Catalysts for halogenated hydrocarbon processing, their precursors and their preparation and use

• US 6,127,585 A
• Filed: 05/27/1998
• Issued: 10/03/2000
• Est. Priority Date: 11/29/1995
• Status: Expired due to Term

• Current Assignee: The Chemours Company FC, LLC (The Chemours Company)
• Original Assignee: E. I. du Pont de Nemours and Company (Corteva, Inc.)
• Inventors: Rao, Velliyur Nott Mallikarjuna, Duzick, Timothy C., Subramanian, Munirpallam A.
• Primary Examiner(s): Wu, David W.
• Assistant Examiner(s): ZALUKAEVA, TATYANA
• Application Number:
  US09/077,267
• Time in Patent Office: 860 Days
• Field of Search: 570/124, 502/181, 502/330, 502/226, 502/228
• US Class Current: 570/124
• CPC Class Codes: B01J 27/13 Platinum group metals
• CPC Class Codes: C07C 17/00 Preparation of halogenated hydrocarbons
• CPC Class Codes: C07C 17/206 the other compound being HX
• CPC Class Codes: C07C 17/23 by dehalogenation
• CPC Class Codes: C07C 17/269 of only halogenated hydrocarbons
• CPC Class Codes: C07C 21/18 containing fluorine

Abstract

Processes are disclosed for decreasing the chlorine to carbon ratio for halogenated hydrocarbons containing chlorine and from 1 to 6 carbon atoms, in the presence of a multiphase catalyst. The processes each involve (1) preparing a single phase solid catalyst precursor which has a structure that collapses at a temperature of about 400° C. or less and has the formula (NH₃)₆ Ru_l-r-s Co_r Cr_s MF₆, where r+s is in the range of 0.00 to 0.99, and M is at least one trivalent metal selected from the group consisting of Al, Cr, Fe, V, Sc and Ga; and (2) producing the multiphase catalyst by heating the single phase solid catalyst precursor to about 400° C. or less in an non-oxidizing atomsphere to produce a multiphase composition wherein a phase containing ruthenium is homogeneously dispersed with a phase containing metal fluoride.

Also disclosed are single phase fluoride compositions having the formula (NH₃)₆ Ru_l-r-s Co_r Cr_s MF₆, where r+s is in the range of 0.00 to 0.99, and M is at least one trivalent element selected from the group consisting of Al, Cr, Fe, V, Sc and Ga; and multiphase catalyst compositions consisting essentially of metallic ruthenium and fluorides of at least one element selected from the group consisting of Al, Co, Cr, Fe, V, Sc and Ga, wherein the ruthenium is homogeneously dispersed with phases of the fluorides.

Claims

1. A process for decreasing the chlorine to carbon ratio for halogenated hydrocarbons containing chlorine and from 1 to 6 carbon atoms, in the presence of a multiphase catalyst, characterized by:

(1) preparing a single phase solid catalyst precursor which has a structure that collapses at a temperature of about 400°

C. or less and has the formula (NH₃)₆ Ru_l-r-s Co_r Cr_s MF₆, where r+s is in the range of 0.00 to 0.99, and M is at least one trivalent metal selected from the group consisting of Al, Cr, Fe, V, Sc and Ga; and

(2) producing said multiphase catalyst by heating said single phase solid catalyst precursor to about 400°

C. or less in a non-oxidizing atmosphere to produce a multiphase composition wherein a phase containing ruthenium is homogeneously dispersed with a phase containing metal fluoride.

2. The process of claim 1 wherein two chlorine substituents are removed from a compound having the formula C_n H_a Cl_b F_c where n is an integer from 1 to 4, a is an integer from 0 to 1, b is an integer from 2 to 9, c is an integer from 0 to 9, where a+b+c equals 2n+2, and where two chlorines that are removed are on the same carbon atom, and the compound is dimerized by reacting said compound with hydrogen in the vapor phase to produce an olefin of the formula C_2n H_2a Cl_2b-4 F_2c.

3. The process of claim 1 wherein a saturated compound having the formula C_m H_d Cl_e F_f where m is an integer from 2 to 6, d is an integer from 0 to 2, e is an integer from 2 to 4, f is an integer from 3 to 12, where d+e +f equals 2m+2, is dehalogenated by reacting said compound with hydrogen in the vapor phase to produce an olefin of the formula C_m H_d Cl_e-y F_f-y, where y is an integer from 1 to 2 when m is an integer from 2 to 3, and y is an integer from 2 to 4 when m is an integer from 4 to 6, provided that a chlorine atom on each of two adjacent carbons or a fluorine and a chlorine atom on two adjacent carbons, but not a fluorine atom on each of two adjacent carbons are removed.

4. The process of claim 3 wherein CClF₂ CHClCF₃ is reacted with hydrogen to produce CF₂ ═

CHCF₃.

5. The process of claim 3 wherein CF₃ CFClCF₂ Cl is reacted with hydrogen to produce CF₃ CF=CF₂.

6. The process of claim 1 wherein the fluorine content of either a saturated compound or an unsaturated olefinic compound having the formula C_j H_g Cl_h F_i where j is an integer from 1 to 6, g is an integer from 0 to 4, h is an integer from 1 to 13, i is an integer from 0 to 13, provided that h is at least 1 when the compound is saturated, is increased by reacting said compound with HF in the vapor phase.

7. The process of claim 1 wherein a cyclic or acyclic compounds having the formula C_k H_p Cl_q F_t where k is an integer from 1 to 6, p is an integer from 0 to 12, q and t are integers from 1 to 13, where p+q+t equals 2k+2, when the compound is saturated and acyclic, equals 2k when the compound is saturated and cyclic or is olefinic and acyclic, and equals 2k-2 when the compound is olefinic and cyclic, is hydrodehalogenated by reacting said compound with hydrogen in the vapor phase.

8. A single phase fluoride composition of the formula (NH₃)₆ Ru_l-r-s Co_r Cr_s MF₆, where r+s is in the range of 0.00 to 0.99, and M is at least one trivalent element selected from the group consisting of Al, Cr, Fe, V, Sc and Ga.

11. A single phase fluoride composition of claim 8 having the formula (NH₃)₆ RuAlF₆.

12. A single phase fluoride composition of claim 8 having the formula (NH₃)₆ RuScF₆.

13. A single phase fluoride composition of claim 8 having the formula (NH₃)₆ RuVF₆.

14. A single phase fluoride composition of claim 8 having the formula (NH₃)₆ RuCrF₆.

15. A single phase fluoride composition of claim 8 having the formula (NH₃)₆ RuGaF₆.

16. A single phase fluoride composition of claim 8 having the formula (NH₃)₆ RuFeF₆.

17. A single phase fluoride composition of claim 8 having the formula (NH₃)₆ Ru₀.8 Co₀.2 AlF₆.

18. A single phase fluoride composition of claim 8 having the formula (NH₃)₆ Ru₀.5 Co₀.5 AlF₆.

9. A multiphase catalyst composition consisting essentially of metallic ruthenium and fluorides of at least one element selected from the group consisting of Al, Co, Cr, Fe, V, Sc and Ga, wherein said ruthenium is homogeneously dispersed with phases of said fluorides.

10. The multiple catalyst composition of claim 9 produced by the process of (1) preparing a single phase solid catalyst precursor which has a structure that collapses at a temperature of about 400°

C. or less and has the formula (NH₃)₆ Ru_l-r-s Co_r Cr_s MF₆, where r+s is in the range of 0.00 to 0.99, and M is at least one trivalent element selected from the group consisting of Al, Cr, Fe, V, Sc and Ga, and (2) producing said multiphase catalyst by heating said single phase solid catalyst precursor to about 400°

C. or less in an non-oxidizing atomsphere to produce a multiphase composition wherein a phase containing ruthenium is homogeneously dispersed with a phase containing metal fluoride.

19. A multiphase catalyst composition of claim 9 consisting essentially of metallic ruthenium and fluorides of Al.

20. A multiphase catalyst composition of claim 9 consisting essentially of metallic ruthenium and fluorides of Cr.