Dehydrogenation of liquid fuel in microchannel catalytic reactor

• US 20060143981A1
• Filed: 01/04/2005
• Published: 07/06/2006
• Est. Priority Date: 01/04/2005
• Status: Active Grant

• Current Assignee: Air Products and Chemicals Incorporated (Linde Plc)
• Original Assignee: Air Products and Chemicals Incorporated (Linde Plc)
• Inventors: Pez, Guido Peter, Puri, Pushpinder Singh, Toseland, Bernard Allen
• Granted Patent: US 7,485,161 B2
• Time in Patent Office: Days
• US Class Current: 48/61
• 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 2219/00783 Laminate assemblies, i.e. the reactor comprising a stack of plates
• 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 2219/00867 Microreactors placed in series, on the same or on different supports
• CPC Class Codes: B01J 2219/00873 Heat exchange
• CPC Class Codes: B01J 2219/00891 Feeding or evacuation
• CPC Class Codes: B01J 2219/00905 Separation
• CPC Class Codes: B01J 2219/00997 Strategical arrangements of multiple microreactor systems
• CPC Class Codes: C01B 3/0015 Organic compounds; Solutions thereof
• CPC Class Codes: C07C 5/32 by dehydrogenation with formation of free hydrogen
• CPC Class Codes: C07C 5/327 Formation of non-aromatic carbon-to-carbon double bonds only
• CPC Class Codes: H01M 8/065 by dissolution of metals or alloys; by dehydriding metallic substances
• CPC Class Codes: Y02E 60/32 Hydrogen storage
• CPC Class Codes: Y02E 60/50 Fuel cells
• CPC Class Codes: Y02P 20/129 Energy recovery, e.g. by cogeneration, H2recovery or pressure recovery turbines

Abstract

The present invention is an improved process for the storage and delivery of hydrogen by the reversible hydrogenation/dehydrogenation of an organic compound wherein the organic compound is initially in its hydrogenated state. The improvement in the route to generating hydrogen is in the dehydrogenation step and recovery of the dehydrogenated organic compound resides in the following steps: introducing a hydrogenated organic compound to a microchannel reactor incorporating a dehydrogenation catalyst; effecting dehydrogenation of said hydrogenated organic compound under conditions whereby said hydrogenated organic compound is present as a liquid phase; generating a reaction product comprised of a liquid phase dehydrogenated organic compound and gaseous hydrogen; separating the liquid phase dehydrogenated organic compound from gaseous hydrogen; and, recovering the hydrogen and liquid phase dehydrogenated organic compound.

Claims

1. In a process for the delivery of hydrogen from an organic compound capable of reversible hydrogenation/dehydrogenation wherein the organic compound is initially in its hydrogenated form and subsequently catalytically dehydrogenated under dehydrogenation conditions in a reactor forming hydrogen and byproduct dehydrogenated organic compound, the improvement in the dehydrogenation step which comprises:

(a) introducing said organic compound capable of reversible hydrogenation/dehydrogenation in liquid form to a microchannel reactor incorporating a dehydrogenation catalyst;

(b) effecting dehydrogenation of said organic compound under liquid phase conditions whereby said organic compound and said byproduct dehydrogenated organic compound remain in the liquid phase;

(c) recovering a reaction product comprised of a byproduct dehydrogenated organic compound and gaseous hydrogen;

(d) separating the reaction product comprised of said liquid phase dehydrogenated organic compound and gaseous hydrogen into a gaseous hydrogen fraction and liquid phase byproduct dehydrogenated organic compound;

(e) recovering the gaseous hydrogen; and

,

(f) recovering the liquid byproduct dehydrogenated organic compound.

2. The process of claim 1 wherein the dehydrogenation in step (b) is carried out at a pressure of from 0.2 atmospheres to 100 atmospheres.

3. The process of claim 2 wherein the temperature of dehydrogenation is from 60 to 300°

C.

4. The process of claim 1 wherein the dehydrogenation is carried out in a plurality of microchannel reactors wherein the pressure in each succeeding reactor is less than the prior reactor.

5. The process of claim 1 wherein the vapor pressure of the organic compound is less than 10 mm mercury at 220°

C.

6. The process of claim 2 wherein the organic compound forms a pi-conjugated substrate on dehydrogenation.

7. The process of claim 4 wherein the volume of hydrogen produced in each microchannel reactor is essentially the same.

8. The process of claim 2 wherein the organic compound is selected from the group consisting of hydrogenated forms of extended polycyclic aromatic hydrocarbons, extended pi-conjugated substrates with nitrogen heteroatoms, extended pi-conjugated substrates with heteroatoms other than nitrogen, pi-conjugated organic polymers and oligomers, ionic pi-conjugated substrates, pi-conjugated monocyclic substrates with multiple nitrogen heteroatoms, pi-conjugated substrates with at least one triple bonded group, a pitch, and any combination of two or more of the foregoing.

9. The process of claim 2, wherein the organic compound in its hydrogenated form is an extended polycyclic aromatic hydrocarbon selected from the group consisting of pyrene, perylene, coronene, ovalene, picene and rubicene, fluorene, indene and acenanaphthylene, pyranthrone;

and any combination of two or more of the foregoing.

10. The process of claim 2, wherein the organic compound is selected from the group consisting of N-methylcarbazole, N-ethylcarbazole, N-n-propylcarbazole and N-iso-propylcarbazole and mixtures thereof.

11. The process of claim 1 wherein the dehydrogenation is carried out in a plurality of microchannel reactors wherein the temperature in each succeeding reactor is higher than the prior reactor.

12. The process of claim 1 wherein alternate or adjacent channels are provided in the reactor channels for use in transporting heat transfer fluid.