Hydrocarbon conversion process

Patent metadata

Field	Value
Publication number	US-9328049-B2
Application number	US-201313865247-A
Country	US
Kind code	B2
Filing date	Apr 18, 2013
Priority date	May 18, 2012
Publication date	May 3, 2016
Grant date	May 3, 2016

Abstract

The invention relates to processes for converting hydrocarbons to phthalic acids such as terephthalic acid. The invention also relates to polymerizing phthalic acid derivatives to produce, e.g., synthetic fibers.

First claim

The invention claimed is:

1. A hydrocarbon conversion process, comprising:
(a) providing a first mixture comprising ≧1.0 wt. % hydrocarbon and ≧1.0 wt. % oxygenate, the weight percents being based on the weight of the first mixture, wherein the oxygenate comprises water obtained from step (d);
(b) exposing the first mixture to a temperature ≧700° C. under pyrolysis conditions to produce a second mixture, wherein (i) the second mixture comprises ≧1.0 wt. % acetylene based on the weight of the second mixture and (ii) ≧95.0 wt. % of the second mixture's acetylene, based on the weight of the second mixture's acetylene, is produced by conversion of at least a portion of the first mixture's hydrocarbon;
(c) converting ≧10.0 wt. % of the second mixture's acetylene to cyclooctatetraene, based on the weight of the second mixture's acetylene, in the presence of a catalyst comprising nickel in order to produce a third mixture, the third mixture comprising at least a portion the cyclooctatetraene produced by the acetylene conversion; and
(d) converting ≧5.0 wt. % of the third mixture's cyclooctatetraene to water and phthalic acids, based on the weight of the third mixture's cyclooctatetraene.

2. The process of claim 1 , wherein the pyrolysis conditions include thermal pyrolysis conditions.

3. The process of claim 1 , wherein the pyrolysis conditions include high-severity pyrolysis conditions.

4. The process of claim 1 , wherein the first mixture's hydrocarbon comprises ≧95.0 wt. % methane, based on the weight of the first mixture's hydrocarbon, and wherein the pyrolysis conditions include conversion of 50.0 wt. % to 70.0 wt. % of the first mixture's methane, a peak pyrolysis temperature ranging from 1400° C. to 1800° C., a pressure in the range of from 1.3 bar (absolute) to 2.0 bar (absolute), and a first mixture residence time in the range of from about 1.0 milliseconds to 50.0 milliseconds.

5. The process of claim 1 , wherein the second mixture has an acetylene:ethylene molar ratio in the range of 2.0 to 10.0 and a molecular hydrogen:acetylene molar in the range of 3.0 to 20.0.

6. The process of claim 1 , wherein the second mixture comprises 2.0 wt. % to 50.0 wt. % methane; 2.0 wt. % to 50.0 wt. % molecular hydrogen; 2.0 wt. % to 40.0 wt. % acetylene; 2.0 wt. % to 20.0 wt. % acetylene; and ≧1.0 wt. % C 3+ , the weight percents being based on the weight of the second mixture.

7. The process of claim 5 , further comprising separating from the second mixture (i) ≧50.0 wt. % of the second mixture's molecular hydrogen, (ii) ≧90.0 wt. % of any oxygen-containing molecules contained in the second mixture, and (iii) ≧90.0 wt. % of the second mixture's C 3+ , the weight percents being based on the weight of the second mixture; the separating being conducted before the converting of step (c).

8. The process of claim 5 , further comprising separating from the second mixture (i) ≧50.0 wt. % of the second mixture's molecular hydrogen, (ii) ≧90.0 wt. % of any oxygen-containing molecules contained in the second mixture, and (iii) ≧90.0 wt. % of the second mixture's C 3+ , the weight percents being based on the weight of the second mixture; the separating being conducted during and/or after the converting of step (c).

9. The process of claim 1 , wherein (i) during step (c) ≧50.0 wt. % of the second mixture's acetylene is catalytically converted to the cyclooctatetraene, and (ii) the first catalyst of step (c) comprises ≧0.1 wt. % nickel based on the weight of the first catalyst.

10. The process of claim 9 , wherein the first catalyst comprises nickel acetylacetonate.

11. The process of claim 10 , wherein the catalytic conversion conditions of step (c) include a temperature in the range of 65° C. to 140° C. and a pressure in the range of 1.0 bar (absolute) to 200 bar (absolute).

12. The process of claim 9 , wherein the cyclooctatetraene constitutes ≧10.0 wt. % of a third mixture, the third mixture (i) being derived from the conversion of step (c) and (ii) further comprising unreacted acetylene.

13. The process of claim 12 , further comprising separating from the third mixture ≧90.0 wt. % of the third mixture's cyclooctatetraene based on the weight of the third mixture.

14. The process of claim 1 , wherein the converting of step (d) includes catalytic conversion, the catalyst comprising ≧1.0 wt. % of chromium atoms that are bound to at least one oxygen atom based on the weight of the catalyst.

15. The process of claim 1 , wherein the converting of step (d) includes catalytic conversion, the catalyst comprising ≧1.0 wt. % chromic acid based on the weight of the catalyst.

16. The process of claim 1 , wherein the converting of step (d) includes a temperature in the range of 0° C. to 150° C., a pressure in the range of 0.1 bar to 100 bar, and a space velocity in the range of 0.1 LHSV to 2000 LHSV.

17. The process of claim 1 , wherein the conversion of step (d) includes oxidizing at least a portion of the cyclooctatetraene utilizing acid and/or hydrogen peroxide to produce the phthalic acid.

18. The process of claim 17 , wherein the oxidant is acetic acid and/or hydrogen peroxide.

19. The process of claim 18 , wherein the oxidant is hydrogen peroxide, and the molar ratio of hydrogen peroxide to cyclooctatetraene in step (d) is in the range of 0.5 to 5.0.

20. The process of claim 1 , wherein the pyrolysis is conducted in a first region, and 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
(iii) the exposing of the first mixture and the oxidizing of the fourth mixture occur at substantially different times.

21. The process of claim 20 , 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.

Assignees

• Exxonmobil Chem Patents Inc

Inventors

• Mohr Gary D
• Keusenkothen Paul F
• Hershkowitz Frank
• Mcconnachie Jonathan M

Classifications

• B01J8/0278

  Feeding reactive fluids (for solid material B01J8/0015) · CPC title

• B01J23/26

  Chromium · CPC title

• C10G9/00

  Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils · CPC title

• C07C51/285

  with peroxy-compounds · CPC title

• B01J8/0496

  Heating or cooling the reactor · CPC title