Normal heptane isomerization

• US 20060270885A1
• Filed: 05/31/2005
• Published: 11/30/2006
• Est. Priority Date: 05/31/2005
• Status: Abandoned Application

• Current Assignee: Catalytic Distillation Technologies (Lummus Technology LLC)
• Original Assignee: Catalytic Distillation Technologies (Lummus Technology LLC)
• Inventors: Dautzenberg, Frits M., Loescher, Mitchell E., Xu, Jinsuo, Boyer, Christopher C.
• Application Number:
  US11/149,504
• Publication Number:
  US 20060270885A1
• Time in Patent Office: Days
• US Class Current: 585/741
• CPC Class Codes: C07C 2521/06 Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
• CPC Class Codes: C07C 2523/10 of rare earths
• CPC Class Codes: C07C 2523/14 of germanium, tin or lead
• CPC Class Codes: C07C 2523/28 Molybdenum
• CPC Class Codes: C07C 2523/30 Tungsten
• CPC Class Codes: C07C 2523/42 Platinum
• CPC Class Codes: C07C 2523/44 Palladium
• CPC Class Codes: C07C 2523/46 Ruthenium, rhodium, osmium or iridium
• CPC Class Codes: C07C 2523/62 with gallium, indium, thallium, germanium, tin or lead
• CPC Class Codes: C07C 2523/745 Iron
• CPC Class Codes: C07C 2523/75 Cobalt
• CPC Class Codes: C07C 2523/755 Nickel
• CPC Class Codes: C07C 2527/053 Sulfates or other compounds comprising the anion (SnO3n+1)2-
• CPC Class Codes: C07C 2527/167 Phosphates or other compounds comprising the anion (PnO3n+1)(n+2)-
• CPC Class Codes: C07C 5/2791 with metals
• CPC Class Codes: C07C 9/16 Branched-chain hydrocarbons
• CPC Class Codes: C10G 45/60 characterised by the catalyst used
• CPC Class Codes: C10G 45/62 containing platinum group metals or compounds thereof
• CPC Class Codes: Y02P 20/10 Process efficiency

Abstract

A process for the isomerization of heptane preferably contained within a naphtha stream is disclosed wherein the naphtha is stripped of the butanes and the pentanes and hexanes are removed for isomerization. The heptanes and heavier are fed to a distillation column reactor containing an isomerization catalyst where the normal heptane is isomerized to mono and di branched heptane and removed as overheads. The cyclic heptanes and heavier are removed as bottoms and for feed to a catalytic reforming process.

Claims

1. A process for the isomerization of normal heptane contained within a hydrocarbon stream comprising the steps of:

(a) concurrently;

(i) contacting normal heptane contained in a hydrocarbon feed containing normal heptane and heavier material with an isomerization catalyst under conditions of temperature and pressure to isomerize normal heptane to branched heptane and

(ii) separating the branched heptane from the normal heptane and heavier material by fractional distillation; and

(b) withdrawing the branched heptane and the heavier material separately.

2. The process according to claim 1 wherein the conditions of temperature and pressure are such that the normal heptane is maintained in contact with the isomerization catalyst so that essentially all of the normal heptane is converted to branched heptane.

3. The process according to claim 1 wherein a portion of the branched heptane formed is isomerized to di branched heptane.

4. The process according to claim 1 wherein said hydrocarbon feed comprises a naphtha stream.

5. The process according to claim 1 wherein the naphtha stream contains butanes and the butanes are removed prior to feeding the naphtha to the isomerization.

6. The process according to claim 1 wherein the naphtha stream contains pentanes and hexanes and the pentanes and hexanes are removed prior to feeding the naphtha to the isomerization.

7. The process according to claim 1 wherein the isomerization catalyst comprises a compound of the generalized formula:

R₁/R₄/R₂—

R₃

wherein;

R₁ is a metal or metal alloy or bimetallic system;

R₂ is any metal dopant;

R₃ is a metallic oxide or mixtures of any metallic oxide;

R₄ is selected from WO_x, MoO_x, SO₄²⁻

or PO₄³⁻

; and

x is a whole or fractional number between and including 2 and 3.

8. The process according to claim 7 wherein

R₁ is a Group VIII noble metal or a combination of Group VIII noble metals;

R₂ is selected from the group consisting of Al³⁺, Ga³⁺, Ce⁴⁺, Sb⁵⁺, Sc³⁺, Md²⁺, Co²⁺, Fe³⁺, Cr³⁺, Y³⁺Si⁴⁺, and In³⁺;

R₃ is zirconium oxide, titanium oxide, tin oxide, ferric oxide, cerium oxide or mixtures thereof;

R₄ is selected from the group consisting of SO₄²⁻

, WO_x, MoO_x, PO₄³⁻

, W₂₀O₅₈, W₁₀O₂₉ and anions and mixtures thereof; and

the ratio of metal dopant to metal in the oxide may be less than or equal to about 0.20.

9. The process according to claim 8 wherein R₁ is platinum, palladium, iridium, rhodium, nickel, cobalt or a combination thereof.

10. The process according to claim 8 wherein R₁ is a Pt—

Sn alloy, Pt—

Pd alloy, Pt—

Ga alloy, Pt—

Ni alloy or bimetallic system thereof.

12. The process according to claim 11 wherein the distillation column reactor is operated such that the normal heptane is maintained in the bed of isomerization catalyst so that essentially all of the normal heptane is converted to branched heptane.

11. A process for the isomerization of normal heptane contained within a naphtha stream comprising the steps of:

(a) feeding a naphtha stream containing normal heptane and heavier material to a distillation column reactor containing a bed of isomerization catalyst;

(b) concurrently in said distillation column reactor,

(i) isomerizing a portion of the normal heptane to branched heptane and

(ii) separating the branched heptane from the normal heptane and heavier material by fractional distillation;

(c) withdrawing branched heptane as overhead product; and

(d) withdrawing the heavier material from the distillation column reactor as bottoms.

13. The process according to claim 11 wherein a portion of the branched heptane formed is isomerized to di branched heptane.

14. The process according to claim 11 wherein the naphtha also contains cyclic heptanes and the cyclic heptanes are removed in said bottoms.

15. The process according to claim 14 wherein said bottoms is fed to a catalytic reforming reactor.

16. The process according to claim 11 wherein the naphtha stream contains butanes and the butanes are removed in a debutanizer prior to feeding the naphtha to the distillation column reactor.

17. The process according to claim 11 wherein the naphtha stream contains pentanes and hexanes and the pentanes and hexanes are removed in a naphtha splitter prior to feeding the naphtha to the distillation column reactor.

18. The process according to claim 17 wherein the removed pentanes and hexanes are fed to a C5/C6 isomerization reactor where a portion of the normal pentanes and normal hexanes are converted to branched pentanes and branched hexanes respectively.

19. The process according to claim 11 wherein said distillation column reactor is operated under the conditions to (i) maintain a selected fraction comprising at least a portion of the normal heptane in the distillation reaction zone to selectively isomerize at least a portion thereof to branched heptanes and (ii) to exclude heavier material from the distillation reaction whereby cracking of heavier material is inhibited.

20. A process for the isomerization of heptanes contained in a naphtha stream comprising the steps of:

(a) feeding naphtha stream containing C₄'"'"'s, C₅'"'"'s, C₆'"'"'s, C₇'"'"'s and C₈'"'"'s and heavier compounds to a debutanizer wherein the C₄'"'"'s and lighter material are taken as a first overhead and the C₅'"'"'s and heavier are taken as a first bottoms;

(b) feeding the first bottoms to a naphtha splitter wherein the C₅'"'"'s and C₆'"'"'s are taken as a second overhead and the C₇'"'"'s and heavier material are taken as a second bottoms;

(c) feeding the second overheads to a C₅/C₆ isomerization reactor where the normal C5'"'"'s and C6'"'"'s are isomerized to branched C₅'"'"'s and C₆'"'"'s;

(d) feeding the second bottoms to a distillation column reactor containing a bed of isomerization catalyst;

(e) concurrently in the distillation column reactor,

(i) isomerizing a portion of the normal C₇'"'"'s to mono branched C₇'"'"'s and a portion of the mono branched C₇'"'"'s to di branched C₇'"'"'s, while maintaining the normal C₇'"'"'s within the catalyst bed and

(ii) separating the branched C₇'"'"'s from the C8'"'"'s and any cyclic C₇'"'"'s;

(f) withdrawing the branched C₇'"'"'s from the distillation column reactor as a third overheads;

(g) withdrawing the C₈'"'"'s and cyclic C₇'"'"'s from the distillation column reactor as a third bottoms; and

(h) feeding the third bottoms to a catalytic reforming reactor to increase the octane.

21. A process for the isomerization of alkanes contained within hydrocarbon stream comprising the steps of:

(a) concurrently;

(i) contacting an alkane having a first skeletal configuration and contained in a hydrocarbon feed with an isomerization catalyst under conditions of temperature and pressure to isomerize the alkane of said first skeletal configuration to a second more highly branched skeletal configuration and

(ii) separating the second more highly branched alkane from the alkane having said first configuration by fractional distillation; and

(b) withdrawing the second more highly branched alkane.