyphenol material is heated to a temperature of at least about 150°C.

18. The method according to any one of claims 1 to 17, wherein the solid biochar-containing material is heated before it comes into contact with the polyphenol material.

19. The method according to any one of claims 1 to 18, wherein the solid biochar-containing material is at a temperature within ±100°C of the temperature of the pyrolysis reactor before it comes into contact with the polyphenol material.

20. The method according to any one of claims 1 to 18, wherein the solid biochar-containing material is at a temperature within ±50°C of the temperature of the pyrolysis reactor before it comes into contact with the polyphenol material.

21. The method according to any one of claims 1 to 20, wherein the intermediate mixture is heated before step (d).

22. The method according to any one of claims 1 to 21, wherein the densification unit is selected from an extruder, a briquette, a pellet mill, or a combination thereof.

23. The method according to any one of claims 1 to 22, wherein the densification unit is operated at a densification temperature higher than 100°C.

24. The method according to any one of claims 1 to 23, wherein in step (d), the densification unit is configured to generate a concentrated polyphenol material on the outer shell of the biochar pellet precursor.

25. The method according to any one of claims 1 to 24, wherein steps (d) and (e) are combined and the densification unit is also configured for drying the biochar pellet precursor.

26. The method according to any one of claims 1 to 25, wherein the biochar pellets have a water content of 0% to about 10% by weight.

27. The method according to any one of claims 1 to 25, wherein the biochar pellets have a water content of 0% to about 5% by weight.

28. The method according to any one of claims 1 to 25, wherein the biochar pellets have a water content of 0% to about 2% by weight.

29. The method according to any one of claims 1 to 28, wherein the biochar pellets have a fixed carbon content of about 50% by weight to about 99% by weight of fixed carbon on a dry basis.

30. The method according to any one of claims 1 to 29, wherein the 24-hour water absorption rate of the biochar pellets is approximately 10% by weight or less, as measured at 25°C and 1 bar.

31. The method according to any one of claims 1 to 29, wherein the 24-hour water absorption rate of the biochar pellets is approximately 6% by weight or less, as measured at 25°C and 1 bar.

32. The biochar pellets are at least about 100 lb at 25°C. f / in 2 A method according to any one of claims 1 to 31, characterized by the pellet compressive strength.

33. The biochar pellets are at least about 100 lb f / in 2 The method according to any one of claims 1 to 32, characterized by the immersion / drying pellet compressive strength, wherein the immersion / drying pellet compressive strength is measured by immersing the biochar pellets in water at 25°C for 24 hours, and then drying the biochar pellets in air at 105°C for 24 hours.

34. The method according to any one of claims 1 to 34, wherein the biochar pellets do not contain a pellet binder other than the polyphenol material.

35. The method according to any one of claims 1 to 35, wherein the biochar pellet is subjected to further thermal decomposition in order to increase the fixed carbon content of the biochar pellet.

36. A method for producing biochar pellets, (a) to thermally decompose a biomass-containing raw material in a thermal decomposition reactor, thereby generating thermal decomposition steam containing solid biochar-containing material and polyphenol material; (b) Introducing the pyrolysis vapor into a thermally controlled multistage separation system configured to separate the pyrolysis condensate in liquid form from a non-condensable gas (where the pyrolysis condensate contains the polyphenol material); (c) Introducing the solid biochar-containing material into a densification unit to generate a first biochar pellet precursor; (d) Adding the polyphenol material to the first biochar pellet precursor to produce a second biochar pellet precursor; and (e) to at least partially dry the second biochar pellet precursor, thereby producing biochar pellets. : includes, The method wherein the biochar pellets are characterized by a 24-hour water absorption rate of approximately 20% by weight or less, as measured at 25°C and 1 bar.

37. A method for producing biochar pellets, (a) to thermally decompose a biomass-containing raw material in a thermal decomposition reactor, thereby generating a solid biochar-containing material and thermal decomposition steam; (b) To provide polyphenol materials; (c) Contacting the solid biochar-containing material with the polyphenol material to produce an intermediate mixture; (d) Introducing the intermediate mixture into a densification unit to generate a biochar pellet precursor; and (e) to at least partially dry the biochar pellet precursor, thereby producing biochar pellets. : includes, The method wherein the biochar pellets are characterized by a 24-hour water absorption rate of approximately 20% by weight or less, as measured at 25°C and 1 bar.

38. The biomass-containing raw materials include coniferous tree chips, hardwood chips, wood harvesting residues, tree branches, tree stumps, leaves, bark, sawdust, corn, corn stover, wheat, wheat straw, rice, rice straw, sugarcane, sugarcane bagasse, sugarcane straw, energy cane, sugar beet, sugar beet pulp, sunflower, sorghum, canola, algae, Japanese pampas grass, alfalfa, switchgrass, fruit, fruit shells, fruit stems, fruit peels, The method according to claim 37, comprising fruit seeds, vegetables, vegetable shells, vegetable stems, vegetable peels, vegetable seeds, grape pomace, almond shells, pecan shells, coconut shells, coffee grounds, food waste, commercial waste, grass pellets, hay pellets, wood pellets, cardboard, paper, paper pulp, paper packaging, paper scraps, food packaging, construction or demolition waste, railway sleepers, lignin, animal manure, municipal solid waste, municipal sewage, or a combination thereof, selected from these.

39. The method according to claim 37, wherein the solid biochar-containing material contains approximately 65% ​​to approximately 95% by weight of fixed carbon.

40. The method according to any one of claims 37 to 39, wherein the polyphenol material contains about 20% to about 80% by weight of fixed carbon.

41. The method according to any one of claims 37 to 40, wherein the polyphenol material has a weight-average molecular weight of about 75 g / mol to about 50,000 g / mol.

42. The method according to any one of claims 37 to 41, wherein the polyphenol material has a viscosity of about 1 cP to about 1000 cP at 25°C.

43. The method according to any one of claims 37 to 42, wherein the polyphenol material contains about 1% to about 60% by weight of water.

44. The method according to any one of claims 37 to 43, wherein the intermediate mixture has a weight ratio of the polyphenol material to the solid biochar-containing material selected from about 0.01 to about 5.

45. The method according to any one of claims 37 to 44, wherein the densification unit is selected from an extruder, a briquette, a pellet mill, or a combination thereof.

46. The method according to any one of claims 37 to 45, wherein the densification unit is operated at a densification temperature higher than 100°C.

47. The method according to any one of claims 37 to 46, wherein in step (d), the densification unit is configured to generate a concentrated polyphenol material on the outer shell of the biochar pellet precursor.

48. The method according to any one of claims 37 to 47, wherein steps (d) and (e) are combined and the densification unit is also configured for drying the biochar pellet precursor.

49. The method according to any one of claims 37 to 48, wherein the biochar pellets have a water content of 0% to about 10% by weight.

50. The method according to any one of claims 37 to 48, wherein the biochar pellets have a water content of 0% to about 5% by weight.

51. The method according to any one of claims 37 to 48, wherein the biochar pellets have a water content of 0% to about 2% by weight.

52. The method according to any one of claims 37 to 51, wherein the biochar pellets have a fixed carbon content of about 50% by weight to about 99% by weight of fixed carbon on a dry basis.

53. The method according to any one of claims 37 to 52, wherein the 24-hour water absorption rate of the biochar pellets is approximately 10% by weight or less, as measured at 25°C and 1 bar.

54. The method according to any one of claims 37 to 52, wherein the 24-hour water absorption rate of the biochar pellets is approximately 6% by weight or less, as measured at 25°C and 1 bar.

55. The biochar pellets are at least about 100 lb at 25°C. f / in 2 A method according to any one of claims 37 to 54, characterized by the pellet compressive strength.

56. The biochar pellets are at least about 100 lb f / in 2 The method according to any one of claims 37 to 55, characterized by the immersion / drying pellet compressive strength, wherein the immersion / drying pellet compressive strength is measured by immersing the biochar pellets in water at 25°C for 24 hours, and then drying the biochar pellets in air at 105°C for 24 hours.

57. The biochar pellets have a bulk density of at least about 40 lb / ft 3 , the method according to any one of claims 37 to 56.

58. The method according to any one of claims 37 to 57, wherein the biochar pellets do not contain a pellet binder other than the polyphenol material.

59. The method according to any one of claims 37 to 58, wherein the biochar pellets are subjected to further thermal decomposition in order to increase the fixed carbon content of the biochar pellets.

60. A method for producing biochar pellets, (a) to thermally decompose a biomass-containing raw material in a thermal decomposition reactor, thereby generating a solid biochar-containing material and thermal decomposition steam; (b) To provide polyphenol materials; (c) Introducing the solid biochar-containing material into a densification unit to generate a first biochar pellet precursor; (d) Adding the polyphenol material to the first biochar pellet precursor to produce a second biochar pellet precursor; and (e) to at least partially dry the second biochar pellet precursor, thereby producing biochar pellets. : includes, The method wherein the biochar pellets are characterized by a 24-hour water absorption rate of approximately 20% by weight or less, as measured at 25°C and 1 bar.

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