Method of Producing Higher Value Hydrocarbons by Isothermal Oxidative Coupling of Methane

Patent metadata

Field	Value
Publication number	US-2016376208-A1
Application number	US-201615180955-A
Country	US
Kind code	A1
Filing date	Jun 13, 2016
Priority date	Jun 23, 2015
Publication date	Dec 29, 2016
Grant date	—

Abstract

A method for producing olefins comprising (a) introducing to an isothermal reactor a reactant mixture comprising CH 4 and O 2 , wherein the reactor comprises a catalyst bed comprising a catalyst, wherein a catalyst bed temperature is 750-1,000° C., and wherein the reactor has a residence time of 1-100 ms; (b) wherein isothermal conditions minimize hot spots in the bed, thereby decreasing deep oxidation reactions; (c) allowing the reactant mixture to contact the catalyst and react via oxidative coupling of CH 4 reaction to form a product mixture comprising C 2+ hydrocarbons (olefins and paraffins; C 2 hydrocarbons and C 3 hydrocarbons) and synthesis gas (H 2 and CO), wherein the product mixture has an olefin/paraffin molar ratio of from 0.5:1 to 20:1, and wherein the product mixture has a H 2 /CO molar ratio of from 0.2:1 to 2.5:1; (d) recovering the product mixture from the reactor; and (e) recovering C 2 hydrocarbons and/or synthesis gas from the product mixture.

First claim

What is claimed is:

1 . A method for producing olefins comprising:
(a) introducing a reactant mixture to an isothermal reactor, wherein the reactant mixture comprises methane (CH4) and oxygen (O2), wherein the isothermal reactor comprises a catalyst bed comprising a catalyst, wherein an isothermal reaction temperature in the catalyst bed is from about 750° C. to about 1,000° C., and wherein the reactor is characterized by a residence time of from about 1 millisecond to about 100 milliseconds in the catalyst bed; (b) wherein isothermal reactor conditions minimize hot spots formation in the catalyst bed, thereby decreasing an incidence of deep oxidation reactions, when compared to an incidence of deep oxidation reactions in an otherwise similar oxidative coupling of CH4 reaction conducted under non-isothermal conditions; (c) allowing at least a portion of the reactant mixture to contact the catalyst and react via an oxidative coupling of CH4 reaction to form a product mixture under isothermal conditions, wherein the product mixture comprises C2+ hydrocarbons and synthesis gas, wherein the C2+ hydrocarbons comprise olefins and paraffins, wherein the C2+ hydrocarbons comprise C2 hydrocarbons and C3 hydrocarbons, wherein the product mixture is characterized by an olefin/paraffin molar ratio of from about 0.5:1 to about 20:1, wherein the synthesis gas comprises hydrogen (H2) and carbon monoxide (CO), and wherein the product mixture is characterized by a H2/CO molar ratio of from about 0.2:1 to about 2.5:1; (d) recovering at least a portion of the product mixture from the reactor; and (e) recovering at least a portion of the C2 hydrocarbons and/or at least a portion of the synthesis gas from the product mixture.

2 . The method of claim 1 , wherein the isothermal reaction temperature in the catalyst bed is less than about 900° C.

3 . The method of claim 1 , wherein the isothermal reactor comprises a reactor vessel located inside a fluidized sand bath reactor.

4 . The method of claim 3 , wherein the isothermal conditions are provided by fluidization of heated microspheres around the isothermal reactor comprising the catalyst bed, wherein the microspheres are heated at a temperature of from about 725° C. to about 1,000° C., and wherein the microspheres comprise sand, metal oxides, quartz sand, aluminum oxide, silicon carbide, or combinations thereof.

5 . The method of claim 1 , wherein a selectivity to C2+ hydrocarbons and synthesis gas is from about 60% to about 99%.

6 . The method of claim 1 , wherein a methane conversion is from about 10% to about 45%.

7 . The method of claim 1 , wherein the C2 hydrocarbons comprise ethylene and ethane and wherein a molar ratio of ethylene to ethane is from about 0.5:1 to about 20:1.

8 . The method of claim 1 , wherein the C3 hydrocarbons comprise propylene and propane and wherein a molar ratio of propylene to propane is from about 0.5:1 to about 50:1.

9 . The method of claim 1 , wherein a selectivity to C2 hydrocarbons is from about 55% to about 95%.

10 . The method of claim 1 , wherein a selectivity to ethylene is from about 20% to about 80%.

11 . The method of claim 1 , wherein a selectivity to C2+ hydrocarbons is from about 60% to about 95%.

12 . The method of claim 1 , wherein equal to or greater than about 5 mol % of the reactant mixture is converted to olefins.

13 . The method of claim 1 , wherein equal to or greater than about 5 mol % of the reactant mixture is converted to synthesis gas.

14 . The method of claim 1 , wherein a selectivity to CO is from about 5% to about 25%.

15 . A method for producing olefins comprising:
(a) introducing a reactant mixture to an isothermal reactor, wherein the reactant mixture comprises methane (CH4) and oxygen (O2), wherein the isothermal reactor comprises a catalyst bed comprising a catalyst, wherein an isothermal reaction temperature in the catalyst bed is from about 750° C. to about 950° C., and wherein the reactor is characterized by a residence time of from about 1 millisecond to about 100 milliseconds in the catalyst bed, and wherein isothermal reactor conditions minimize hot spots formation within the reactor; (b) allowing at least a portion of the reactant mixture to contact the catalyst and react via an oxidative coupling of CH4 reaction to form a product mixture, wherein the product mixture comprises olefins, and wherein a selectivity to olefins is increased by equal to or greater than about 10% when compared to a selectivity of an otherwise similar oxidative coupling of CH4 reaction conducted under non-isothermal conditions; and (c) recovering at least a portion of the product mixture from the reactor.

16 . The method of claim 15 further comprising minimizing deep oxidation of methane to carbon dioxide (CO2).

17 . The method of claim 15 , wherein the product mixture comprises less than about 10 mol % carbon dioxide (CO2).

18 . The method of claim 15 , wherein the product mixture comprises synthesis gas.

19 . A method for producing ethylene comprising:
(a) introducing a reactant mixture to an isothermal reactor, wherein the reactant mixture comprises methane (CH4) and oxygen (O2), wherein the reactant mixture is characterized by a CH4/O2 molar ratio of from about 4:1 to about 8:1, wherein the isothermal reactor comprises a catalyst bed comprising a catalyst, wherein an isothermal reaction temperature in the catalyst bed is from about 800° C. to about 900° C., and wherein the reactor is characterized by a residence time of from about 10 millisecond to about 50 milliseconds in the catalyst bed; (b) allowing at least a portion of the reactant mixture to contact the catalyst and react via an oxidative coupling of CH4 reaction to form a product mixture, wherein the product mixture comprises ethylene, and wherein a selectivity to ethylene is increased by equal to or greater than about 40% when compared to a selectivity of an otherwise similar oxidative coupling of CH4 reaction conducted under non-isothermal conditions; (c) recovering at least a portion of the product mixture from the reactor; and (d) separating at least a portion of the ethylene from the product mixture by cryogenic distillation to yield recovered ethylene.

20 . The method of claim 19 , wherein the product mixture comprises synthesis gas, and wherein the synthesis gas is separated from the product mixture by cryogenic distillation to yield recovered synthesis gas.

Assignees

• Sabic Global Technologies Bv

Inventors

• SARSANI Vidya Sagar Reddy
• West David
• Mamedov Aghaddin
• Liang Wugeng
• Lowrey James
• Lengyel Istvan

Classifications

• C07C2521/08

  Silica · CPC title

• C01B2203/0261

  containing a catalytic partial oxidation step [CPO] · CPC title

• C07C2523/34

  Manganese · CPC title

• C07C2523/04

  Alkali metals · CPC title

• C07C2523/30

  Tungsten · CPC title