Heavy Fossil Hydrocarbon Conversion and Upgrading Using Radio-Frequency or Microwave Energy

• US 20180237704A1
• Filed: 01/02/2018
• Published: 08/23/2018
• Est. Priority Date: 02/21/2012
• Status: Active Grant

• Current Assignee: Battelle Memorial Institute
• Original Assignee: Battelle Memorial Institute
• Inventors: Strohm, James J., Roberts, Benjamin Q., Smurthwaite, Tricia D., Bergsman, Theresa M., Bearden, Mark D.
• Granted Patent: US 11,268,036 B2
• Time in Patent Office: Days
• CPC Class Codes: B01J 19/0093 Microreactors, e.g. miniaturised or microfabricated reactors laboratory containers with capillary fluid transport in microfabricated channels or chambers B01L3/5027
• CPC Class Codes: B01J 19/088 giving rise to electric discharges for heating purposes H05B7/00; for the production of ozone C01B13/11, H01T19/00
• CPC Class Codes: B01J 19/126 Microwaves
• CPC Class Codes: B01J 2219/00792 One or more tube-shaped elements
• CPC Class Codes: B01J 2219/00822 Metal
• CPC Class Codes: B01J 2219/00826 Quartz
• CPC Class Codes: B01J 2219/00835 Comprising catalytically active material
• CPC Class Codes: B01J 2219/0086 Dimensions of the flow channels
• CPC Class Codes: B01J 2219/00941 Microwaves
• CPC Class Codes: B01J 2219/0894 Processes carried out in the presence of a plasma
• CPC Class Codes: B01J 2219/1215 Single reactor
• CPC Class Codes: B01J 2219/1227 Reactors comprising tubes with open ends
• CPC Class Codes: B01J 2219/1239 Means for feeding and evacuation
• CPC Class Codes: B01J 2219/1245 Parts of the reactor being microwave absorbing, dielectric
• CPC Class Codes: B01J 2219/1269 Microwave guides
• CPC Class Codes: B01J 2219/1272 Materials of construction
• CPC Class Codes: C10G 1/002 in combination with oil conversion- or refining processes
• CPC Class Codes: C10G 15/08 by electric means or by electromagnetic or mechanical vibrations
• CPC Class Codes: C10G 2300/1033 Oil well production fluids
• 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 29/205 : by reaction with hydrocarbons added to the hydrocarbon oil
• CPC Class Codes: H05H 1/46 : using applied electromagnetic fields, e.g. high frequency or microwave energy H05H1/26 takes precedence
• CPC Class Codes: H05H 1/4622 : using waveguides

Abstract

Conversion of heavy fossil hydrocarbons (HFH) to a variety of value-added chemicals and/or fuels can be enhanced using microwave (MW) and/or radio-frequency (RE) energy. Variations of reactants, process parameters, and reactor design can significantly influence the relative distribution of chemicals and fuels generated as the product. In one example, a system for flash microwave conversion of HFH includes a source concentrating microwave or RF energy in a reaction zone having a pressure greater than 0.9 atm, a continuous feed having HFH and a process gas passing through the reaction zone, a HFH-to-liquids catalyst contacting the HFH in at least the reaction zone, and dielectric discharges within the reaction zone. The HFH and the catalyst have a residence time in the reaction zone of less than 30 seconds. In some instances, a plasma can form in or near the reaction zone.

Claims

1. :

A method for selectively preparing paraffins from heavy fossil hydrocarbons (HFH), the method comprising;

providing reactants to a reaction zone, the reactants comprising HFH, catalyst, and methane;

exposing the reactants in the reaction zone to microwave or RF energy, the exposing selectively converting at least a portion of the HFH to paraffins; and

recovering at least the paraffins from the reaction zone.

2. :

The method of claim 1, wherein the catalyst comprises one or more of iron, char, and/or a promoter of dielectric discharge.

3. :

The method of claim 1, wherein the pressure in the reaction zone is from between 0.9 atm and 7 atm.

4. :

The method of claim 1, wherein the reactants are exposed within the reaction zone for residence time from between 5 milliseconds and 30 seconds.

5. :

The method of claim 1 wherein the paraffins comprise straight chained hydrocarbons.

6. :

The method of claim 1 wherein the exposing selectively converts the HFH to paraffins rather than aromatic hydrocarbons.

7. :

A method for converting aromatic hydrocarbons of heavy fossil fuel (HFH) to alkylated aromatic hydrocarbons, the method comprising;

providing reactants to a reaction zone, the reactants comprising HFH, catalyst, and methane, wherein the HFH comprises aromatic hydrocarbons;

exposing the reactants in the reaction zone to microwave or RF energy to form a product, the exposing selectively converting at least a portion of the aromatic hydrocarbons to methylated aromatic hydrocarbons; and

recovering at least a portion of the product from the reaction zone, the portion of the product comprising at least a portion of the alkylated aromatic hydrocarbons.

8. :

The method of claim 7, wherein the reactants are exposed within the reaction zone for residence time from between 5 milliseconds and 30 seconds.

9. :

The method of claim 7, further comprising separating a flowable portion of the product from a remainder of the product, the flowable portion of the product comprising alkylated aromatic hydrocarbons and paraffins.

10. :

The method of claim 9 wherein the remainder of the product comprises unflowable aromatic hydrocarbons.

11. :

A method for selectively preparing paraffins from heavy fossil hydrocarbon (HFH), the method comprising;

providing reactants to a reaction zone, the reactants comprising HFH, catalyst, and methane;

exposing the reactants in the reaction zone to microwave or RF energy, the exposing selectively converting at least a portion of the HFH to product, the product comprising paraffins and aromatics, wherein the ratio of paraffins to aromatics is greater than 0.05;

1; and

recovering at least the paraffins from the reaction zone.

12. :

The method of claim 11 wherein the product comprises gaseous, liquid flowable, and non-flowable materials, and wherein the method further comprises separating at least one of the gaseous, liquid flowable, and non-flowable materials from the product of the reaction zone.

13. :

The method of claim 12 wherein the liquid flowable material comprises paraffins.

14. :

The method of claim 12 wherein the liquid flowable material comprises alkylated aromatics.

15. :

The method of claim 12 wherein the liquid flowable material comprises both alkylated aromatics and paraffins.

16. :

The method of claim 12 wherein the gaseous material comprises single ring aromatics.

17. :

A heavy fossil hydrocarbon (HFH) reaction product comprising paraffins in substantially higher concentration than single ring aromatics, the product prepared according to the following process;

providing reactants to a reaction zone, the reactants comprising HFH, catalyst, and methane; and

exposing the reactants in the reaction zone to microwave or RF energy, the exposing selectively converting at least a portion of the HFH to the product comprising paraffins in substantially higher concentration than single ring aromatics.

18. :

The HFH reaction product of claim 17, wherein the reaction zone comprises one or more of a fluidized bed reactor, an entrained flow reactor, a free fall reactor, an ebulating bed reactor, and/or a moving bed reactor.

19. :

The HFH reaction product of claim 17, wherein the catalyst comprises one or more of nickel, cobalt, molybdenum, carbon, copper, alumina, silica, and/or oxygen.

20. :

The HFH reaction product of claim 17, wherein the catalyst and the HFH are admixed.

21. :

The HFH reaction product of claim 17, further comprising a plasma in or near the reaction zone.

22. :

The HFH reaction product of claim 17, wherein the catalyst has a concentration between 0.5 and 10 wt % relative to the HFH.