PROCESSES AND SYSTEMS FOR RECAPTURING CARBON FROM BIOMASS PYROLYSIS LIQUIDS
This disclosure provides a method of making a high-fixed-carbon material comprising pyrolyzing biomass to generate intermediate solids and a pyrolysis vapor; condensing the pyrolysis vapor to generate pyrolysis liquid; blending the pyrolysis liquid with the intermediate solids, to generate a mixture; and further pyrolyzing the mixture to generate a high-fixed-carbon material. A process can comprise: pyrolyzing a biomass-comprising feedstock in a first pyrolysis reactor to generate a first biogenic reagent and a first pyrolysis vapor; introducing the first pyrolysis vapor to a condensing system to generate a condenser liquid; contacting the first biogenic reagent with the condenser liquid, thereby generating an intermediate material; further pyrolyzing the intermediate material in a second pyrolysis reactor to generate a second biogenic reagent and a second pyrolysis vapor; and recovering the second biogenic reagent as a high-yield biocarbon composition. The process can further comprise pelletizing the intermediate material. Many process and system configurations are disclosed.
1 . A process for producing a biocarbon composition, the process comprising:
pyrolyzing a feedstock in a first pyrolysis reactor, wherein the feedstock comprises biomass, thereby generating a first biogenic reagent and a first pyrolysis vapor;
introducing the first pyrolysis vapor to a condensing system, thereby generating a condenser liquid and a condenser vapor;
contacting the first biogenic reagent with the condenser liquid, thereby generating an intermediate material, wherein the intermediate material comprises the first biogenic reagent and the condenser liquid;
thermally treating the intermediate material in a thermal-treatment unit, thereby generating a second biogenic reagent and an off-gas;
recovering the second biogenic reagent as a biocarbon composition.
2 . The process of claim 1 , wherein the feedstock is selected from softwood chips, hardwood chips, timber 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 beets, sugar beet pulp, sunflowers, sorghum, canola, algae, miscanthus, alfalfa, switchgrass, fruits, fruit shells, fruit stalks, fruit peels, fruit pits, vegetables, vegetable shells, vegetable stalks, vegetable peels, vegetable pits, grape pumice, 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 trimmings, food packaging, construction and/or demolition waste, railroad ties, lignin, animal manure, municipal solid waste, municipal sewage, or a combination thereof.
3 . The process of claim 1 , further comprising pelletizing the first biogenic reagent.
4 . The process of claim 1 , further comprising pelletizing the intermediate material.
5 . The process of claim 4 , wherein the contacting and the pelletizing the intermediate material are integrated.
6 . The process of claim 4 , wherein the pelletizing the intermediate material occurs after the contacting.
7 . The process of claim 4 , wherein the pelletizing the intermediate material comprises introducing a binder to the intermediate material.
8 . The process of claim 7 , wherein the binder is selected from starch, thermoplastic starch, crosslinked starch, starch polymers, cellulose, cellulose ethers, hemicellulose, methylcellulose, chitosan, lignin, lactose, sucrose, dextrose, maltodextrin, banana flour, wheat flour, wheat starch, soy flour, corn flour, wood flour, coal tars, coal fines, met coke, asphalt, coal-tar pitch, petroleum pitch, bitumen, pyrolysis tars, gilsonite, bentonite clay, borax, limestone, lime, waxes, vegetable waxes, baking soda, baking powder, sodium hydroxide, potassium hydroxide, iron ore concentrate, silica fume, gypsum, Portland cement, guar gum, xanthan gum, polyvidones, polyacrylamides, polylactides, phenol-formaldehyde resins, vegetable resins, recycled shingles, recycled tires, derivatives thereof, or a combination of the foregoing.
9 . The process of claim 4 , wherein the pelletizing the intermediate material does not comprise introducing an external binder to the intermediate material.
10 . The process of claim 1 , wherein a carbon recapture unit is disposed upstream of the thermal-treatment unit.
11 . The process of claim 1 , wherein a carbon recapture unit is a first stage of the thermal-treatment unit.
12 . The process of claim 1 , wherein the condensing system comprises multiple condenser stages.
13 . The process of claim 12 , wherein the condenser liquid is a condensed product of a first stage of the multiple condenser stages.
14 . The process of claim 12 , wherein the condenser liquid is a condensed product of a plurality of stages of the multiple condenser stages.
15 . The process of claim 14 , wherein the plurality of stages does not include the final stage of the multiple condenser stages.
16 . The process of claim 1 , further comprising introducing the off-gas to the condensing system.
17 . The process of claim 1 , wherein the intermediate material comprises the condenser liquid adsorbed onto a surface of the first biogenic reagent.
18 . The process of claim 1 , wherein the intermediate material comprises the condenser liquid absorbed into a bulk phase of the first biogenic reagent.
19 . The process of claim 1 , wherein the thermal-treatment unit is a second pyrolysis reactor operated at a temperature of at least about 250° C., and wherein the second pyrolysis reactor is configured for pyrolyzing the intermediate material.
20 . The process of claim 1 , wherein the thermal-treatment unit is operated at a temperature selected from about 80° C. to about 250° C.
21 . The process of claim 1 , wherein the thermal-treatment unit contains an internal oxygen-free environment.
22 . The process of claim 1 , wherein an inert gas is introduced to the thermal-treatment unit.
23 . The process of claim 1 , wherein the thermal-treatment unit is operated under vacuum.
24 . The process of claim 1 , wherein the thermal-treatment unit is configured for drying the second biogenic reagent.
25 . The process of claim 1 , wherein the process further comprises drying of the biocarbon composition after the thermally treating.
26 . The process of claim 19 , wherein the first pyrolysis reactor is distinct from the second pyrolysis reactor.
27 . The process of claim 19 , wherein the first pyrolysis reactor and the second pyrolysis reactor are the same unit, and wherein the pyrolyzing and the thermally treating are conducted at different times.
28 . The process of claim 1 , comprising performing fixed-carbon formation reactions of the condenser liquid, wherein the performing utilizes the first biogenic reagent as a catalyst or wherein the performing utilizes the first biogenic reagent as a reaction matrix.
29 . The process of claim 1 , wherein the condenser liquid comprises total carbon, and wherein the process further comprises converting at least 25 wt % of the total carbon comprised within the condenser liquid to fixed carbon comprised within the second biogenic reagent.
30 . The process of claim 1 , wherein the condenser liquid comprises total carbon, and wherein the process further comprises converting at least 50 wt % of the total carbon comprised within the condenser liquid to fixed carbon comprised within the second biogenic reagent.
31 . The process of claim 1 , wherein the condenser liquid comprises total carbon, and wherein the process further comprises converting at least 75 wt % of the total carbon comprised within the condenser liquid to fixed carbon comprised within the second biogenic reagent.
32 . The process of claim 1 , wherein at least about 10 wt % to at most about 80 wt % of fixed carbon in the second biogenic reagent is derived from the condenser liquid.
33 . The process of claim 1 , wherein at least about 20 wt % to at most about 60 wt % of fixed carbon in the second biogenic reagent is derived from the condenser liquid.
34 . The process of claim 1 , wherein all of the condenser liquid is contacted with the first biogenic reagent.
35 . The process of claim 1 , wherein less than all of the condenser liquid is contacted with the first biogenic reagent.
36 . The process of claim 1 , wherein the condenser liquid is contacted with the first biogenic reagent without any intermediate chemical processing.
37 . The process of claim 1 , wherein the condenser liquid is chemically processed prior to contacting with the first biogenic reagent.
38 . The process of claim 37 , wherein the condenser liquid is subjected to a purification step prior to contacting with the first biogenic reagent.
39 . The process of claim 37 , wherein the condenser liquid is subjected to a reaction step prior to contacting with the first biogenic reagent.
40 . The process of claim 1 , wherein the pyrolyzing is conducted at a first pyrolysis temperature of at least about 250° C. to at most about 1250° C.
41 . The process of claim 40 , wherein the first pyrolysis temperature is at least about 300° C. to at most about 700° C.
42 . The process of claim 19 , wherein the pyrolyzing the intermediate material is conducted at a second pyrolysis temperature of at least about 250° C. to at most about 1250° C.
43 . The process of claim 42 , wherein the second pyrolysis temperature is at least about 300° C. to at most about 700° C.
44 . The process of claim 1 , wherein the pyrolyzing is conducted for a first pyrolysis time of at least about 10 seconds to at most about 24 hours.
45 . The process of claim 19 , wherein the pyrolyzing the intermediate material is conducted for a second pyrolysis time of at least about 10 seconds to at most about 24 hours.
46 . The process of claim 1 , further comprising oxidizing the condenser vapor, thereby generating heat.
47 . The process of claim 1 , further comprising oxidizing the off-gas, thereby generating heat.
48 . The process of claim 1 , further comprising milling the first biogenic reagent using a mechanical-treatment apparatus, wherein the mechanical-treatment apparatus is selected from a hammer mill, an extruder, an attrition mill, a disc mill, a pin mill, a ball mill, a cone crusher, a jaw crusher, or a combination thereof.
49 . The process of claim 1 , further comprising milling the intermediate material using a mechanical-treatment apparatus, wherein the mechanical-treatment apparatus is selected from a hammer mill, an extruder, an attrition mill, a disc mill, a pin mill, a ball mill, a cone crusher, a jaw crusher, or a combination thereof.
50 . The process of claim 4 , wherein the pelletizing the intermediate material utilizes a pelletizing apparatus selected from an extruder, a ring die pellet mill, a flat die pellet mill, a roll compactor, a roll briquetter, a wet agglomeration mill, a dry agglomeration mill, or a combination thereof.
51 . The process of claim 1 , further comprising generating fines, in the thermal-treatment unit, wherein the fines comprise carbon; and further comprising recycling the fines to the step of contacting the first biogenic reagent with the condenser liquid.
52 . The process of claim 1 , further comprising generating fines, in the thermal-treatment unit, wherein the fines comprise carbon; and further comprising recycling the fines to the step of recovering the second biogenic reagent.
53 . The process of claim 1 , wherein the biocarbon composition is in the form of a powder.
54 . The process of claim 1 , further comprising drying the second biogenic reagent, and further comprising pelletizing the second biogenic reagent to generate pellets, wherein the pelletizing the second biogenic reagent occurs during the drying, after the drying, or after the recovering.
55 . The process of claim 54 , further comprising powderizing the pellets to form a powder.
56 . The process of claim 1 , wherein the biocarbon composition comprises at least 50 wt % fixed carbon.
57 . The process of claim 1 , wherein the biocarbon composition comprises at least 60 wt % fixed carbon.
58 . The process of claim 1 , wherein the biocarbon composition comprises at least 70 wt % fixed carbon.
59 . The process of claim 1 , wherein the biocarbon composition comprises at least 80 wt % fixed carbon.
60 . The process of claim 1 , wherein the biocarbon composition comprises at least 90 wt % fixed carbon.
61 . The process of claim 1 , wherein the biocarbon composition comprises less than 10 wt % ash.
62 . The process of claim 1 , wherein the biocarbon composition comprises less than 5 wt % ash.
63 . The process of claim 1 , wherein the biocarbon composition comprises less than 1 wt % ash.
64 . The process of claim 1 , wherein the condenser liquid comprises less than 1 wt % ash.
65 . The process of claim 1 , wherein the condenser liquid comprises less than 0.1 wt % ash.
66 . The process of claim 1 , wherein the condenser liquid comprises essentially no ash.
67 . The process of claim 1 , wherein total carbon within the biocarbon composition is at least 50% renewable as determined from a measurement of the 14 C/ 12 C isotopic ratio of the total carbon.
68 . The process of claim 1 , wherein total carbon within the biocarbon composition is at least 90% renewable as determined from a measurement of the 14 C/ 12 C isotopic ratio of the total carbon.
69 . The process of claim 1 , wherein total carbon within the biocarbon composition is fully renewable as determined from a measurement of the 14 C/ 12 C isotopic ratio of the total carbon.
70 . The process of claim 1 , wherein the biocarbon composition is characterized by a bulk density of at least about 5 lb/ft 3 on a dry basis.
71 . The process of claim 1 , wherein the biocarbon composition is characterized by a bulk density of at least about 10 lb/ft 3 on a dry basis.
72 . The process of claim 1 , wherein the biocarbon composition is characterized by a bulk density of at least about 20 lb/ft 3 on a dry basis.
73 . The process of claim 1 , wherein the biocarbon composition is characterized by at most 20 wt % water uptake at 25° C. after 24 hours of soaking in water.
74 . The process of claim 1 , wherein the biocarbon composition is characterized as non-self-heating when subjected to a self-heating test according to Manual of Tests and Criteria , Seventh revised edition 2019, United Nations, Page 375, 33.4.6 Test N.4: “Test method for self-heating substances”.
75 . The process of claim 1 , wherein the biocarbon composition is in the form of a pellet.
76 . The process of claim 75 , wherein the pellet is characterized by a bulk density of at least about 10 lb/ft 3 on a dry basis.
77 . The process of claim 75 , wherein the pellet is characterized by a bulk density of at least about 25 lb/ft 3 on a dry basis.
78 . The process of claim 75 , wherein the pellet is characterized by a bulk density of at least about 35 lb/ft 3 on a dry basis.
79 . The process of claim 75 , wherein the pellet is characterized by a Hardgrove Grindability Index of at least 30.
80 . The process of claim 75 , wherein the pellet is characterized by a Hardgrove Grindability Index of at least 50.
81 . The process of claim 75 , wherein the pellet is characterized by a Hardgrove Grindability Index of at least 70.
82 . The process of claim 75 , wherein the pellet is characterized by a pellet compressive strength at 25° C. of at least about 100 lb f /in 2 .
83 . The process of claim 75 , wherein the pellet is characterized by a pellet compressive strength at 25° C. of at least about 150 lb f /in 2 .
84 . A system for producing a biocarbon composition, the system comprising:
a first pyrolysis reactor configured for pyrolyzing a feedstock comprising biomass to generate a first biogenic reagent and a first pyrolysis vapor;
a condensing system in flow communication with the first pyrolysis reactor, wherein the condensing system is configured for condensing the first pyrolysis vapor to generate a condenser liquid and a condenser vapor;
a mixing unit in flow communication with the first biogenic reagent and the condensing system, wherein the mixing unit is configured for contacting the first biogenic reagent with the condenser liquid to generate an intermediate material;
a thermal-treatment unit in flow communication with the mixing unit, wherein the thermal-treatment unit is configured for thermally treating the intermediate material to generate a second biogenic reagent and an off-gas; and
a system output disposed in the thermal-treatment unit or in flow communication with the thermal-treatment unit, wherein the system output is configured for recovering the second biogenic reagent as a biocarbon composition.
85 . The system of claim 84 , wherein the mixing unit is a pelletizing unit.
86 . The system of claim 84 , wherein the system comprises a pelletizing unit that is distinct from the mixing unit, and wherein the pelletizing unit is disposed between the mixing unit and the thermal-treatment unit.
87 . The system of claim 84 , wherein the condensing system comprises multiple condenser stages.
88 . The system of claim 84 , further comprising a recycle line configured to recycle the off-gas to the condensing system.
89 . The system of claim 84 , wherein the thermal-treatment unit is a second pyrolysis reactor.
90 . The system of claim 84 , wherein the thermal-treatment unit is a dryer.
91 . The system of claim 84 , further comprising a mechanical-treatment apparatus configured to mill the first biogenic reagent, wherein the mechanical-treatment apparatus is selected from a hammer mill, an extruder, an attrition mill, a disc mill, a pin mill, a ball mill, a cone crusher, a jaw crusher, or a combination thereof.
92 . The system of claim 84 , further comprising a mechanical-treatment apparatus configured to mill the intermediate material, wherein the mechanical-treatment apparatus is selected from a hammer mill, an extruder, an attrition mill, a disc mill, a pin mill, a ball mill, a cone crusher, a jaw crusher, or a combination thereof.
93 . The system of claim 84 , further comprising a pelletizing apparatus configured to pelletize the intermediate material, wherein the pelletizing apparatus is selected from an extruder, a ring die pellet mill, a flat die pellet mill, a roll compactor, a roll briquetter, a wet agglomeration mill, a dry agglomeration mill, or a combination thereof.