Ring opening cross metathesis of vinyl terminated polymers and their functionalized derivatives for fouling mitigation in hydrocarbon refining processes
A compound useful for reducing fouling in a hydrocarbon refining process is provided. A method for preparing the compound includes functionalizing a polymer having a vinyl chain end to obtain a terminal group having one or more anhydride units, and reacting the anhydride units with a polyamine. Methods of using the compound and compositions thereof are also provided.
1. A method for reducing fouling in a hydrocarbon refining process comprising
providing a crude hydrocarbon for a refining process; and
adding an additive to the crude hydrocarbon, the additive being represented by:
wherein R 1 is a branched or straight-chained C 10 -C 800 alkyl or alkenyl group;
y is an integer between 1 to 20 inclusive;
m is an integer between 0 and 10 inclusive;
a and b are C—C bonds in cis-configuration with respect to each other and in either cis- or trans-configuration with respect to bond c;
R 2 and R 3 are each independently a C 1 -C 4 branched or straight chained alkylene group;
R 31 is hydrogen or —R 8 -R 9 , wherein either (a) R 8 is C 1 -C 4 branched or straight chained alkylene group, and R 9 is
wherein R 91 is a branched or straight-chained C 10 -C 800 alkyl or alkenyl group, the asterisk (*) indicates a connecting point with R 8 , d and e are C—C bonds in cis-configuration with respect to each other and in either cis- or trans-configuration with respect to bond f, and z is an integer between 1 to 20 inclusive; or (b) R 8 and R 9 together are a C 1 -C 4 branched or straight chained alkyl group optionally substituted with one or more amine groups; and wherein the —N(R 31 )—R 3 — repeat unit is optionally interrupted in one or more places by a nitrogen-containing heterocyclic cycloalkyl group;
wherein R 4 and R 5 are each independently selected from (a) hydrogen, (b) —R 6 -R 7 , wherein R 6 is C 1 -C 4 branched or straight chained alkylene group, and R 7 is
wherein R 71 is a branched or straight-chained C 10 -C 800 alkyl or alkenyl group, the asterisk (*) indicates a connecting point with R 6 , g and h are C—C bonds in cis-configuration with respect to each other and in either cis- or trans-configuration with respect to bond j, and q is an integer between 1 to 20 inclusive; or (c) a bond connected to R 31 in the m-th —N(R 31 )—R 3 — repeat unit.
2. The method of claim 1 , wherein at least one of R 1 , R 71 , and R 91 comprises polypropylene.
3. The method of claim 1 , wherein the polypropylene is atactic polypropylene, isotactic polypropylene, or syndiotactic polypropylene.
4. The method of claim 1 , wherein the polypropylene is amorphous.
5. The method of claim 1 , wherein the polypropylene includes isotactic or syndiotactic crystallizable units.
6. The method of claim 1 , wherein the polypropylene includes meso diads constituting from about 30% to about 99.5% of the total diads of the polypropylene.
7. The method of claim 1 , wherein at least one of R 1 , R 71 , and R 91 has a number-averaged molecular weight of from about 300 to about 30000 g/mol.
8. The method of claim 1 , wherein at least one of R 1 , R 71 , and R 91 has a number-averaged molecular weight of from about 500 to about 5000 g/mol.
9. The method of claim 1 , wherein at least one of R 1 , R 71 , and R 91 comprises polyethylene.
10. The method of claim 1 , wherein at least one of R 1 , R 71 , and R 91 comprises poly(ethylene-co-propylene).
11. The method of claim 10 , wherein at least one of R 1 , R 71 , and R 91 comprises from about 1 mole % to about 90 mole % of ethylene units and from about 99 mole % to about 10 mole % propylene units.
12. The method of claim 11 , wherein at least one of R 1 , R 71 , and R 91 comprises from about 10 mole % to about 50 mole % of ethylene units.
13. The method of claim 1 , wherein at least one of R 1 , R 71 , and R 91 comprises poly(higher alpha-olefin), the higher alpha-olefin including two or more carbon atoms on each side chain.
14. The method of claim 1 , wherein at least one of R 1 , R 71 , and R 91 comprises poly(propylene-co-higher alpha-olefin), the higher alpha-olefin including two or more carbon atoms on each side chain.
15. The method of claim 1 , wherein the nitrogen content in the additive is about 1 wt % to about 10 wt % based on the total weight of the additive.
16. The method of claim 1 , wherein R 3 is —CH 2 —CH 2 —, and R 31 is hydrogen.
17. The method of claim 16 , wherein the —N(R 31 )—R 3 — repeat unit is interrupted in one or more places by a 1,4-diethylenediamine ring.
18. A system for refining hydrocarbons comprising:
at least one crude hydrocarbon refinery component; and
crude hydrocarbon in fluid communication with the at least one crude hydrocarbon refinery component, the crude hydrocarbon comprising an additive represented by
wherein R 1 is a branched or straight-chained C 10 -C 800 alkyl or alkenyl group;
y is an integer between 1 to 20 inclusive;
m is an integer between 0 and 10 inclusive;
a and b are C—C bonds in cis-configuration with respect to each other and in either cis- or trans-configuration with respect to bond c;
R 2 and R 3 are each independently a C 1 -C 4 branched or straight chained alkylene group;
R 31 is hydrogen or —R 8 -R 9 , wherein either (a) R 8 is C 1 -C 4 branched or straight chained alkylene group, and R 9 is
wherein R 91 is a branched or straight-chained C 10 -C 800 alkyl or alkenyl group, the asterisk (*) indicates a connecting point with R 8 , d and e are C—C bonds in cis-configuration with respect to each other and in either cis- or trans-configuration with respect to bond f, and z is an integer between 1 to 20 inclusive; or (b) R 8 and R 9 together are a C 1 -C 4 branched or straight chained alkyl group optionally substituted with one or more amine groups; and wherein the —N(R 31 )—R 3 — repeat unit is optionally interrupted in one or more places by a nitrogen-containing heterocyclic cycloalkyl group; and
wherein R 4 and R 5 are each independently selected from (a) hydrogen, (b) —R 6 -R 7 , wherein R 6 is C 1 -C 4 branched or straight chained alkylene group, and R 7 is
wherein R 71 is a branched or straight-chained C 10 -C 800 alkyl or alkenyl group, the asterisk (*) indicates a connecting point with R 6 , g and h are C—C bonds in cis-configuration with respect to each other and in either cis- or trans-configuration with respect to bond j, and q is an integer between 1 to 20 inclusive; or (c) a bond connected to R 31 in the m-th —N(R 31 )—R 3 — repeat unit.
19. The system of claim 18 , wherein the at least one crude hydrocarbon refinery component is selected from a heat exchanger, a furnace, a crude preheater, a coker preheater, a FCC slurry bottom, a debutanizer exchanger, a debutanizer tower, a feed/effluent exchanger, a furnace air preheater, a flare compressor component, a steam cracker, a steam reformer, a distillation column, a fractionation column, a scrubber, a reactor, a liquid-jacketed tank, a pipestill, a coker, and a visbreaker.