Polyalkylene epoxy polyamine additives for fouling mitigation in hydrocarbon refining processes
The present invention provides a method for reducing fouling, including particulate-induced fouling, in a hydrocarbon refining process including the steps of providing a crude hydrocarbon for a refining process and adding an antifouling agent containing a polymer base unit and a polyamine group to the crude hydrocarbon. The antifouling agent can be obtained by reacting an epoxidation reagent with a vinyl-terminated polymer, such as polypropylene or poly(ethylene-co-propylene), to form a terminal epoxy group, followed by reacting a polyamine with the epoxy group.
1. A method for reducing fouling in a hydrocarbon refining process comprising providing a crude hydrocarbon for a refining process;
adding an additive to the crude hydrocarbon, the additive being a reaction product of
(a) a polymer base unit R 11 , which is a branched or straight-chained C 10 -C 800 alkyl or alkenyl group having a vinyl terminal group;
(b) an epoxidation reagent capable of converting the vinyl terminal group of R 11 to an epoxy group; and
(c) a polyamine represented by
wherein R 12 is hydrogen or a C 1 -C 10 branched or straight chained alkyl optionally substituted with one or more amine groups, R 13 is a C 1 -C 10 branched or straight chained alkylene group, and x is an integer between 1 and 10 inclusive.
2. The method of claim 1 , wherein the polyamine is selected from the group consisting of diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, and hexaethyleneheptamine.
3. The method of claim 1 , wherein R 11 comprises polypropylene.
4. The method of claim 3 , wherein the mole ratio between R 11 and polyamine is about 2:1 or about 1:1.
5. The method of claim 3 , wherein R 11 has a number-averaged molecular weight of 300 to 30000 g/mol.
6. The method of claim 5 , wherein R 11 has a number-averaged molecular weight of 500 to 5000 g/mol.
7. The method of claim 3 , wherein the polypropylene is atactic polypropylene or isotactic polypropylene.
8. The method of claim 1 , wherein R 11 comprises polyethylene.
9. The method of claim 1 , wherein R 11 comprises poly(ethylene-co-propylene).
10. The method of claim 9 , wherein R 11 contains about 1 to about 90 mole % of ethylene units and about 99 to about 10% propylene units.
11. The method of claim 10 , wherein R 11 contains about 10 to about 50 mole % of ethylene units.
12. The method of claim 1 , wherein the epoxidation reagent comprises an organic peroxy acid.
13. The method of claim 12 , wherein the organic peroxy acid is m-chloroperoxybenzoic acid (MCPBA).
14. The method of claim 1 , wherein the epoxidation reagent comprises (A) an oxidation agent selected from the group consisting of molecular oxygen, hydrogen peroxide, and alkyl peroxide; and (B) an epoxidation catalyst.
15. The method of claim 14 , wherein the epoxidation catalyst is selected from the group consisting of metalloporphyrin, a transition metal zeolite, and a transition metal complex.
16. The method of claim 1 , wherein at least 50% of the terminal vinyl group is an allylic vinyl group.