# US 2025/0084016 A1 · Liquid organic hydrogen carrier process and catalyst system

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- Number: US 2025/0084016 A1
- Document ID: US20250084016A1
- Status: Published application
- Kind: A1
- Application number: 18/744,983
- Filed: 2024-06-17
- Published: 2025-03-13
- Earliest claimed: 2023-09-11
- Assignees: Uop LLC
- Applicants: Uop LLC
- Inventors: Nirlipt Mahapatra; Priyank Tiwari; Srinivasan Ramanujam; Priyesh Jayendrakumar Jani; Gautam Pandey; Pankaj Kumar Singh; Raymond S. Chan; Bryan J. Egolf; Elie J. Fayad; David S. Lafyatis; Clayton C. Sadler
- Web page: https://patentgrep.com/patent/US20250084016A1

## CPC

- C07C 5/10: of aromatic six-membered rings
- B01D 53/22: by diffusion (manufacturing semi-permeable membranes B01D67/00; form, structure or properties of semi-permeable membranes B01D69/00; material for semi-permeable membranes B01D71/00)
- C01B 3/501: by diffusion
- C01B 3/56: by contacting with solids; Regeneration of used solids
- C07C 5/322: {with metal oxides or metal sulfides}
- C07C 5/367: Formation of an aromatic six-membered ring from an existing six-membered ring, e.g. dehydrogenation of ethylcyclohexane to ethylbenzene
- B01D 2256/16: Hydrogen
- C07C 2521/04: Alumina
- C07C 2601/14: The ring being saturated
- C07C: ACYCLIC OR CARBOCYCLIC COMPOUNDS
- B01D: SEPARATION (separating solids from solids by wet methods B03B, B03D; by pneumatic jigs or tables B03B; by other dry methods B07; magnetic or electrostatic separation of solid materials from solid materials or fluids, separation by high-voltage electric fields B03C; centrifuges, vortex apparatus B04; presses per se for squeezing-out liquid from liquid-containing material B30B9/02; treatment of water C02F, e.g. softening by ion-exchange C02F1/42; {arrangements of air intake cleaners in gas turbine plants F02C7/05} ; arrangements or mounting of filters in air-conditioning, air-humidification or ventilation F24F13/28)
- C01B: NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; {METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C}

## Abstract

Processes for hydrogenating toluene to methylcyclohexane (MCH) and dehydrogenating MCH to toluene with minimal to no by-products, thereby ensuring minimal loss of hydrogen are described. MCH acts as a liquid organic hydrogen carrier, and it can be transferred in storage vessels and/or pipelines for several thousands of miles to the final destination with very minimal to no degradation.

## Claims

### Claim 1

A process for transporting hydrogen by saturating toluene to methylcyclohexane comprising:
splitting a hydrocarbon feed stream comprising toluene into at least first and second hydrocarbon streams;
saturating at least a portion of the toluene in the first hydrocarbon stream in a first hydrogenation reactor of a hydrogenation reaction section comprising at least one hydrogenation reactor in the presence of hydrogen and a first hydrogenation catalyst having very high methyl cyclohexane selectivity to produce a first saturated effluent stream comprising methylcyclohexane, the first hydrogenation reactor operating in vapor phase;
passing the first saturated effluent stream and the second hydrocarbon stream to a second hydrogenation reactor in the hydrogenation reaction section in the presence of hydrogen and a second hydrogenation catalyst to produce a second saturated effluent stream comprising additional methylcyclohexane, the second hydrogenation reactor operating in vapor phase;
passing the second saturated effluent stream to a polishing reactor in the presence of a polishing hydrogenation catalyst to produce a polishing reactor effluent stream, the polishing reactor operating in vapor phase;
separating the polishing reactor effluent stream in a high pressure separator into a liquid stream comprising the methylcyclohexane and a vapor stream comprising hydrogen, wherein the vapor stream comprises at least a portion of the hydrogen in the first or second hydrogenation reactors;
splitting the liquid stream into an optional recycle hydrocarbon stream and a second liquid stream;
optionally recycling the recycle hydrocarbon stream to the hydrocarbon feed stream, the first hydrocarbon stream, the second hydrocarbon stream, the first hydrogenation reactor, the second hydrogenation reactor, or combinations thereof;
stabilizing the second liquid stream to form a product stream comprising methylcyclohexane; and
transporting the product stream to a second location.

### Claim 2 (depends on 1)

The process of claim 1 further comprising:
passing a portion of the vapor stream through a membrane or a sponge oil system to remove light ends to form a hydrogen rich stream and a reject stream; and
compressing the hydrogen rich stream and sending the compressed hydrogen rich stream to the hydrocarbon feed stream, first hydrocarbon stream, the second hydrocarbon stream, the first hydrogenation reactor, the second hydrogenation reactor, or combinations thereof.

### Claim 3 (depends on 2)

The process of claim 2 wherein 0.01-35% of the vapor stream is passed through the membrane or the sponge oil system.

### Claim 4 (depends on 1)

The process of claim 1 wherein the hydrocarbon feed stream is pre-heated using heat of reaction from the first hydrogenation reactor, the second hydrogenation reactor, or both.

### Claim 5 (depends on 1)

The process of claim 1 further comprising:
superheating a steam stream generated from heat of reaction of one of the hydrogenation reactors using heat of reaction of another hydrogenation reactor.

### Claim 6 (depends on 1)

The process of claim 1 further comprising:
passing the second liquid stream through a pressure recovery turbine before stabilizing the second liquid stream to generate power and utilizing the power in the process or exporting the power to a second process.

### Claim 7 (depends on 5)

The process of claim 5 further comprising:
generating power from the superheated steam stream.

### Claim 8 (depends on 5)

The process of claim 5 wherein the steam stream has a pressure in the range of 350 kPa (g) to 2500 kPa (g) (3.5 barg to 25 barg).

### Claim 9 (depends on 1)

The process of claim 1 further comprising:
pre-treating the hydrocarbon feed stream, the hydrogen, or both in an adsorbent bed to remove contaminants.

### Claim 10 (depends on 1)

The process of claim 1 further comprising:
recycling part of an off-gas stream from a stabilizer overhead stream to a make-up gas compressor suction.

### Claim 11 (depends on 1)

The process of claim 1 wherein the first hydrogenation catalyst or the second hydrogenation catalyst or both comprises a metal of Group VIII of the Periodic Table and optionally a metal of Group I of the Periodic Table.

### Claim 12 (depends on 1)

The process of claim 1 wherein the first hydrogenation catalyst or the second hydrogenation catalyst or both comprises 0.05 wt % to 30 wt % of a metal of Group VIII of the Periodic Table and optionally 0.1 wt % to 3 wt % of a metal of Group I of the Periodic Table.

### Claim 13 (depends on 1)

The process of claim 1 wherein the hydrogenation reaction section further comprises an intermediate hydrogenation reactor between the first and second hydrogenation reactors, the process further comprising:
splitting the hydrocarbon feed stream comprising toluene into at least the first and second hydrocarbon streams and a third hydrocarbon stream;
before passing the second hydrocarbon stream to the second hydrogenation reactor, passing the first saturated effluent stream and the third hydrocarbon stream to the intermediate hydrogenation reactor in the presence of hydrogen and an intermediate hydrogenation catalyst to form an intermediate saturated effluent stream comprising additional methylcyclohexane, the intermediate hydrogenation reactor operating in the vapor phase; and
passing the intermediate saturated effluent stream to the second hydrogenation reactor.

### Claim 14 (depends on 13)

The process of claim 13 where the polishing reactor has an inlet temperature at least 20° C. higher than a dew point of the second or intermediate reactor effluent stream.

### Claim 15

A process for transporting hydrogen by saturating toluene to methylcyclohexane comprising:
splitting a hydrocarbon feed stream comprising toluene into first, intermediate, and second hydrocarbon streams;
saturating at least a portion of the toluene in the first hydrocarbon stream in a first hydrogenation reactor of a hydrogenation reaction section comprising at least a first hydrogenation reactor, an intermediate hydrogenation reactor, and a second hydrogenation reactor in the presence of hydrogen and a first hydrogenation catalyst having very high methyl cyclohexane selectivity to produce a first saturated effluent stream comprising methylcyclohexane, the first hydrogenation reactor operating in vapor phase;
passing the first saturated effluent stream and the intermediate hydrocarbon stream to the intermediate hydrogenation reactor in the presence of hydrogen and an intermediate hydrogenation catalyst to produce an intermediate saturated effluent stream comprising additional methylcyclohexane, the intermediate hydrogenation reactor operating in vapor phase;
passing the intermediate saturated effluent stream and the second hydrocarbon stream to the second hydrogenation reactor in the presence of hydrogen and a second hydrogenation catalyst to produce a second saturated effluent stream comprising additional methylcyclohexane, the second hydrogenation reactor operating in vapor phase;
passing the second saturated effluent stream to a polishing reactor in the presence of a polishing hydrogenation catalyst to produce a polishing reactor effluent stream, the polishing reactor operating in vapor phase;
separating the polishing reactor effluent stream in a high pressure separator into a liquid stream comprising the methylcyclohexane and a vapor stream comprising hydrogen, wherein the vapor stream comprises at least a portion of the hydrogen in the first, intermediate, or second hydrogenation reactors;
splitting the liquid stream into a recycle hydrocarbon stream and a second liquid stream;
recycling the recycle hydrocarbon stream to the hydrocarbon feed stream, the first hydrocarbon stream, the intermediate hydrocarbon stream, the second hydrocarbon stream, the first hydrogenation reactor, the intermediate hydrogenation reactor, the second hydrogenation reactor, or combinations thereof;
stabilizing the second liquid stream to form a product stream comprising methylcyclohexane;
pre-heating the hydrocarbon feed stream using heat of reaction of the first hydrogenation reactor, the intermediate hydrogenation reactor, the second hydrogenation reactor, or combinations thereof; and
superheating a steam stream generated from the heat of reaction of one of the hydrogenation reactors using a heat of reaction of another hydrogenation reactor; and
transporting the product stream to a second location.

### Claim 16 (depends on 15)

The process of claim 15 further comprising:
passing a portion of the vapor stream through a membrane or a sponge oil system to remove light ends to form a hydrogen rich stream and a reject stream; and
compressing the hydrogen rich permeate and sending the compressed hydrogen rich permeate to the hydrocarbon feed stream, the first hydrocarbon stream, the intermediate hydrocarbon stream, the second hydrocarbon stream, the first hydrogenation reactor, the intermediate reactor, the second hydrogenation reactor, or combinations thereof.

### Claim 17

A process for transporting hydrogen by saturating toluene to methylcyclohexane comprising:
splitting a hydrocarbon feed stream comprising toluene into at least first and second hydrocarbon streams;
saturating at least a portion of the toluene in the first hydrocarbon stream in a first hydrogenation reactor of a hydrogenation reaction section comprising at least one hydrogenation reactor in the presence of hydrogen and a first hydrogenation catalyst having very high methyl cyclohexane selectivity to produce a first saturated effluent stream comprising methylcyclohexane, the first hydrogenation reactor operating in vapor phase;
passing the first saturated effluent stream and the second hydrocarbon stream to a second hydrogenation reactor in the hydrogenation reaction section in the presence of hydrogen and a second hydrogenation catalyst to produce a second saturated effluent stream comprising additional methylcyclohexane, the second hydrogenation reactor operating in vapor phase;
passing the second saturated effluent stream to a polishing reactor in the presence of a polishing hydrogenation catalyst to produce a polishing reactor effluent stream, the polishing reactor operating in vapor phase;
separating the polishing reactor effluent stream in a high pressure separator into a liquid stream comprising the methylcyclohexane and a vapor stream comprising hydrogen, wherein the vapor stream comprises at least a portion of the hydrogen in the first or second hydrogenation reactors;
splitting the liquid stream into an optional recycle hydrocarbon stream and a second liquid stream;
optionally recycling the recycle hydrocarbon stream to the hydrocarbon feed stream, the first hydrocarbon stream, the second hydrocarbon stream, the first hydrogenation reactor, the second hydrogenation reactor, or combinations thereof;
stabilizing the second liquid stream to form a product stream comprising methylcyclohexane;
transporting the product stream to a second location;
dehydrogenating the methylcyclohexane in the product stream in a dehydrogenation reaction section comprising one or more dehydrogenation reactors in the presence of a dehydrogenation catalyst to form a toluene stream comprising toluene and a hydrogen product stream comprising hydrogen;
passing the toluene stream to a stabilizer column to recover a toluene product stream; and
recovering the hydrogen product stream.

### Claim 18 (depends on 17)

The process of claim 17 wherein the dehydrogenation catalyst comprises Al2O3, a noble metal, and an alkali or alkaline earth metal to achieve a selectivity in the dehydrogenation of methylcyclohexane to toluene and hydrogen in excess of 99.8%.

### Claim 19 (depends on 17)

The process of claim 17 further comprising:
passing the dehydrogenated product into a gas/liquid separator followed by stabilization of the separator liquid stream and passing the stabilized product through a deisoheptanizer column for further fractionation into a C6/C7 stream comprising hexane and heptane, the recycle methylcyclohexane stream and the toluene product stream, where in the toluene product stream can be shipped back to the hydrogenation unit.

### Claim 20 (depends on 19)

The process of claim 19 further comprising:
splitting the separator gas stream into a recycle hydrogen stream and a product hydrogen stream for further compression and distribution.