Activated carbon as a high value product of hydropyrolysis

• US 10,647,933 B2
• Filed: 11/12/2015
• Issued: 05/12/2020
• Est. Priority Date: 11/12/2015
• Status: Active Grant

• Current Assignee: Gas Technology Institute
• Original Assignee: Gas Technology Institute
• Inventors: Marker, Terry L., Linck, Martin B., Roberts, Michael J.
• Primary Examiner(s): Hendrickson, Stuart L
• Application Number:
  US14/940,024
• Publication Number:
  US 20170137294A1
• Time in Patent Office: 1,643 Days
• CPC Class Codes: C01B 2203/0405 Purification by membrane separation
• CPC Class Codes: C01B 2203/043 Regenerative adsorption process in two or more beds, one for adsorption, the other for regeneration
• CPC Class Codes: C01B 2203/06 Integration with other chemical processes
• CPC Class Codes: C01B 3/34 by reaction of hydrocarbons with gasifying agents
• CPC Class Codes: C01B 32/30 Active carbon
• CPC Class Codes: C01B 32/318 characterised by the starting materials
• CPC Class Codes: C10G 1/06 by destructive hydrogenation
• CPC Class Codes: C10G 3/50 in the presence of hydrogen, hydrogen donors or hydrogen generating compounds
• CPC Class Codes: C10L 1/06 for spark ignition
• CPC Class Codes: C10L 1/08 for compression ignition
• CPC Class Codes: C10L 2200/0423 Gasoline
• CPC Class Codes: C10L 2200/0446 Diesel
• CPC Class Codes: Y02E 50/10 Biofuels, e.g. bio-diesel
• CPC Class Codes: Y02P 20/145 the feedstock being materials of biological origin
• CPC Class Codes: Y02P 30/20 using bio-feedstock

Abstract

Hydropyrolysis processes that accompany the generation of activated carbon as an end product, as well as processes for the production of activated carbon from hydropyrolysis char, are described. Representative processes comprise upgrading, by steam activation, char that is formed from solid biomass-containing feedstocks and/or solid biomass derived feedstocks, such as lignocellulosic feedstocks (e.g., wood). Such processes are associated with a number of advantages in terms of achieving operating synergies, obtaining desirable intermediate material and end product properties, reducing environmental impact, and significantly improving economic attractiveness.

Claims

1. A hydropyrolysis process, comprising:

(a) feeding both (i) hydrogen and (ii) a biomass-containing feedstock or a biomass-derived feedstock, to a hydropyrolysis reactor vessel, under hydropyrolysis conditions for hydropyrolyzing the biomass-containing feedstock or the biomass-derived feedstock;

(b) withdrawing from the hydropyrolysis reactor vessel a hydropyrolysis reactor output comprising solid char particles, at least one non-condensable gas, and a partially deoxygenated hydropyrolysis product;

(c) separating at least a portion of the solid char particles, as hydropyrolysis char, from the hydropyrolysis reactor output;

(d) contacting the hydropyrolysis char, separated in step (c), with steam to provide an activated carbon having a surface area of at least about 300 square meters per gram (m²/g) and to further provide an activation effluent gas; and

(e) reforming methane present in the activation effluent gas to generate at least a portion of the hydrogen in step (a).

2. The process of claim 1, wherein, in step (b), the hydropyrolysis reactor output is withdrawn from the hydropyrolysis reactor vessel as a vapor stream having the solid char particles entrained therein.

3. The process of claim 1, wherein, in step (c), the solid char particles are separated using a mechanical gas-solid separation device selected from the group consisting of a filter, a cyclone separator, an electrostatic precipitator, and combinations thereof.

4. The process of claim 1, wherein, in step (d), the hydropyrolysis char is contacted with steam in a steam activation vessel, wherein the steam is present in a fluidizing activation gas.

5. The process of claim 4, wherein conditions in the steam activation vessel include an activation temperature of at least about 500°

C. (932°

F.) and a residence time of at least about 30 minutes.

6. The process of claim 4, further comprising:

(e) feeding a hydropyrolysis reactor vapor, obtained from the hydropyrolysis reactor output following the separation of the solid char particles in step (c), to a hydroconversion reactor vessel;

(f) hydroconverting at least a portion of the hydropyrolysis reactor vapor in a hydroconversion zone to obtain a hydroconversion zone output;

(g) recovering, by condensing a substantially fully deoxygenated hydrocarbon liquid from the hydroconversion zone output, a hydroconversion gaseous mixture; and

(h) introducing at least a portion of the hydroconversion gaseous mixture to a steam reformer that provides a net production of hydrogen, together with unconsumed steam, in a steam reformer effluent;

wherein the fluidizing activation gas comprises at least a portion of the steam reformer effluent.

7. The process of claim 6, further comprising:

(i) withdrawing, from the steam activation vessel, an activation effluent gas that is enriched in hydrogen, relative to the fluidizing activation gas.

8. The process of claim 7, wherein hydrogen fed to the hydropyrolysis reactor vessel in step (a) or a separate source of hydroconversion hydrogen fed to the hydroconversion reactor vessel in step (f) includes hydrogen in the activation effluent gas.

9. The process of claim 8, further comprising:

(j) condensing the steam in the activation effluent gas to provide a steam-depleted activation effluent vapor fraction, and

(k) feeding the activation effluent vapor fraction to the steam reformer, wherein at least a portion of the net production of hydrogen in step (h) is obtained by reforming of methane in the steam-depleted activation effluent vapor fraction.

10. The process of claim 6, wherein the hydropyrolyzing in step (a) and the hydroconverting in step (f) are net exothermic process steps resulting in the generation of both hydropyrolysis reaction heat and hydroconversion reaction heat, and wherein at least a portion of the hydropyrolysis reaction heat or the hydroconversion reaction heat at least partially satisfies a heat requirement for providing the activated carbon in step (d).

11. The process of claim 6, wherein the unconsumed steam in the steam reformer effluent satisfies a steam requirement for providing the activated carbon in step (d).

12. The process of claim 6, further comprising fractionating the substantially fully deoxygenated hydrocarbon liquid, to obtain a gasoline fraction comprising gasoline boiling-range hydrocarbons and/or a diesel fuel fraction comprising diesel fuel boiling-range hydrocarbons, wherein, in step (d), activated carbon is provided substantially without adding to the carbon footprint of the gasoline fraction and/or the diesel fuel fraction, based on a lifecycle assessment (LCA) of greenhouse gas (GHG) emissions.

13. A process for producing activated carbon, the process comprising contacting hydropyrolysis char with steam to provide an activated carbon having a surface area of greater than about 300 square meters per gram (m²/g), and to further provide an activation effluent gas, the process further comprising

reforming methane present in the activation effluent gas to generate hydrogen.

14. The process of claim 13, wherein the hydropyrolysis char has a surface area of less than about 5 m²/g.

15. The process of claim 13, wherein the hydropyrolysis char has a total content of Hg, Se, Be, Cd, As, and Cr of less than 5 parts per million by weight (wt-ppm).

16. The process of claim 13, wherein the hydropyrolysis char has a content of mercury of less than about 10 parts per billion by weight (wt-ppb).

17. The process of claim 13, wherein substantially all carbon in the hydropyrolysis char is obtained from biomass.

18. The process of claim 13, wherein substantially all of the atomic oxygen content of the steam is biomass oxygen.

19. The process of claim 13, wherein the hydropyrolysis char has an ash content of less than about 1% by weight.