Fluidized upgrading/hydrostabilizing of pyrolysis vapors

Patent metadata

Field	Value
Publication number	US-10377953-B2
Application number	US-201715807267-A
Country	US
Kind code	B2
Filing date	Nov 8, 2017
Priority date	Nov 9, 2016
Publication date	Aug 13, 2019
Grant date	Aug 13, 2019

Abstract

The present disclosure relates to processes and systems that convert biomass to stable intermediate hydrocarbon products that having a greatly decreased oxygen content. This stabilized intermediate hydrocarbon product may be easily be stored for an extended period of time, further refined into liquid transportation fuels (either alone or mixed with petroleum-derived hydrocarbons), or blended with petroleum-derived blendstocks to produce a finished liquid transportation fuel.

First claim

We claim:

1. A process for pyrolyzing biomass and upgrading/hydrostabilizing the vapors, comprising:
a) pyrolyzing a feedstock that is derived from biomass in a first reactor for a residence time of less than 10 seconds in the absence of a catalyst and the presence of a heavy stabilized hydrocarbon fraction consisting of hydrocarbon molecules characterized by a boiling point (at 1 atm.) that is greater than 321° C., to produce a primary pyrolysis product comprising condensable pyrolysis vapors and char;
b) conveying the condensable pyrolysis vapors to a second reactor containing hydrogen and at least one fluidized bed of at least one catalyst, and contacting the condensable pyrolysis vapors with the at least one catalyst at conditions of temperature that facilitate the production of a stabilized hydrocarbon product, wherein the stabilized hydrocarbon product comprises hydrocarbons having less than 0.1 wt. percent aldehyde functional groups and less than 0.1 wt percent carboxylic acid functional groups;
c) fractionating the stabilized hydrocarbon product to produce the heavy stabilized hydrocarbon fraction of a), and fuel-range stabilized hydrocarbons characterized by a boiling point ranging from between 25° C. and 321° C.

2. The process of claim 1 , wherein the fuel-range stabilized hydrocarbons comprises a light stabilized hydrocarbon fraction characterized by a boiling point ranging from between 25° C. and 193° C., and a medium stabilized hydrocarbon fraction characterized by a boiling point ranging from between 193° C. and 321° C.

3. The process of claim 1 , wherein the boiling point of at least 90 wt % of hydrocarbon molecules in the heavy stabilized hydrocarbon fraction is greater than 343° C.

4. The process of claim 1 , further comprising co-feeding the light stabilized hydrocarbon fraction, the medium stabilized hydrocarbon fraction, or both, with petroleum-derived hydrocarbons to a refinery process.

5. The process of claim 1 , further comprising condensing and storing the light stabilized hydrocarbon fraction, the medium stabilized hydrocarbon fraction, or both, for a period in excess of seven days prior to use.

6. The process of claim 1 , wherein the fractionating of c) comprises selective condensation of the heavy stabilized fraction.

7. The process of claim 1 , further comprising blending the light stabilized hydrocarbon fraction, the medium stabilized hydrocarbon fraction, or both, with conventional petroleum-derived hydrocarbons to produce a finished liquid transportation fuel.

8. The process of claim 1 , wherein recycling of the heavy stabilized hydrocarbon fraction to the pyrolysis reactor decreases the partial pressure of hydrogen required in the second reactor by at least 50 psig.

9. A system for the production and upgrading/hydrostabilizing of a stabilized pyrolysis product, comprising:
a. a pyrolysis reactor that does not contain a catalyst and that is configured to fluidize and rapidly pyrolyze a feedstock comprising biomass for a residence time of between 1 and 20 seconds to produce a gaseous product comprising non-condensable light gases, condensable pyrolysis vapors, and char, wherein the pyrolysis reactor comprises:
a first inlet configured to receive a stabilized heavy hydrocarbon fraction comprising stabilized hydrocarbons that are characterized by a boiling point greater than 350° C.,
a second inlet configured to receive the biomass feedstock,
at least one outlet configured to remove the gaseous product from the reactor,
at least one inlet configured to receive a carrier gas and operable to fluidize the feedstock;

b. a second reactor containing at least one catalyst in a fluidized bed configuration, wherein the second reactor is configured to receive the gaseous product and maintain a temperature and pressure that facilitate the catalytic conversion of the condensable pyrolysis vapors to produce a stabilized hydrocarbon product;
c. a fractionation device configured to separate the stabilized hydrocarbon product to produce a heavy stabilized hydrocarbon fraction, the fractionation further comprising an outlet for the heavy stabilized hydrocarbon fraction;
d. a conduit operably connected to receive the heavy stabilized hydrocarbon fraction and convey it to the pyrolysis reactor.

10. The system of claim 9 , wherein the pyrolysis reactor additionally contains a fluidizable bed of a heat carrier, the heat carrier comprising a particulate solid.

11. The system of claim 9 , wherein the pyrolysis reactor is configured to pyrolyze the biomass feedstock at a temperature in the range from 300° C. to 650° C. and for a residence time of less than 10 sec.

12. The system of claim 9 , wherein the second reactor comprises a fluidized bed of at least one upgrading/hydrostabilizing catalyst, wherein the second reactor is configured to catalytically convert the condensable pyrolysis vapors to produce a stabilized hydrocarbon product that is a member selected from the list consisting of: a co-feed for a conventional refinery process, a liquid hydrocarbon transportation fuel or a component thereof.

13. The system of claim 9 , further comprising a separator that is directly coupled to the second reactor and configured to receive the stabilized hydrocarbon product from the second reactor and to remove water and flue gas from the stabilized hydrocarbon product to produce a dewatered stabilized hydrocarbon product.

14. The system of claim 9 , further comprising a fractionation device that is directly coupled to the separator and configured to receive the dewatered stabilized hydrocarbon product from the separator, wherein the fractionation device is configured to receive and fractionate the dewatered stabilized hydrocarbon product into two or more fractions based upon boiling point, including the stabilized heavy hydrocarbon fraction.

Assignees

• Phillips 66 Co

Inventors

• Gong Kening
• Zhang Liang
• Copeland John R
• Eisenhart Reed J

Classifications

• Y02P30/20

  using bio-feedstock · CPC title

• C10G2300/104

  Light gasoline having a boiling range of about 20 - 100 °C · CPC title

• C10B53/02 Primary

  of cellulose-containing material (production of pyroligneous acid C10C5/00) · CPC title

• C10G55/04

  including at least one thermal cracking step · CPC title

• G01N2030/025

  Gas chromatography · CPC title