Methods for making linear internal olefins from mixtures of linear and branched olefins
Processes for producing a linear internal olefin product include the steps of contacting an olefin feed containing C 10 -C 20 vinylidenes and a C 10 -C 20 normal alpha olefin and/or C 10 -C 20 linear internal olefins, a first acid catalyst, and a C 1 to C 18 carboxylic acid to form a first reaction product containing linear internal olefins, trisubstituted olefins, and secondary esters, then removing all or a portion of the secondary esters from the first reaction product, followed by contacting the secondary esters and a second acid catalyst to form a second reaction product comprising linear internal olefins, and then removing all or a portion of the linear internal olefins from the second reaction product to form the linear internal olefin product. Linear alkanes subsequently can be produced by hydrogenating the linear internal olefin product to form a linear alkane product.
1. A process comprising:
(a) contacting an olefin feed comprising C 10 to C 20 vinylidenes and a C 10 to C 20 normal alpha olefin and/or C 10 to C 20 linear internal olefins, a first acid catalyst, and a C 1 to C 18 carboxylic acid to form a first reaction product comprising linear internal olefins, trisubstituted olefins, and secondary esters;
(b) removing all or a portion of the secondary esters from the first reaction product to form a secondary ester product;
(c) contacting the secondary ester product and a second acid catalyst at a temperature from 50° C. to 120° C. to form a second reaction product comprising linear internal olefins, wherein the second acid catalyst comprises a solid acid catalyst resin; and
(d) removing all or a portion of the linear internal olefins from the second reaction product to form a linear internal olefin product.
2. The process of claim 1 , wherein the first acid catalyst and the second acid catalyst independently comprise a sulfonated copolymer of styrene-divinylbenzene.
3. The process of claim 1 , wherein the olefin feed comprises:
from 50 wt. % to 99 wt. % of the C 10 to C 20 normal alpha olefin and/or C 10 to C 20 linear internal olefins; and
from 1 wt. % to 50 wt. % of Cm to C 20 vinylidenes.
4. The process of claim 3 , wherein the C 10 to C 20 normal alpha olefin comprises 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, or any combination thereof.
5. The process of claim 1 , wherein:
a molar ratio of moles of the carboxylic acid to moles of olefin in the olefin feed in step (a) is from 1:4 to 4:1; and
the carboxylic acid comprises formic acid, acetic acid, propionic acid, butyric acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, or any combination thereof.
6. The process of claim 1 , wherein a weight ratio of the olefin feed to the acid catalyst in step (a) is from 1:1 to 100:1.
7. The process of claim 1 , wherein the first reaction product comprises:
less than or equal to 10 wt. % of C 10 to C 20 normal alpha olefin;
less than or equal to 10 wt. % of dimer; and
less than or equal to 2 wt. % more branched olefins than an amount of branched olefins in the olefin feed.
8. The process of claim 1 , wherein the first reaction product comprises:
from 1 wt. % to 15 wt. % of the trisubstituted olefins; and
from 10 to 50 mol % of the secondary esters, based on moles of the C 10 to C 20 normal alpha olefin and/or C 10 to C 20 linear internal olefins in the olefin feed.
9. The process of claim 1 , wherein the removing in step (b) comprises flashing, wiped film evaporation, distillation, short path distillation, or any combination thereof.
10. The process of claim 1 , wherein a weight ratio of the secondary esters to the second acid catalyst in step (c) is from 1:1 to 100:1.
11. The process of claim 1 , wherein the second reaction product comprises, based on hydrocarbons:
at least 95 wt. % linear internal olefins; and
less than or equal to 4 wt. % branched olefins.
12. The process of claim 1 , wherein removing in step (d) comprises flashing, wiped film evaporation, distillation, short path distillation, or any combination thereof.
13. The process of claim 1 , wherein the linear internal olefin product comprises:
at least 95 wt. % linear internal olefins; and
less than or equal to 4 wt. % branched olefins.
14. The process of claim 1 , wherein the linear internal olefin product comprises:
at least 99 wt. % linear internal olefins; and
less than or equal to 1 wt. % branched olefins.
15. The process of claim 1 , further comprising a step of (e) hydrogenating the linear internal olefin product to form a linear alkane product.
16. The process of claim 15 , wherein the linear alkane product comprises:
at least 95 wt. % linear alkane; and
less than or equal to 4 wt. % branched alkanes.
17. The process of claim 15 , wherein the linear alkane product comprises:
at least 99 wt. % linear alkane; and
less than or equal to 1 wt. % branched alkanes.
18. The process of claim 17 , wherein the first acid catalyst and the second acid catalyst independently comprise a sulfonated copolymer of styrene-divinylbenzene.
19. The process of claim 17 , wherein:
the C 10 to C 20 normal alpha olefin comprises 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, or any combination thereof; and
the linear alkane comprises decane, dodecane, tetradecane, hexadecane, octadecane, or any combination thereof.
20. The process of claim 17 , wherein:
the removing in step (b) comprises flashing, wiped film evaporation, distillation, short path distillation, or any combination thereof; and
the removing in step (d) comprises flashing, wiped film evaporation, distillation, short path distillation, or any combination thereof.
21. A process comprising:
(a) contacting an olefin feed comprising C 10 to C 20 vinylidenes and a C 10 to C 20 normal alpha olefin and/or C 10 to C 20 linear internal olefins, a first acid catalyst, and a Ci to Cis carboxylic acid to form a first reaction product comprising linear internal olefins, trisubstituted olefins, and secondary esters;
(b) removing all or a portion of the secondary esters from the first reaction product to form a secondary ester product;
(c) contacting the secondary ester product and a second acid catalyst comprising a solid acid catalyst resin at a temperature from 80° C. to 150° C. to form a second reaction product comprising, based on hydrocarbons:
at least 95 wt. % linear internal olefins; and
less than or equal to 4 wt. % branched olefins; and
(d) removing all or a portion of the linear internal olefins from the second reaction product to form a linear internal olefin product.
22. The process of claim 21 , wherein the linear internal olefin product comprises at least 99 wt. % linear internal olefins.
23. The process of claim 22 , further comprising a step of (e) hydrogenating the linear internal olefin product to form a linear alkane product.
24. The process of claim 23 , wherein the linear alkane product comprises decane, dodecane, tetradecane, hexadecane, octadecane, or any combination thereof.
25. The process of claim 21 , wherein the olefin feed comprises:
from 50 wt. % to 99 wt. % of the C 10 to C 20 normal alpha olefin and/or C 10 to C 20 linear internal olefins; and
from 1 wt. % to 50 wt. % of he C 10 to C 20 vinylidenes.
26. The process of claim 25 , wherein:
the C 10 to C 20 normal alpha olefin comprises 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, or any combination thereof;
the first acid catalyst and the second acid catalyst independently comprise a sulfonated copolymer of styrene-divinylbenzene; and
the carboxylic acid comprises formic acid, acetic acid, propionic acid, butyric acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, or any combination thereof.
27. The process of claim 26 , wherein:
the removing in step (b) comprises flashing, wiped film evaporation, distillation, short path distillation, or any combination thereof; and
the removing in step (d) comprises flashing, wiped film evaporation, distillation, short path distillation, or any combination thereof.