Oxidative coupling of methane at near ambient feed temperature
Methods of performing a startup of an oxidative coupling of methane reaction to produce C2+ hydrocarbons are described. The methods can include incrementally varying startup parameters of the oxidative methane reactor and using the feed gas as a coolant such that high C2+ hydrocarbon selectivity is achieved.
1. A method of igniting an oxidative coupling of methane reaction to produce C 2 + hydrocarbons, the method comprising the steps of:
(a) preheating a gaseous feed stream to a temperature of at least 400° C., wherein the gaseous feed stream comprises methane (CH 4 ) and oxygen (O 2 ) having an initial CH 4 :O 2 molar ratio;
(b) introducing the preheated gaseous feed stream to an adiabatic reactor, wherein the adiabatic reactor includes a catalyst bed comprising an oxidative coupling of methane catalyst;
(c) igniting the oxidative coupling of methane reaction; and
(d) after igniting the oxidative coupling of methane reaction, incrementally reducing both the temperature and the CH 4 :O 2 molar ratio of the gaseous feed stream introduced into the adiabatic reactor to an operating temperature of 10° C. to 350° C. and a final CH 4 :O 2 molar ratio of 9:1 to 3:1 over a startup period such that, at the operating temperature, the oxidative coupling of methane reaction remains ignited and the reactor is in an autothermal state.
2. The method of claim 1 , wherein the initial CH 4 :O 2 molar ratio is 8:1 to 40:1 and the final CH 4 :O 2 molar ratio is 9:1 to 3:1 after incremental reduction.
3. The method of claim 2 , wherein the temperature is reduced in 1 to 10° C. increments and the molar ratio is reduced in 0.01 to 1 molar increments.
4. The method of claim 1 , wherein a final catalyst operating temperature is 750° C. to 1100° C.
5. The method of claim 1 , wherein the gaseous feed stream is preheated to 400° C. to 750° C.
6. The method of claim 1 , further comprising:
adding 1 mol % to 10 mol % of a gas more reactive than methane to the gaseous feed stream prior to ignition; and
discontinuing the addition after ignition.
7. The method of claim 1 , wherein the gaseous feed stream has a residence time of 0.1 to 1000 milliseconds in the catalyst bed before and during ignition, and the method further comprises decreasing the residence time to 0.1 to 20 milliseconds after ignition.
8. The method of claim 1 , further comprising continuing the oxidative coupling of methane reaction after step (d) to produce a product stream comprising C 2 + hydrocarbons.
9. The method of claim 8 , wherein the product stream further comprises hydrogen (H 2 ) and carbon monoxide (CO), carbon dioxide (CO 2 ), water (H 2 O) or mixtures thereof.
10. The method of claim 1 , wherein the catalyst comprises a metal oxide, a supported metal oxide, a mixed metal oxide, a supported mixed metal oxide, or any mixture thereof.
11. The method of claim 10 , wherein the catalyst is La 2 O 3 /CeO 2 , SrO/La 2 O 3 , Yb 2 O 3 —SrO—CeO 2 , Li/MgO, Na 2 WO 4 —Mn—O/SiO 2 , or any combination thereof.
12. The method of claim 1 , wherein the selectivity of C 2 + hydrocarbons is 30% to 95% after ignition.