Hydropyrolysis of biomass for producing high quality liquid fuels

• US 9,447,328 B2
• Filed: 03/15/2013
• Issued: 09/20/2016
• Est. Priority Date: 04/07/2009
• Status: Active Grant

• Current Assignee: Gas Technology Institute
• Original Assignee: Gas Technology Institute
• Inventors: Marker, Terry L, Felix, Larry G, Linck, Martin B
• Primary Examiner(s): HINES, LATOSHA D
• Application Number:
  US13/843,367
• Publication Number:
  US 20130338412A1
• Time in Patent Office: 1,285 Days
• Field of Search: 585/240
• US Class Current: 1/1
• CPC Class Codes: C01B 2203/0205 containing a reforming step
• CPC Class Codes: C01B 2203/0233 the reforming step being a steam reforming step
• CPC Class Codes: C01B 2203/0283 containing a CO-shift step, i.e. a water gas shift step
• CPC Class Codes: C01B 2203/042 Purification by adsorption on solids
• 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 2203/0475 the impurity being carbon dioxide
• CPC Class Codes: C01B 2203/0811 by combustion of fuel
• CPC Class Codes: C01B 2203/0822 the fuel containing hydrogen
• CPC Class Codes: C01B 2203/0827 at least part of the fuel being a recycle stream
• CPC Class Codes: C01B 2203/1241 Natural gas or methane
• CPC Class Codes: C01B 2203/1247 Higher hydrocarbons
• CPC Class Codes: C01B 2203/1258 Pre-treatment of the feed
• CPC Class Codes: C01B 2203/148 involving a recycle stream to the feed of the process for making hydrogen or synthesis gas
• CPC Class Codes: C01B 3/34 by reaction of hydrocarbons with gasifying agents
• CPC Class Codes: C01B 3/56 by contacting with solids; Regeneration of used solids C01B3/508 takes precedence
• CPC Class Codes: C10G 1/002 in combination with oil conversion- or refining processes
• CPC Class Codes: C10G 2300/1011 Biomass
• CPC Class Codes: C10G 2300/4018 Spatial velocity, e.g. LHSV, WHSV
• CPC Class Codes: C10G 2300/4081 Recycling aspects
• CPC Class Codes: C10G 2400/02 Gasoline
• CPC Class Codes: C10G 2400/04 : Diesel oil
• CPC Class Codes: C10G 3/42 : Catalytic treatment
• CPC Class Codes: C10G 3/46 : in combination with chromium, molybdenum, tungsten metals or compounds thereof
• CPC Class Codes: C10G 3/50 : in the presence of hydrogen, hydrogen donors or hydrogen generating compounds
• CPC Class Codes: C10G 3/60 : Controlling or regulating the processes
• CPC Class Codes: C10K 1/32 : with selectively adsorptive solids, e.g. active carbon
• CPC Class Codes: C10K 3/04 : reducing the carbon monoxide content , e.g. water-gas shift [WGS]
• CPC Class Codes: C10L 1/04 : essentially based on blends of hydrocarbons
• CPC Class Codes: Y02E 50/10 : Biofuels, e.g. bio-diesel
• CPC Class Codes: Y02P 20/10 : Process efficiency
• CPC Class Codes: Y02P 30/20 : using bio-feedstock

Abstract

A self-sustaining process for producing liquid fuels from biomass in which the biomass is hydropyrolyzed in a reactor vessel containing molecular hydrogen and a deoxygenating catalyst, producing a partially deoxygenated pyrolysis liquid, which is hydrogenated using a hydroconversion catalyst, producing a substantially fully deoxygenated pyrolysis liquid and a gaseous mixture comprising CO and light hydrocarbon gases (C₁-C₄). The gaseous mixture is reformed in a steam reformer, producing reformed molecular hydrogen, which is then introduced into the reactor vessel for hydropyrolizing the biomass. The deoxygenated liquid product is further processed to produce diesel fuel and gasoline.

Claims

1. A process for a producing a liquid hydrocarbon-containing product from biomass, the process comprising:

(a) pyrolyzing the biomass in the presence of hydrogen and a deoxygenation catalyst to provide a hydropyrolysis effluent comprising a partially deoxygenated hydropyrolysis product and char, and

(b) hydroconverting the partially deoxygenated hydropyrolysis product in the presence of a hydroconversion catalyst to provide a hydroconversion effluent comprising the liquid hydrocarbon-containing product, a water-containing product, and a gaseous mixture comprising CO and C₁-C₃ hydrocarbons, and

(c) steam reforming at least a portion of the gaseous mixture,

wherein deoxygenation in step (a) and hydroconversion in step (b) are carried out to an extent whereby the liquid hydrocarbon-containing product has an oxygen content of less than 2% by weight, such that the liquid-hydrocarbon-containing product is phase-separable from the water-containing product.

2. The process of claim 1, further comprising, in step (b) separating the liquid hydrocarbon-containing product from the water-containing product by phase separation.

3. The process of claim 2, wherein, following separation in step (b), the water-containing product contains less than 2000 ppm dissolved total organic carbon (TOC).

4. The process of claim 2, wherein steam reforming in step (c) is carried out using at least a portion of the water-containing product following separation from the liquid hydrocarbon-containing product.

5. The process of claim 4, wherein a net excess of the water-containing product is generated, beyond an amount used in the steam reforming step (c).

6. The process of claim 4, wherein the steam reforming step (c) generates a reformer effluent comprising H₂ and CO₂.

7. The process of claim 6, wherein the H₂ in the reformer effluent is utilized in the hydropyrolysis step (a).

8. The process of claim 7, wherein the reformer effluent is subjected to pressure swing absorption (PSA) to remove CO₂ and provide a PSA effluent comprising purified hydrogen that is utilized in hydropyrolysis step (a).

9. The process of claim 1, wherein the hydropyrolysis step (a) is carried out in a fluidized bed hydropyrolysis reactor.

10. The process of claim 9, wherein the deoxygenation catalyst has an attrition resistance of less than about 2 weight % per hour, as determined in a standard, high velocity jet cup attrition index test.

11. The process of claim 10, wherein the deoxygenation catalyst has an attrition resistance of less than about 1 weight % per hour, as determined in a standard, high velocity jet cup attrition index test.

12. The process of claim 1, wherein the deoxygenation catalyst and the hydroconversion catalyst are each independently selected from the group consisting of sulfided NiMo catalyst, sulfided CoMo catalyst, and mixtures thereof.

13. The process of claim 1, wherein the deoxygenation catalyst is used in a fluidized bed hydropyrolysis reactor and has a higher attrition resistance than the hydroconversion catalyst.

14. The process of claim 1, wherein the hydroconversion catalyst catalyzes a water-gas-shift reaction to produce hydrogen.

15. The process of claim 1, wherein the hydroconversion step (b) is carried out at a lower temperature than the hydropyrolysis step (a).

19. The process of claim 1, wherein the pyrolyzing step (a) and hydroconverting step (b) are exothermic.

22. The process of claim 1, wherein, following steps (a), (b), and (c), over 95% of oxygen in the biomass is converted to CO₂.

16. A process for a producing a liquid hydrocarbon-containing product from biomass, the process comprising:

(a) pyrolyzing the biomass in the presence of hydrogen and a deoxygenation catalyst to provide a hydropyrolysis effluent comprising a partially deoxygenated hydropyrolysis product and char;

(b) hydroconverting the partially deoxygenated hydropyrolysis product in the presence of a hydroconversion catalyst to provide a hydroconversion effluent comprising the liquid hydrocarbon-containing product, a liquid water-containing product, and a gaseous mixture comprising CO and C₁-C₃ hydrocarbons; and

(c) steam reforming at least a portion of the gaseous mixture, using at least a portion of the liquid water-containing product,

wherein the liquid hydrocarbon-containing product has an oxygen content of less than 5% by weight.

17. The process of claim 16, wherein the liquid water-containing product contains less than 2000 ppm dissolved total organic carbon (TOC).

20. The process of claim 16, wherein the pyrolyzing step (a) and hydroconverting step (b) are exothermic.

23. The process of claim 16, wherein, following steps (a), (b), and (c), over 95% of oxygen in the biomass is converted to CO₂.

18. A process for a producing a liquid hydrocarbon-containing product from biomass, the process comprising:

a) pyrolyzing the biomass in the presence of hydrogen and a deoxygenation catalyst to provide a hydropyrolysis effluent comprising a partially deoxygenated hydropyrolysis product and char;

b) hydroconverting the partially deoxygenated hydropyrolysis product in the presence of a hydroconversion catalyst to provide a hydroconversion effluent comprising the liquid hydrocarbon-containing product, a water-containing product, and a gaseous mixture comprising CO and C₁-C₃ hydrocarbons, and separating the liquid hydrocarbon-containing product, the water-containing product, and the gaseous mixture; and

c) steam reforming at least a portion of the gaseous mixture, using at least a portion of the water-containing product following separation in step (b),

wherein (i) steam reforming step (c) generates sufficient H₂ for consumption in hydropyrolysis step (a) and hydroconversion step (b), and (ii) steps (a), (b), and (c) are operated with a net production of water.

21. The process of claim 18, wherein the pyrolyzing step (a) and hydroconverting step (b) are exothermic.

24. The process of claim 18, wherein, following steps (a), (b), and (c), over 95% of oxygen in the biomass is converted to CO₂.