Co-processing for control of hydropyrolysis processes and products thereof

• US 10,392,566 B2
• Filed: 04/27/2015
• Issued: 08/27/2019
• Est. Priority Date: 04/27/2015
• Status: Active Grant

• Current Assignee: Gas Technology Institute (GTI Energy)
• Original Assignee: Gas Technology Institute (GTI Energy)
• Inventors: Linck, Martin B., Marker, Terry L., Roberts, Michael J., Felix, Larry G.
• Primary Examiner(s): Bullock, In Suk C
• Assistant Examiner(s): Fadhel, Ali Z
• Application Number:
  US14/696,632
• Publication Number:
  US 20160312125A1
• Time in Patent Office: 1,583 Days
• CPC Class Codes: C10G 1/002 in combination with oil conversion- or refining processes
• CPC Class Codes: C10G 1/06 by destructive hydrogenation
• CPC Class Codes: C10G 1/08 with moving catalysts
• CPC Class Codes: C10G 2300/1011 Biomass
• CPC Class Codes: C10G 2300/1014 of vegetal origin
• CPC Class Codes: C10G 2300/1018 of animal origin
• CPC Class Codes: C10G 2300/1022 Fischer-Tropsch products
• CPC Class Codes: C10G 2300/301 Boiling range
• CPC Class Codes: C10G 2300/305 Octane number, e.g. motor octane number [MON], research octane number [RON]
• CPC Class Codes: C10G 2300/307 Cetane number, cetane index
• CPC Class Codes: C10G 2400/02 Gasoline
• CPC Class Codes: C10G 2400/04 Diesel oil
• CPC Class Codes: C10G 2400/08 Jet fuel
• CPC Class Codes: C10G 3/42 Catalytic treatment
• CPC Class Codes: C10G 3/50 in the presence of hydrogen, hydrogen donors or hydrogen generating compounds
• CPC Class Codes: Y02E 50/10 Biofuels, e.g. bio-diesel
• CPC Class Codes: Y02P 30/20 using bio-feedstock

Abstract

Hydropyrolysis processes are described, in which differing types of feedstocks, including at least one biorenewable feedstock, namely a biomass-containing feedstock, may be co-processed to allow enhancements in operating conditions and/or product properties, depending on changing customer requirements and/or overall market demands. According to specific embodiments, an aliphatic hydrocarbon precursor or an aromatic hydrocarbon precursor is co-processed with the biomass-containing feedstock to enhance an operating condition (e.g., a reactor temperature profile) of the hydropyrolysis process and/or a property (e.g., cetane number) of a liquid product (e.g., a diesel boiling range fraction) obtained from a substantially fully deoxygenated hydrocarbon liquid.

Claims

1. A process for producing liquid products comprising:

a) hydropyrolyzing a biomass-containing feedstock, and a separate co-feed different from the biomass-containing feedstock, in a hydropyrolysis reactor vessel comprising a deoxygenating catalyst and operating at a hydrogen partial pressure from about 7 barg (102 psig) to about 55 barg (798 psig) to produce a hydropyrolysis reactor output comprising at least one non-condensable gas, a partially deoxygenated hydropyrolysis product and char;

b) removing substantially all char particles from the hydropyrolysis reactor output to provide a purified hydropyrolysis reactor vapor stream having reduced char content;

c) hydroconverting at least a portion of the purified hydropyrolysis reactor vapor stream in a hydroconversion reactor vessel comprising a hydroconversion catalyst to produce a hydroconversion reactor output; and

d) recovering a substantially fully deoxygenated hydrocarbon liquid and a gaseous mixture from the hydroconversion reactor output;

wherein the separate co-feed comprises an oxygenated plastic; and

wherein oxygen present in the oxygenated plastic is at least partly removed in the hydropyrolysis reactor vessel and a structure of the oxygenated plastic, following oxygen removal, is used to generate aliphatic hydrocarbons or aromatic hydrocarbons in the substantially fully deoxygenated hydrocarbon liquid,

wherein the oxygenated plastic comprises poly(methyl methacrylate) or polyamide, and a feed rate of the oxygenated plastic is adjusted in response to a measured or desired change in a yield or cetane number of a diesel boiling range fraction of the substantially fully deoxygenated hydrocarbon liquid, or

wherein the oxygenated plastic comprises polycarbonate or polyethylene terephthalate, and a feed rate of the oxygenated plastic is adjusted in response to a measured or desired change in a yield or octane number of a gasoline boiling range fraction of the substantially fully deoxygenated hydrocarbon liquid.

2. The process claim 1, wherein the hydropyrolysis reactor vessel is a fluidized bed reactor and the hydroconversion reactor vessel is a fixed bed reactor.

3. The process of claim 1, wherein a poison of the hydroconversion catalyst is removed in the char particles prior to hydroconverting step (c).

4. The process of claim 1, wherein the hydrogen partial pressure is from about 13.8 barg (200 psig) to about 34.5 barg (500 psig).

5. The process of claim 1, wherein the deoxygenating catalyst comprises at least one Group VIII metal and at least one Group VI metal on a support comprising a refractory inorganic oxide.

6. The process of claim 1, wherein the oxygenated plastic is present in municipal solid waste (MSW).

7. The process of claim 1, wherein the biomass-containing feedstock comprises wood.

8. The process of claim 1, further comprising removing spent deoxygenating catalyst from a fluidized bed in the hydropyrolysis reactor vessel and replacing the spent deoxygenating catalyst with fresh deoxygenating catalyst.

9. The process of claim 1, further comprising steam reforming at least a portion of the gaseous mixture, producing reformed hydrogen.

10. The process of claim 9, further comprising recycling at least a portion of the reformed hydrogen to the hydropyrolysis reactor vessel.

11. The process of claim 1, wherein steps a) and c) are operated at conditions under which at least about 20% of oxygen in the feedstock is converted to CO and CO₂, following the hydropyrolyzing and hydroconverting steps.

12. The process of claim 1, wherein the hydropyrolyzing step is exothermic.

13. The process of claim 1, wherein the hydroconverting step is exothermic.

14. The process of claim 1, wherein the substantially fully deoxygenated hydrocarbon liquid has a total oxygen content of less than about 2% by weight.

15. The process of claim 1, wherein the diesel boiling range fraction of the substantially fully deoxygenated hydrocarbon liquid complies with diesel fuel specifications of a minimum cetane number of 41, a maximum water content of 0.05 wt-%, a maximum sulfur content of 15 ppm, and a maximum cold filter plugging point of 12°

C.

16. The process of claim 1, wherein the gasoline boiling range fraction of the substantially fully deoxygenated hydrocarbon liquid complies with gasoline specifications of a minimum motor octane number of 82, a maximum water content of 0.05 wt-%, a maximum sulfur content of 50 ppm, and a maximum benzene content of 3.8 vol-%.

17. The method of claim 1, further comprising condensing an aqueous phase hydroconversion product from the hydroconversion reactor output.

18. The method of claim 1, wherein the diesel boiling range fraction and the gasoline boiling range fraction are obtained from distillation of the substantially fully deoxygenated hydrocarbon liquid.