Hydrocarbon conversion process

Patent metadata

Field	Value
Publication number	US-9815919-B2
Application number	US-201615099844-A
Country	US
Kind code	B2
Filing date	Apr 15, 2016
Priority date	Jan 19, 2011
Publication date	Nov 14, 2017
Grant date	Nov 14, 2017

Abstract

The invention relates to a process for converting hydrocarbons into products containing aldehydes and/or alcohols. The invention also relates to producing olefins from the aldehyde and alcohol, to polymerizing the olefins, and to equipment useful for these processes.

First claim

The invention claimed is:

1. A hydrocarbon conversion process, comprising:
(a) providing a first mixture comprising hydrocarbon and oxygenate wherein the hydrocarbon is natural gas and the oxygenate is air;
(b) exposing the first mixture to a temperature ≧1.4×10 3 ° C. at a total pressure ≧0.1 bar absolute under high-severity thermal pyrolysis conditions in a first region to produce a second mixture, the second mixture comprising molecular hydrogen, carbon monoxide, ≧1.0 wt. % ethylene, and ≧1.0 wt. % of acetylene based on the weight of the second mixture, the second mixture having an acetylene:ethylene molar ratio in the range of 0.5 to 20.0 and a carbon monoxide:C 2 unsaturates molar ratio in the range of 0.15 to 2.0;
(c) transferring the second mixture away from the first region;
(d) providing a fourth mixture comprising fuel and oxidant, and at least partially oxidizing the fourth mixture in a second region to produce a fifth mixture comprising water and/or carbon dioxide, the first and second regions being at least partially coextensive and the oxidizing being conducted at a different time than the exposing;
(e) transferring the fifth mixture away from the second region;
(f) separating from the second mixture (i) a third mixture having a CO:C 2 unsaturates ratio in the range of 0.15 to 2.0 and comprising molecular hydrogen, carbon monoxide, methane, and ≧1.0 wt. % ethylene based on the weight of the third mixture and (ii) a composition comprising >90.0 wt. % of the second mixture's acetylene based on the weight of the second mixture's acetylene;
(g) hydroformylating at least a portion of the third mixture to produce a product comprising ≧1.01 wt. % propanal and/or 1.0 wt. % propanol based on the weight of the product; and
(h) converting at least a portion of the composition to one or more of ethylene, ethylene glycol, acetic acid, acrylic acid, benzene, toluene, or xylene, styrene, or butadiene;
wherein:
(i) steps (a)-(e) are conducted in sequence continuously or semi-continuously; and/or
(ii) heat is provided to the coextensive portion of the first region, at least a portion of the heat being derived from the oxidizing of step (d).

2. The process of claim 1 , wherein the acetylene of step (f) (ii) is separated from the second mixture by contacting the second mixture with a polar liquid.

3. A hydrocarbon conversion process, comprising:
(a) providing a first mixture comprising hydrocarbon and oxygenate, wherein the hydrocarbon is natural gas and the oxygenate is air;
(b) exposing the first mixture to a temperature ≧1.40×10 3 ° C. at a total pressure ≧0.1 bar absolute under high-severity thermal pyrolysis conditions in a first region to produce a second mixture, the second mixture comprising molecular hydrogen, carbon monoxide, ≧1.0 wt. % ethylene, and ≧1.0 wt. % of acetylene based on the weight of the second mixture, the second mixture having an acetylene:ethylene molar ratio in the range of 0.5 to 20.0 and a carbon monoxide:C 2 unsaturates molar ratio in the range of 0.10 to 2.0;
(c) transferring the second mixture away from the first region, dividing the second mixture into first and second portions, and deriving a third mixture from the first portion; the third mixture (i) comprising carbon monoxide and ≧1.0 wt. % of acetylene based on the weight of the third mixture and (ii) having a CO:C 2 unsaturates molar ratio in the range of 0.15 to 2.0 and a molecular hydrogen:acetylene molar ratio ≧0.75;
(d) providing a fourth mixture comprising fuel and oxidant, and at least partially oxidizing the fourth mixture in a second region to heat the first region and to produce a fifth mixture comprising water and/or carbon dioxide, the first and second regions being at least partially coextensive and the oxidizing being conducted at a different time than the exposing;
(e) transferring the fifth mixture away from the second region;
(f) hydroformylating at least a portion of the third mixture to form a first product comprising ≧1.0 wt. % of propanal and/or ≧1.0 wt. % propanol based on the weight of the product; and
(g) converting at least a portion of the second portion to form a second product comprising ≧2.0 wt. % ethylene and ≦1.0 wt. % C 3+ unsaturates based on the weight of the second product.

4. The process of claim 3 , further comprising at least one of:
(h) converting at least a portion of the second mixture's acetylene to ethylene before the deriving of step (c);
(i) separating from the second mixture and/or the second portion at least a portion of any heteroatom molecules, the separating being conducted upstream of the converting; or
(j) adding carbon monoxide and/or hydrogen to the second portion upstream of the hydroformylation.

5. The process of claim 4 , wherein at least a portion of the added carbon monoxide and/or added hydrogen are derived from syngas.

6. The process of claim 3 , further comprising at least one of:
(i) converting at least a portion of the propanal and/or propanol to propylene and polymerizing at least a portion of the propylene; or
(ii) polymerizing at least a portion of the second product's ethylene.

7. A hydrocarbon conversion process, comprising:
converting a first mixture to a second mixture, the first mixture having a first STP enthalpy H i and comprising hydrocarbon and oxygenate and the second mixture having a carbon monoxide:C 2 unsaturates molar ratio ≧0.50 and a second STP enthalpy H o ; wherein (a) the second mixture comprises carbon monoxide, ethylene, and ≧1.0 wt. % of acetylene based on the weight of the second mixture; (b) the second mixture has (i) a CO:C 2 unsaturates molar ratio in the range of 0.1 to 2.0, and (ii) a molecular hydrogen:acetylene molar ratio ≧0.75; and (c) H o -H i ≧0.0 kcal per mole of hydrocarbon in the first mixture; wherein the converting is carried out by exposing the first mixture to a temperature ≧1.4×10 3 ° C. at a total pressure ≧0.1 bar absolute under high-severity thermal pyrolysis conditions in a first region to produce the second mixture; and then catalytically converting at least a portion of the second mixture to form a product comprising ≧1.0 wt. % of propanal and/or propanol based on the weight of the product.

8. The process of claim 7 , wherein:
(i) the hydrocarbon of the first mixture comprises ≧90.0 wt. % methane, based on the weight of the first mixture's hydrocarbon;
(ii) ≧99.0 wt. % of the first mixture is converted to the second mixture; and
(iii) H o -H i ≧10.0 kcal per mole of the methane in the first mixture.

Assignees

• Exxonmobil Chemical Patents Inc

Inventors

• Keusenkothen Paul F
• Hershkowitz Frank

Classifications

• C07C2/48

  of only hydrocarbons containing a carbon-to-carbon triple bond · CPC title

• C07C11/21

  Alkatrienes; Alkatetraenes; Other alkapolyenes · CPC title

• C08F110/06 Primary

  Propene · CPC title

• C07C1/20

  starting from organic compounds containing only oxygen atoms as heteroatoms · CPC title

• C07C31/10

  containing three carbon atoms · CPC title