# US 2018/0022667 A1 · Hydrocarbon Dehydrocyclization in the Presence of Carbon Dioxide

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- Number: US 2018/0022667 A1
- Document ID: US20180022667A1
- Status: Published application
- Kind: A1
- Application number: 15/702,174
- Filed: 2017-09-12
- Published: 2018-01-25
- Earliest claimed: 2015-09-25
- Applicants: ExxonMobil Chemical Patents Inc.
- Inventors: John S. Buchanan; Paul F. Keusenkothen; David W. Maher; Jaime A. Valencia
- Web page: https://patentgrep.com/patent/US20180022667A1

## CPC

- C07C 2/76: by condensation of hydrocarbons with partial elimination of hydrogen
- B01J 8/0278: {Feeding reactive fluids (for solid material B01J8/0015)}
- B01J 23/462: {Ruthenium}
- B01J 23/464: {Rhodium}
- B01J 23/58: with alkali- or alkaline earth metals
- B01J 23/63: with rare earths or actinides
- B01J 23/6522: {Chromium}
- B01J 23/6562: {Manganese}
- B01J 23/755: Nickel
- B01J 23/78: with alkali- or alkaline earth metals
- B01J 23/83: with rare earths or actinides
- B01J 23/866: {Nickel and chromium}
- B01J 23/8892: {Manganese}
- B01J 29/06: Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J 29/405: {containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead}
- B01J 29/48: containing arsenic, antimony, bismuth, vanadium, niobium tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J 29/655: {containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead}
- B01J 29/69: containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J 29/708: {MRE-type, e.g. ZSM-48}
- B01J 29/7084: {MTW-type, e.g. ZSM-12, NU-13, TPZ-12 or Theta-3}
- B01J 29/7088: {MWW-type, e.g. MCM-22, ERB-1, ITQ-1, PSH-3 or SSZ-25}
- B01J 29/7092: {TON-type, e.g. Theta-1, ISI-1, KZ-2, NU-10 or ZSM-22}
- B01J 29/7096: {MTT-type, e.g. ZSM-23, KZ-1, ISI-4 or EU-13}
- B01J 29/7269: {MTW-type, e.g. ZSM-12, NU-13, TPZ-12 or Theta-3}
- B01J 29/7861: {MRE-type, e.g. ZSM-48}
- B01J 29/7869: {MTW-type, e.g. ZSM-12, NU-13, TPZ-12 or Theta-3}
- B01J 29/7876: {MWW-type, e.g. MCM-22, ERB-1, ITQ-1, PSH-3 or SSZ-25}
- B01J 29/7884: {TON-type, e.g. Theta-1, ISI-1, KZ-2, NU-10 or ZSM-22}
- B01J 29/7892: {MTT-type, e.g. ZSM-23, KZ-1, ISI-4 or EU-13}
- B01J 35/19: {Catalysts containing parts with different compositions}
- B01J 37/08: Heat treatment {(B01J37/0009, B01J37/0018 take precedence)}
- B01J 37/16: Reducing
- C07C 1/12: from carbon dioxide with hydrogen
- C07C 9/04: Methane (production by treatment of sewage C02F11/04; natural gas, synthetic natural gas C10L3/06)
- C07C 15/04: Benzene
- B01J 2208/02: with stationary particles
- B01J 2229/12: to alter the outside of the crystallites, e.g. selectivation
- B01J 2229/18: to introduce other elements into or onto the molecular sieve itself
- B01J 2229/37: Acid treatment
- C07C 2529/06: Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- Y02P 20/52: using catalysts, e.g. selective catalysts
- C07C: ACYCLIC OR CARBOCYCLIC COMPOUNDS
- B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- Y02P: CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS

## Abstract

The invention relates to converting non-aromatic hydrocarbon in the presence of CO2 to produce aromatic hydrocarbon. CO2 methanation using molecular hydrogen produced during the aromatization increases aromatic hydrocarbon yield. The invention also relates to equipment and materials useful in such upgrading, to processes for carrying out such upgrading, and to the use of such processes for, e.g., natural gas upgrading.

## Claims

### Claim at position 1

1-10. (canceled)

### Claim 11

An active material for hydrocarbon aromatization in the presence of CO2, the active material comprising:
(a) ≧10 wt. % a first catalyst, wherein the first catalyst comprises (i) ≧0.005 wt. % of a dehydrogenation component which includes one or more of Ga, Zn, Mo, W, La, Pt, and Pd, and
(ii) ≧10 wt. % of a molecular sieve component which comprises at least one molecular sieve having a Constraint Index in the range of from 1 to 12; and
(b) ≧10 wt. % of a second catalyst, wherein the second catalyst comprises ≧0.005 wt. % of a CO2 conversion component which includes one or more of Ru, Rh, Ni, Co, and Fe.

### Claim 12 (depends on 11)

The active material of claim 11, wherein the first catalyst comprises ≧0.1 wt. % of the dehydrogenation component, and the dehydrogenation component includes one or more of Ga, Zn, Mo, W, and La.

### Claim 13 (depends on 11)

The active material of claim 11, wherein he first catalyst comprises ≧1 wt. % of the dehydrogenation component, and the dehydrogenation component comprises ≧95 wt. % of (i) Ga and/or (ii) Zn.

### Claim 14 (depends on 11)

The active material of claim 11, wherein the molecular sieve component comprises one or more of MCM-22, ZSM-5, ZSM-11, ZSM-12, ZSM-22, ZSM-23, ZSM-35, and ZSM-48.

### Claim 15 (depends on 11)

The active material of claim 11, wherein the molecular sieve component comprises ≧90 wt. % of aluminosilicate having a silica : alumina ratio in the range of from in the range of from 10 to 80.

### Claim 16 (depends on 11)

The active material of claim 11, wherein, the second catalyst includes ≧0.1 wt. % of the CO2 conversion component, and the CO2 conversion component includes one or more of Ru, Rh, and Ni.

### Claim 17 (depends on 11)

The active material of claim 11, wherein, the second catalyst includes ≧1 wt. % of the CO2 conversion component, the CO2 conversion component comprises ≧95 wt. % of (i) Ru and/or (ii) Ni, and the second catalyst further comprises ≧1 wt. % of one or more of oxide of chromium, oxide of aluminum, oxide of magnesium, oxide of manganese, oxide of cerium, oxide of zirconium, oxide of titanium, and oxide of thorium.

### Claim 18 (depends on 11)

The active material of claim 11, wherein the first and second catalyst each comprise ≦0.1 wt. % of binder.

### Claim 19 (depends on 11)

The active material of claim 11, wherein the active material has the form of a composite, wherein the composite comprises ≧20 wt. % of the first catalyst and ≧20 wt. % of the second catalyst.

### Claim 20 (depends on 11)

The active material of claim 11, wherein the first catalyst has the form of a first particulate, the second catalyst has the form of a second particulate, the active material has the form of a mixture of the first and second particulates, and the active material comprises ≧20 wt. % of the first catalyst and ≧20 wt. % of the second catalyst.

### Claim 21

A process for making an active material for hydrocarbon aromatization in the presence of CO2, the process comprising:
(a) providing at least one molecular sieve, the molecular sieve having a Constraint Index in the range of from 1 to 12;
(b) providing a first precursor, the first precursor comprising a dehydrogenation component which includes one or more of Ga, Zn, Mo, W, La, Pt, and Pd;
(c) contacting the molecular sieve and the first precursor under conditions effective for transferring to the molecular sieve at least a portion of the dehydrogenation component to produce a loaded molecular sieve comprising ≧0.005 wt. % of one or more of Ga, Zn, Mo, W, La, Pt, and Pd;
(d) providing an oxide matrix which includes one or more of oxide of chromium, oxide of aluminum, oxide of magnesium, oxide of manganese, oxide of cerium, oxide of zirconium, oxide of titanium, and oxide of thorium;
(e) providing a second precursor, the second precursor comprising a CO2 conversion component which includes one or more of Ru, Rh, Ni, Co, and Fe;
(f) contacting the matrix and the second precursor under conditions effective for transferring to the matrix at least a portion of the CO2 conversion component to produce a loaded matrix comprising ≧0.005 wt. % of one or more of Ru, Rh, Ni, Co, and Fe;
(g) calcining the loaded molecular sieve and the loaded matrix; and
(h) reducing the calcined loaded molecular sieve and the calcined loaded matrix to produce the active material.

### Claim 22 (depends on 21)

The process of claim 21, wherein the loaded molecular sieve is the form of a first particulate, the loaded matrix is in the form of a second particulate, and further comprising combining the first and second particulates before step (g), after step (g) or after step (h).

### Claim 23

A process for making an active material for hydrocarbon aromatization in the presence of CO2, the process comprising:
(a) providing at least one molecular sieve, the molecular sieve having a Constraint Index in the range of from 1 to 12;
(b) providing a first precursor, the first precursor comprising a dehydrogenation component which includes one or more of Ga, Zn, Mo, W, La, Pt, and Pd;
(c) providing a second precursor, the second precursor comprising a CO2 conversion component which includes one or more of Ru, Rh, Ni, Co, and Fe;
(d) producing a loaded molecular sieve by contacting the molecular sieve with the first and second precursors under conditions effective for transferring to the molecular sieve (i) at least a portion of the dehydrogenation component and (ii) at least a portion of the CO2 conversion component, the loaded molecular sieve comprising ≧0.005 wt. % of one or more of Ga, Zn, Mo, W, La, Pt, and Pd and ≧0.005 wt. % of one or more of Ru, Rh, Ni, Co, and Fe;
(e) calcining the loaded molecular; and
(f) reducing the calcined loaded molecular sieve to produce the active material.

### Claim 24 (depends on 23)

The active material product of claim 23.

### Claim 25

An aromatization apparatus, the apparatus comprising:
(a) a reactor having an internal volume which includes at least one reaction zone;
(b) at least one feed conduit in fluidic communication with a hydrocarbon source located upstream of the reactor, wherein (i) the feed conduit is configured to establish a flow of hydrocarbon feed from the hydrocarbon source to the reaction zone and (ii) the hydrocarbon feed comprises ≧10 wt. % of C2+ non-aromatic hydrocarbon and ≧5 wt. % of CO2;
(c) at least one catalyst bed located in the reaction zone, the catalyst bed being configured to (i) convert a first portion of the feed's C2+ non-aromatic hydrocarbon to aromatic hydrocarbon and molecular hydrogen, (ii) react at least a portion of the molecular hydrogen with ≧50 wt. % of the hydrocarbon feed's CO2 to produce methane and water, (iii) convert a second portion of the natural gas's C2+ non-aromatic hydrocarbon to additional aromatic hydrocarbon and additional molecular hydrogen, and (iv) establish a flow of reactor effluent, the reactor effluent comprising ≧90 wt. % of the aromatic hydrocarbon and ≧90 wt. % additional aromatic hydrocarbon; and
(d) at least one product conduit in fluidic communication with the reaction zone, the product conduct being configured for conducting the reactor effluent away from the reactor.