Isomerization of normal paraffins
Isomerization of normal paraffins to form branched paraffins may be complicated by significant cracking of C 7+ paraffins under isomerization reaction conditions. This issue may complicate upgrading of hydrocarbon feeds having significant quantities of heavier normal paraffins. Cracking selectivity may be decreased by combining one or more naphthenic compounds with a feed mixture comprising at least one C 7+ normal paraffin and/or by utilizing tungstated zirconium catalysts having decreased tungsten loading. Further, C 5 and C 6 normal paraffins may undergo isomerization in the presence of C 7+ normal paraffins. Methods for isomerizing normal paraffins may comprise: providing a feed mixture comprising at least C 5 -C 7 normal paraffins and lacking normal paraffins larger than C 8 ; and contacting the feed mixture with a bifunctional mixed metal oxide catalyst under isomerization reaction conditions effective to form a product mixture comprising one or more branched paraffins formed from each of the C 5 -C 7 normal paraffins.
1. A method comprising:
providing a first bifunctional mixed metal oxide catalyst comprising a first bifunctional mixed metal oxide impregnated with noble metal, the first bifunctional mixed metal oxide catalyst comprising about 40 wt. % to about 70 wt. % zirconium, a first amount of tungsten, and about 0.01 wt. % to about 5 wt. % variable oxidation state metal, each based on total mass of the mixed metal oxide;
providing a second bifunctional mixed metal oxide catalyst comprising a bifunctional mixed metal oxide impregnated with a noble metal, the second bifunctional mixed metal oxide catalyst comprising a second amount of tungsten, the first amount of tungsten, relative to a weight of the first bifunctional mixed metal catalyst, being higher than the second amount of tungsten relative to a weight of the second bifunctional mixed metal catalyst,
wherein the second bifunctional mixed metal oxide catalyst comprises about 40 wt. % to about 70 wt. % zirconium and about 0.01 wt. % to about 5 wt. % variable oxidation state metal, each based on total mass of the bifunctional mixed metal oxide, and an amount of tungsten effective to isomerize n-heptane to one or more branched paraffins at about 70% to about 80% conversion under isomerization reaction conditions with a selectivity ratio of conversion to cracking for n-heptane of about 11 or greater;
sequentially contacting the first bifunctional mixed metal oxide catalyst and the second bifunctional mixed metal oxide catalyst under the isomerization reaction conditions with a feed mixture comprising at least one C 7+ normal paraffin; and
obtaining one or more branched paraffins formed from the at least one C 7+ normal paraffin under the isomerization reaction conditions.
2. The method of claim 1 , wherein the selectivity ratio ranges from about 11 to about 14.
3. The method of claim 1 , wherein the first amount of tungsten is effective to isomerize n-heptane at about 70% to about 80% conversion with a cracking yield for n-heptane of about 8 wt. % or less.
4. The method of claim 1 , wherein the first amount of tungsten effective to isomerize n-heptane ranges from about 13 wt. % to about 16 wt. %, based on total mass of the bifunctional mixed metal oxide.
5. The method of claim 1 , wherein the variable oxidation state metal comprises Fe.
6. The method of claim 1 , wherein the first bifunctional mixed metal oxide catalyst and the second bifunctional mixed metal oxide catalyst are arranged in a stacked bed configuration.
7. The method of claim 1 , wherein the feed mixture does not contain normal paraffins larger than C 8 .
8. The method of claim 1 , wherein the feed mixture comprises at least C 5 -C 7 normal paraffins.
9. The method of claim 1 , wherein the feed mixture further comprises one or more branched paraffins.