Hydrocarbon conversion process
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.
1. A hydrocarbon conversion process, comprising:
(a) providing a first mixture, the first mixture comprising hydrocarbon and oxygenate, wherein (i) the first mixture's hydrocarbon comprises hydrocarbon in natural gas and (ii) the first mixture's oxygenate comprises carbon dioxide in natural gas;
(b) exposing the first mixture a temperature ≧1.40×10 3 ° C. in a first region under thermal pyrolysis conditions which include at a total pressure ≧0.1 bar absolute to produce a second mixture, the second mixture comprising molecular hydrogen, carbon monoxide, and ≧1.0 wt. % of C 2 unsaturates based on the weight of the second mixture, wherein the second mixture has a carbon monoxide:C 2 unsaturates molar ratio in the range of 0.1 to 2;
(c) transferring to at least one converter (i) at least a portion of the second mixture and/or (ii) a third mixture derived from the second mixture, the transferred mixture comprising hydrogen, carbon monoxide, and ≧1.0 wt. % of C 2 unsaturates based on the weight of the transferred mixture, wherein the transferred mixture has a CO:C 2 unsaturates molar ratio in the range of 0.1 to 2.0; and
(d) converting ≧10.0 wt. % of the transferred mixture's C 2 unsaturates, based on the weight of the transferred mixture's C 2 unsaturates, to form a product comprising ≧1.0 wt. % of C 3+ aldehyde and/or ≧1.0 wt. % C 3+ alcohol based on the weight of the product, wherein the C 3+ aldehyde is propanal and the C 3+ alcohol is propanol.
2. The process of claim 1 , wherein the conversion of step (d) includes hydroformylation, the hydroformylation being conducted at least partially in the vapor phase under catalytic conversion conditions in the presence of a catalytically effective amount of a catalyst comprising at least one of cobalt, iron, iridium, or rhodium.
3. The process of claim 1 , wherein:
(i) the first mixture comprises 1.0 wt. % to 50.0 wt. % of the oxygenate based on the weight of the first mixture, and
(ii) the second mixture has at least one of (1) an acetylene:ethylene molar ratio in the range of about 0.5 to about 20.0, (2) a CO:C 2 unsaturates molar ratio in the range of 0.15 to 2.0, (3) a carbon dioxide:C 2 unsaturates molar ratio ≦0.30; or (4) a molecular hydrogen:acetylene molar ratio ≧0.75.
4. The process of claim 1 , further comprising:
(e) providing a fourth mixture, and at least partially oxidizing the fourth mixture in a second region to produce a fifth mixture, the first and second regions being at least partially coextensive;
wherein:
(i) the fourth mixture comprises fuel and oxidant;
(ii) the fifth mixture comprises water and/or carbon dioxide; and
(iii) the exposing of the first mixture and the oxidizing of the fourth mixture occur at substantially different times.
5. The process of claim 4 , further comprising repeating steps (a)-(e) in sequence, wherein (i) at least a portion of the fifth mixture is conducted away from the second region before step (a) and (ii) the exposure temperature in the first region results at least in part from the heat generated during the oxidizing of the fourth mixture in the second region.
6. The process of claim 4 , further comprising at least one of:
(i) separating from the fifth mixture a byproduct comprising oxygenate and utilizing at least a portion of the separated byproduct to produce the first and/or fourth mixtures; or
(ii) separating from the second mixture a second byproduct comprising hydrocarbon and hydrogen and utilizing at least a portion of the separated second byproduct to produce the first and/or fourth mixtures.
7. The process of claim 3 , wherein the transferred mixture comprises the third mixture, the third mixture being derived from the second mixture by:
(i) separating from the second mixture at least one of acetylene, C 3+ , heteroatom species, hydrogen, diluent, or saturated hydrocarbons; and/or
(ii) combining carbon monoxide and/or molecular hydrogen, with the second mixture.
8. The process of claim 7 , further comprising converting at least a portion of the separated acetylene to one or more of ethylene, ethylene glycol, acetic acid, acrylic acid, benzene, toluene, or xylene, styrene, or butadiene; the acetylene conversion being conducted in the presence of hydrogen and/or carbon monoxide separated from the product.
9. The process of claim 4 , wherein the process further comprises at least one of (f) (i) contacting at least a portion of the product and molecular hydrogen in the vapor phase in the presence of a second catalyst, the second catalyst containing a catalytically effective amount of at least one element from Group VIII of the Periodic Table to produce a second product comprising C 3+ olefin and (ii) polymerizing at least a portion of the C 3+ olefin or (g) condensing the product to one or more oligomers of order ≧2.
10. The process of claim 1 , wherein the first mixture comprises ≧50.0 ppm sulfur, the weight percents being based on the weight of the first mixture.
11. The process of claim 1 , wherein:
(i) the first mixture has a hydrogen content in the range of 20.0 wt. % to 25.0 wt. % based on the weight of the first mixture; and
(ii) the first mixture comprises 5.0 wt. % to 25.0 wt. % of molecular hydrogen based on the weight of the first mixture, at least 15.0 wt. % of the molecular hydrogen in the first mixture being derived from the second mixture and/or the product.
12. The process of claim 1 , wherein:
(i) the exposing of step (b) is conducted under high-severity conditions;
and
(ii) the first mixture comprises 10.0 wt. % to 95.0 wt. % hydrocarbon and 5.0 wt. % to 60.0 wt. % oxygenate based on the weight of the first mixture.
13. The process of claim 8 , further comprising:
dividing the second mixture into first and second portions, the third mixture being derived from the first portion, and catalytically converting at least a portion of the second portion's acetylene to a third product comprising at least one of ethylene, ethylene glycol, acetic acid, acrylic acid, benzene, toluene, or xylene, styrene, or butadiene.
14. The process of claim 13 , wherein the acetylene conversion catalyst comprises at least one of Ni, Pd, or Pt; and further comprising one or more of:
(i) polymerizing at least a portion of the third product's ethylene;
(ii) polymerizing at least a portion of the third product's styrene and/or butadiene; or
(iii) copolymerizing at least a portion of the second product's propylene with at least a portion of one or more of the third product's ethylene, butadiene, or styrene.
15. The process of claim 8 , further comprising:
(i) converting at least a portion of the first product to propylene;
(ii) polymerizing at least a portion of the propylene;
(iii) polymerizing at least a portion of the ethylene converted from the acetylene; or (iv) copolymerizing (i) at least a portion of the ethylene converted from the acetylene and (ii) at least a portion of the propylene.