Systems and methods for the oxidative coupling of methane

Patent metadata

Field	Value
Publication number	US-10836689-B2
Application number	US-201816030298-A
Country	US
Kind code	B2
Filing date	Jul 9, 2018
Priority date	Jul 7, 2017
Publication date	Nov 17, 2020
Grant date	Nov 17, 2020

Abstract

The present disclosure provides systems and methods for producing olefins via an oxidative coupling of methane (OCM) process. The systems and methods may comprise the use of a staged process comprising at least one non-adiabatic section that is in thermal communication with a heat transfer medium and at least one substantially adiabatic section. The systems and methods may also comprise the use of a diluent stream which may improve methane conversion in an OCM reactor and an ethylene/ethane ratio in a post-bed cracking unit. The methods and systems may further comprise injecting oxygen (O 2 ) and a paraffin into a gas stream containing a radical transfer agent to provide a reaction mixture. The reaction mixture may be held in a vessel for a time period greater than an auto-ignition delay time (AIDT), such that the reaction mixture may ignite to liberate heat and convert to a product mixture comprising olefins.

First claim

What is claimed is:

1. A method for producing an olefin, the method comprising:
(a) providing a reactor comprising two sections: an isothermal tubular section and a substantially adiabatic section, wherein said isothermal tubular section contains a first oxidative coupling of methane (OCM) catalyst configured to promote a first OCM reaction and is in thermal communication with a heat transfer medium;
(b) introducing a gas mixture into the isothermal tubular section of the reactor, which gas mixture comprises oxygen (O 2 ) and methane (CH 4 ), whereby at least about 75 mol % of the O 2 reacts with the CH 4 to produce an intermediate gas stream comprising hydrocarbon compounds having two or more carbon atoms (C 2+ compounds) and non-C 2+ impurities, wherein said first OCM catalyst undergoes deactivation over time such that (i) an outlet temperature of the isothermal tubular section decreases over time, (ii) an oxygen concentration at the outlet of the isothermal tubular section increases over time, and (iii) the oxygen concentration at the outlet of the isothermal tubular section is at least about 500 parts per million (ppm);
(c) injecting the intermediate gas stream into said substantially adiabatic section, wherein said substantially adiabatic section contains a second OCM catalyst to promote a second OCM reaction, wherein said second OCM catalyst undergoes deactivation over time such that (i) an outlet temperature of said substantially adiabatic section increases over time and (ii) an oxygen concentration at an outlet of said substantially adiabatic section is less than about 100 ppm; and
(d) generating a reactor effluent gas stream from said intermediate gas stream, wherein the reactor effluent gas stream comprises hydrocarbon compounds having C 2+ compounds and non-C 2+ impurities.

2. The method of claim 1 , wherein the first OCM reaction has a selectivity for C 2+ compounds of at least about 50% at 700° C.

3. The method of claim 1 , further comprising:
directing said reactor effluent gas stream into a post-bed cracking (PBC) section in fluid communication with and downstream of said substantially adiabatic section, wherein said PBC section converts ethane (C 2 H 6 ) in said reactor effluent gas stream into ethylene (C 2 H 4 ) using heat derived from the second OCM reaction.

4. The method of claim 1 , wherein the heat transfer medium is a molten salt.

5. The method of claim 1 , wherein the first OCM catalyst provides for the first OCM reaction to have a selectivity for C 2+ compounds of at least about 30% at 550° C.

6. The method of claim 1 , wherein the first OCM catalyst provides for the first OCM reaction to have a selectivity for C 2+ compounds of at least about 40% at 600° C.

7. The method of claim 1 , wherein the reactor further comprises a light off section in fluid communication with and upstream of the isothermal tubular section, which light-off section is in thermal communication with an additional heat transfer medium comprising a molten salt, and a heating section in fluid communication with and upstream of the light-off section, which heating section is in thermal communication with a further additional heat transfer medium, which further additional heat transfer medium comprises a molten salt.

8. The method of claim 1 , wherein the gas mixture has a temperature between about 450° C. and about 580° C.

9. The method of claim 1 , wherein the intermediate gas stream has a temperature between about 650° C. and about 750° C.

10. The method of claim 1 , wherein the gas mixture contains between about 15 mol % and about 20 mol % O 2 .

11. The method of claim 1 , wherein the intermediate gas stream contains at least about 1 mol % O 2 .

12. The method of claim 1 , wherein between about 1 mol % and about 5 mol % of the CH 4 from the intermediate gas mixture is converted to C 2+ compounds and non-C 2+ impurities in the substantially adiabatic section.

13. The method of claim 1 , wherein the first OCM catalyst comprises nanowires.

14. The method of claim 1 , wherein the second OCM catalyst comprises nanowires.

15. The method of claim 1 , wherein at least about 10 mol % of the O 2 from the gas mixture reacts with the CH 4 to produce C 2+ compounds and non-C 2+ impurities in the substantially adiabatic section of the reactor.

16. The method of claim 1 ,
wherein the second OCM catalyst has a different deactivation than a deactivation of the first OCM catalyst.

17. The method of claim 1 , wherein the second OCM reaction has a net selectivity for C 2+ compounds of at least about 5% at greater than 850° C.

18. The method of claim 1 , wherein said intermediate gas stream comprises unreacted CH 4 and wherein less than about 10 mol % of the unreacted CH 4 is reformed into CO and H 2 .

19. The method of claim 3 , further comprising:
injecting between about 1 mol % and 5 mol % of ethane (C 2 H 6 ) via an additional gas stream into the reactor gas effluent stream near an inlet of the PBC section; and
converting at least a portion of the C 2 H 6 in said additional gas stream into ethylene (C 2 H 4 ) using heat derived from the second OCM reaction.

Assignees

• Lummus Technology Inc

Inventors

• Cizeron Joel
• Sheridan David
• Turk Gregory J
• Lakhapatri Satish
• Fan Rong
• Radaelli Guido
• Martens Franciscus J A
• Mccormick Jarod
• Grauer David C
• Zurcher Fabio R
• Rosenberg Daniel

Classifications

• C07C2523/02

  of the alkali- or alkaline earth metals or beryllium · CPC title

• C07C2521/10

  Magnesium; Oxides or hydroxides thereof · CPC title

• C07C2521/06

  Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof · CPC title

• C07C11/06

  Propene · CPC title

• C07C2/84 Primary

  catalytic · CPC title