High-carbon biogenic reagents and uses thereof
View Patent ↗This invention provides processes and systems for converting biomass into high-carbon biogenic reagents that are suitable for a variety of commercial applications. Some embodiments employ pyrolysis in the presence of an inert gas to generate hot pyrolyzed solids, condensable vapors, and non-condensable gases, followed by separation of vapors and gases, and cooling of the hot pyrolyzed solids in the presence of the inert gas. Additives may be introduced during processing or combined with the reagent, or both. The biogenic reagent may include at least 70 wt %, 80 wt %, 90 wt %, 95 wt %, or more total carbon on a dry basis. The biogenic reagent may have an energy content of at least 12,000 Btu/lb, 13,000 Btu/lb, 14,000 Btu/lb, or 14,500 Btu/lb on a dry basis. The biogenic reagent may be formed into fine powders, or structural objects. The structural objects may have a structure and/or strength that derive from the feedstock, heat rate, and additives.
1. A process for producing high-carbon biogenic reagent comprising the steps of:
(a) providing a carbon-containing feedstock comprising biomass, said biomass comprising not more than about 50% water, by weight;
(b) in a pyrolysis zone, pyrolyzing said carbon-containing feedstock in the presence of a substantially inert gas for at least about 10 minutes and with a pyrolysis temperature selected from about 250° C. to about 700° C., to generate hot pyrolyzed solids, condensable vapors, and non-condensable gases;
(c) separating at least a portion of said condensable vapors and at least a portion of said non-condensable gases from said hot pyrolyzed solids;
(d) in a cooling zone, cooling said hot pyrolyzed solids, in the presence of said substantially inert gas for at least about 5 minutes and with a cooling zone temperature less than said pyrolysis temperature, to generate warm pyrolyzed solids;
(e) in a cooling unit that is separate from said cooling zone, cooling said warm pyrolyzed solids to generate cool pyrolyzed solids;
(f) recovering a high-carbon biogenic reagent comprising at least a portion of said cool pyrolyzed solids, and
(g) introducing at least one additive selected from acids, bases, or salts thereof, and/or introducing at least one additive selected from the group consisting of a metal, a metal oxide, a metal hydroxide, a metal halide, and combinations thereof.
2. The process of claim 1 , wherein each of said zones is located within a single reactor, or wherein each of said zones is located in a separate reactor.
3. The process of claim 1 , wherein at least some of said substantially inert gas includes one or more non-condensable gas species recycled from step (c).
4. The process of claim 1 , wherein said pyrolysis zone and said cooling zone each comprise a gas phase containing less than about 5 wt % oxygen, or about 1 wt % oxygen or less.
5. The process of claim 1 , wherein said process is continuous or semi-continuous.
6. The process of claim 5 , wherein said inert gas flows substantially countercurrent relative to the direction of solids flow, or wherein said inert gas flows substantially cocurrent relative to the direction of solids flow.
7. The process of claim 1 , said process further comprising monitoring and controlling said process with at least one reaction gas probe, or with at least two reaction gas probes.
8. The process of claim 1 , said process further comprising one or more of:
process gas heating of at least a portion of said condensable vapors with an oxygen-containing gas, optionally assisted with combustion of natural gas,
using process gas heating, at least in part, for drying said feedstock to remove at least a portion of moisture contained within said feedstock, and
using process gas heating, at least in part, to heat said substantially inert gas, and optionally introducing the heated substantially inert gas to said pyrolysis zone.
9. The process of claim 1 , said process further comprising combining at least a portion of said condensable vapors, in at least partially condensed form, with said cooled pyrolyzed solids and/or with said warm pyrolyzed solids, to increase the carbon content of said high-carbon biogenic reagent.
10. The process of claim 1 , wherein:
the at least one additive is selected from the group consisting of sodium hydroxide, potassium hydroxide, magnesium oxide, hydrogen bromide, hydrogen chloride, sodium silicate, potassium permanganate, and combinations thereof, and/or
the at least one additive is 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, dolomitic lime, fluorite, fluorospar, bentonite, calcium oxide, lime, and combinations thereof.
11. The process of claim 1 , wherein the at least one additive is introduced:
prior to or during step (b),
during step (d),
during step (e),
between steps (d) and (e),
after step (e), or
to said warm pyrolyzed solids in an aqueous solution, vapor, or aerosol to assist with cooling of said warm pyrolyzed solids in step (e).
12. The process of claim 1 , said process further comprising:
introducing at least a portion of said cool pyrolyzed solids to a separate unit for additional pyrolysis, in the presence of a second substantially inert gas for at least 30 minutes and with a pyrolysis temperature selected from about 200° C. to about 600° C., to generate a solid product having higher carbon content than said cool pyrolyzed solids; and
optionally process gas heating at least a portion of said condensable vapors with an oxygen-containing gas, wherein heat produced from said process gas heating is utilized, at least in part, to heat said second substantially inert gas prior to introduction to said separate unit for additional pyrolysis.
13. The process of claim 1 further comprising a step of drying the carbon-containing feedstock prior to step (b),
wherein the cooling unit is operated:
to cool said warm pyrolyzed solids with steam to generate cool pyrolyzed solids and superheated steam and wherein the step of drying is carried out, at least in part, with said superheated steam; and/or
to first cool said warm pyrolyzed solids with steam to reach a first cooler temperature, and then with air to reach a second cooler temperature, wherein said second cooler temperature is lower than said first cooler temperature and is associated with a reduced combustion risk for said warm pyrolyzed solids in the presence of said air.
14. The process of claim 1 , wherein said high-carbon biogenic reagent contains at least 35%, at least 50%, or at least 70% of the carbon contained in said feedstock.
15. The process of claim 1 , wherein said high-carbon biogenic reagent contains at least 70 wt %, at least 80 wt %, at least 90 wt %, or at least 95 wt % carbon on a dry basis, wherein said carbon optionally includes fixed carbon and carbon from volatile matter.
16. The process of claim 1 , wherein said high-carbon biogenic reagent has an energy content, on a dry basis, of at least 11,000 Btu/lb, at least 12,000 Btu/lb on a dry basis, at least 13,000 Btu/lb, at least 14,000 Btu/lb, at least 14,500 Btu/lb, or at least 14,700 Btu/lb.
17. The process of claim 1 , wherein said high-carbon biogenic reagent is formed into a fine powder by particle-size reduction, is formed into a structural object by pressing, binding, pelletizing, or agglomeration, or is in the form of structural objects whose structure and/or strength substantially derive from said feedstock, optionally wherein said high-carbon biogenic reagent is in substantially the same structural form as said feedstock.