Catalytic devulcanization of rubber
View Patent ↗The present invention relates generally to the delulcanization of rubber. More specifically, the present invention relates to a process for the hydro-devulcanization of vulcanized rubber utilizing a rubber swelling solvent, a source of reactive hyrogen and elevated temperature and, optimally, also uses a dispersed molecular-scale hydrogenation catalyst that is introduced into the vulcanized rubber in a catalytically inert form that is soluable in the rubber swelling solvent.
1. A process for the devulcanization of rubber comprising the steps of:
a) contacting vulcanized rubber with a rubber-swelling solvent capable of swelling the rubber to form solvent-swollen vulcanized rubber;
b) heating the solvent-swollen vulcanized rubber in the presence of a hydrogen source to initiate a devulcanzation reaction; and,
c) allowing the devulcanization reaction to proceed for a time sufficient to effectively devulcanize the vulcanized rubber
wherein step a) includes contacting vulcanized rubber with a hydrogenation catalyst precursor dissolved in the rubber-swelling solvent to form solvent-swollen vulcanized rubber containing the hydrogenation catalyst precursor; and step b) includes heating the solvent-swollen vulcanized rubber to convert the catalyst precursor to an active catalyst in the presence of the hydrogen source to initiate the devulcanzation reaction.
2. The process of claim 1 wherein the rubber-swelling solvent is selected from any one of or a combination of toluene, o-xylene, p-xylene, dodecane, n-heptane, cyclohexane, tetralin and decalin.
3. The process of claim 1 wherein the rubber-swelling solvent is inert with respect to reaction with the catalyst precursor, active catalyst and vulcanized and devulcanized rubber.
4. The process of claim 1 wherein the solvent provides a source of hydrogen during steps b) and c).
5. The process of claim 1 wherein the catalyst precursor is soluble in the swelling solvent.
6. The process of claim 1 wherein the catalyst precursor is an organometallic compound of a transition metal.
7. The process of claim 1 wherein the catalyst precursor is converted to the active catalyst by reaction with elemental sulphur or organic sulphur compounds within the vulcanized rubber.
8. The process of claim 7 wherein the active catalyst is a transition metal sulphide.
9. The process of claim 1 wherein the catalyst precursor is a organometallic compound, M-R x , where M is a transition metal and R x is an organic ligand having any one of or a combination of a carbonyl, naphthenate, carboxylate, phosphine, amine, nitrosyl, or cyclopentadienyl group.
10. The process of claim 1 wherein the catalyst precursor is molybdenum ethylhexanoate.
11. The process of claim 1 wherein the catalyst precursor is selected from any one of or a combination of molybdenum carbonyl, molybdenum naphthenate, nickel carbonyl, nickel naphthenate, cobalt carbonyl, cobalt naphthenate, iron carbonyl, ruthenium carbonyl, tungsten carbonyl and osmium carbonyl.
12. The process of claim 1 wherein the vulcanized rubber is incubated with the solvent prior to contact with the catalyst precursor.
13. The process of claim 1 wherein the vulcanized rubber is incubated with the swelling solvent for a time sufficient to effect saturation of the swelling solvent and catalyst precursor within the vulcanized rubber.
14. The process of claim 1 wherein in step a) the catalyst precursor is mixed with the swelling-solvent, and the vulcanized rubber is then contacted with the solvent/precursor mixture.
15. The process of claim 1 wherein the process is carried out in a controlled anaerobic, reducing atmosphere.
16. The process of claim 1 wherein the process is carried out within a batch or continuous flow reactor.
17. The process of claim 1 wherein wherein steps b) and c) are performed at a temperature of 50-450° C.
18. The process of claim 1 wherein steps b) and c) are performed at a temperature of 50-250° C.
19. The process of claim 1 wherein the reaction time of steps b) and c) is less than 180 minutes.
20. The process of claim 1 wherein the reaction time of steps b) and c) is less than 90 minutes.
21. The process of claim 1 wherein the hydrogen source is any one of or a combination of hydrogen gas, decalin, tetralin, or a hydroaromatic compound.
22. The process of claim 1 wherein step a) includes adding a sulphiding agent for activating the catalyst precursor.
23. The process of claim 22 wherein the sulphiding agent is dimethyldisulphide.
24. The process of claim 1 further comprising the step of quenching the reaction after step c).
25. The process of claim 24 further comprising the step of separating unreacted vulcanized rubber and carbon black from the devulcanized rubber.
26. The process of claim 1 wherein the molar mass of the devulcanized rubber is controlled by adjustment of the reaction time of step c) and the upper temperature of step b).
27. A process for devulcanizing rubber comprising contacting and heating an amount of vulcanized rubber with an effective amount of a rubber swelling solvent and a hydrogenation catalyst precursor soluble in the solvent.
28. A monophasic devulcanization solution comprising a hydrogenation catalyst precursor and a rubber swelling solvent.
29. A rubber-swelling solvent and an organo-transition metal catalyst precursor in solution for use in the devulcanization of vulcanized rubber in an anaerobic environment in the presence of a hydrogen source.
30. A rubber devulcanization process comprising the steps of:
a) contacting vulcanized rubber with a mixture of a hydrogenation catalyst precursor and a rubber swelling solvent;
b) activating the hydrogenation catalyst precursor with heat and a source of sulphur to cause devulcanization in the presence of reactive hydrogen.
31. A rubber devulcanization process comprising the steps of converting a catalyst precursor, M-R x , where M is a transition metal and R x is an organic or other ligand capable of coordination with the transition metal in a charged or uncharged state, to an active catalyst by reaction of the catalyst precursor with sulphur within solvent-swollen vulcanized rubber, R′—S z —R″, where R′ and R″ are rubber polymers or rubber polymer additives and —S z — are sulphur crosslinks within the vulcanized rubber and wherein the reaction is carried out in the presence of reactive hydrogen.