Fouling protection for an oligomerization reactor inlet
Disclosed herein are systems and processes which prevent fouling of a reactor inlet of an oligomerization reactor. The systems and processes involve placement of an inlet sleeve around at least a portion of a reactor inlet such that a curtain of inert material flows through an annular space coaxially with respect to an outer surface of the end of the reactor inlet and into the reactor.
1. A process for introducing reactants into an oligomerization reactor inlet, the process comprising:
flowing ethylene into an oligomerization reactor via the oligomerization reactor inlet such that the ethylene is introduced to an interior of the oligomerization reactor via an end of the oligomerization reactor inlet; and
flowing a saturated hydrocarbon into the oligomerization reactor coaxially with respect to an outer surface of the end of the oligomerization reactor inlet; and
wherein the saturated hydrocarbon flows coaxially with respect to the outer surface of the end of the oligomerization reactor inlet via an annular space formed between an inner surface of an inlet sleeve and the outer surface of the oligomerization reactor inlet.
2. The process of claim 1 , further comprising feeding a catalyst system to the oligomerization reactor via a catalyst inlet or via the oligomerization reactor inlet, the catalyst system comprising
1) a chromium component comprising a chromium compound, a heteroatomic ligand, and an aluminoxane; or
2) a chromium component comprising a heteroatomic ligand chromium compound complex, and an aluminoxane.
3. The process of claim 1 , further comprising feeding a catalyst system to the oligomerization reactor via a catalyst inlet or via the oligomerization reactor inlet, the catalyst system comprising:
1) i) a chromium component comprising an N 2 -phosphinyl formamidine chromium compound complex, an N 2 -phosphinyl amidine chromium compound complex, an N 2 -phosphinyl guanidine chromium compound complex, or any combination thereof, and
ii) an aluminoxane;
2) i) a chromium component comprising a chromium compound having the formula CrX p ,
ii) a heteroatomic ligand having the formula
(R 1s ) m X 1s (L 1s )X 2s (R 2s ) n or
and
iii) an aluminoxane; or
3) i) a chromium component comprising a heteroatomic ligand chromium compound complex having the formula
and
ii) an aluminoxane;
wherein each X 1s and each X 2s is independently selected from the group consisting of N, P, O, and S,
wherein each L 1s is an independent linking group between the respective X 1s s and X 2s s and independently are an organylene group, an amin-di-yl group, or a phosphin-di-yl group,
wherein each R 1s and each R 2s are independently hydrogen, an organyl group or a heterohydrocarbyl group, where when there are two or more R 1s s and/or two R 2s s, each R 1s can be the same or different and/or each R 2s can be the same or different,
wherein each m and each n are independently 1 or 2, and
wherein X represents a monoanionic ligand selected from a halide, a carboxylate, a β-diketonate, a hydrocarboxide, a nitrate, or a chlorate, and p can be from 2 to 4.
4. The process of claim 3 , wherein the catalyst system comprises
i) an N 2 -phosphinyl formamidine chromium compound complex having structure
an N 2 -phosphinyl amidine chromium compound complex having structure
an N 2 -phosphinyl guanidine chromium compound complex having the structure
and
wherein
R 1 is a C 1 to C 20 alkyl group, a C 1 to C 20 substituted alkyl group, a C 4 to C 20 cycloalkyl group, a C 4 to C 20 substituted cycloalkyl group, a C 6 to C 20 aryl group, a C 6 to C 20 substituted aryl group, a C 7 to C 20 aralkyl group, or a C 7 to C 20 substituted aralkyl group,
R 2 is a C 1 to C 20 alkyl group, a C 1 to C 20 substituted alkyl group, a C 4 to C 20 cycloalkyl group, a C 4 to C 20 substituted cycloalkyl group, a C 6 to C 20 aryl group, a C 6 to C 20 substituted aryl group, a C 7 to C 20 aralkyl group, or a C 7 to C 20 substituted aralkyl group,
R 2a and R 2b independently are C 1 to C 20 alkyl group, a C 1 to C 20 substituted alkyl group, a C 4 to C 20 cycloalkyl group, a C 4 to C 20 substituted cycloalkyl group, a C 6 to C 20 aryl group, a C 6 to C 20 substituted aryl group, a C 7 to C 20 aralkyl group, or a C 7 to C 20 substituted aralkyl group,
L 12 and L 23 independently are a C 2 to C 20 organylene group consisting of inert functional groups,
L 22 is a C 3 to C 20 organylene group consisting of inert functional groups,
R 3 is hydrogen, a C 1 to C 20 alkyl group, a phenyl group, or a C 6 to C 20 substituted phenyl group,
R 4 and R 5 are each independently a C 1 to C 20 alkyl group, a C 1 to C 20 substituted alkyl group, a C 4 to C 20 cycloalkyl group, a C 4 to C 20 substituted cycloalkyl group, a C 6 to C 20 aryl group, a C 6 to C 20 substituted aryl group, a C 7 to C 20 aralkyl group, or a C 7 to C 20 substituted aralkyl group,
CrX p represents the chromium salt where X is a C 1 to C 20 carboxylate, a C 1 to C 20 β-diketonate, or a halide, and p ranges from 2 to 3,
Q is a neutral ligand and each neutral ligand independently is a C 2 to C 20 nitrile or a C 2 to C 40 ether,
a ranges from 0 to 6, and
wherein each substituent independently can be a halide, a hydrocarbyl group, or a hydrocarboxy group, and
ii) an aluminoxane comprising methylaluminoxane, modified methylaluminoxane, ethylaluminoxane, n-propylaluminoxane, iso-propylaluminoxane, n-butylaluminoxane, sec-butylaluminoxane, iso-butylaluminoxane, t-butyl aluminoxane, 1-pentylaluminoxane, 2-pentylaluminoxane, 3-pentylaluminoxane, iso-pentylaluminoxane, neopentylaluminoxane, and mixtures thereof.
5. The process of claim 4 , wherein
R 1 is a phenyl group or a C 6 to C 10 substituted phenyl group,
R 2 is a C 6 to C 10 aryl group, a C 6 to C 10 substituted aryl group, a C 7 to C 10 aralkyl group, or a C 7 to C 10 substituted aralkyl group,
R 2a and R 2b independently are a C 1 to C 5 alkyl group, a C 4 to C 10 cycloalkyl group, a phenyl group, or a C 6 to C 10 substituted phenyl group,
L 12 and L 23 independently are C 2 to C 10 hydrocarbylene group,
L 22 is a C 4 to C 10 hydrocarbylene group,
R 3 is hydrogen,
R 4 and R 5 are each independently a C 1 to C 10 alkyl group, a C 4 to C 10 cycloalkyl group, a phenyl group, or a C 6 to C 20 substituted phenyl group.
6. The process of claim 3 , wherein the catalyst system comprises
1) i) a chromium component comprising a chromium compound having the formula CrX p ,
ii) a heteroatomic ligand having the formula R 1s S(L 1s )SR 2s , (R 1s ) 2 P(L 1s )P(R 2s ) 2 , or (R 1s ) 2 N(L 1s )N(R 2s ) 2 , and
iii) an aluminoxane; or
2) i) a chromium component comprising a heteroatomic ligand chromium compound complex having the formula
and
ii) an aluminoxane;
wherein L 1s has the -(L 3s )NR 5s (L 4s )-, -(L 3s )PR 5s (L 4s )-, —N(R 5s )—, or —P(R 5s )— where L 3s and L 4s independently are a C 1 to C 20 organylene group consisting of inert functional groups and R 5s is a C 1 to C 20 alkyl group, a substituted C 1 to C 20 alkyl group, a C 4 to C 20 cycloalkyl group, a substituted C 4 to C 20 cycloalkyl group, a C 6 to C 20 aryl group, a substituted C 6 to C 20 aryl group, a C 7 to C 20 aralkyl group, or a C 7 to C 20 substituted aralkyl group where each substituent of the substituted alkyl group, substituted cycloalkyl group, substituted aryl group, or substituted aralkyl group is a halogen, hydrocarbyl group, or a hydrocarboxyl group;
wherein each R 1s and each R 2s independently are a C 1 to C 20 alkyl group, a substituted C 1 to C 20 alkyl group, a C 4 to C 20 cycloalkyl group, a substituted C 4 to C 20 cycloalkyl group, a C 6 to C 20 aryl group, a substituted C 6 to C 20 aryl group, a C 7 to C 20 aralkyl group, or a C 7 to C 20 substituted aralkyl group;
where X is a halide, a C 1 to C 20 carboxylate, a C 1 to C 20 β-diketonate, or a halide, and p ranges from 2 to 3; and
wherein the aluminoxane comprises methylaluminoxane, modified methylaluminoxane, ethylaluminoxane, n-propylaluminoxane, iso-propylaluminoxane, n-butylaluminoxane, sec-butylaluminoxane, iso-butylaluminoxane, t-butyl aluminoxane, 1-pentylaluminoxane, 2-pentylaluminoxane, 3-pentylaluminoxane, iso-pentylaluminoxane, neopentylaluminoxane, and mixtures thereof.
7. The process of claim 6 , wherein
L 3s and L 4s independently are a C 1 to C 10 hydrocarbylene group;
R 5s is a C 1 to C 10 alkyl group, a C 5 to C 10 cycloalkyl group, a substituted C 5 to C 10 cycloalkyl group, a phenyl group or a C 6 to C 10 substituted phenyl group, or a C 7 to C 10 aralkyl group, where each substituent independently is an alkyl group; and
wherein each R 1s and each R 2s are independently C 1 to C 10 alkyl group, a C 4 to C 10 cycloalkyl group, a C 6 to C 10 aryl group, or a C 7 to C 10 aralkyl group where each substituent independently is an alkyl group.
8. The process of claim 1 , wherein the end of the oligomerization reactor inlet extends into the interior of the oligomerization reactor, and wherein an end of the inlet sleeve extends into the interior of the oligomerization reactor.
9. The process of claim 1 , further comprising:
flowing the saturated hydrocarbon into the oligomerization reactor via the oligomerization reactor inlet such that a mixture of ethylene and saturated hydrocarbon is introduced to the interior of the oligomerization reactor via the end of the oligomerization reactor inlet,
wherein the saturated hydrocarbon which flows into the oligomerization reactor via the oligomerization reactor inlet is a primary source of the saturated hydrocarbon for an oligomerization reaction in the oligomerization reactor, and
wherein the saturated hydrocarbon which flow's coaxially into the oligomerization reactor is a secondary source of the saturated hydrocarbon for the oligomerization reaction in the oligomerization reactor.
10. The process of claim 1 , wherein the saturated hydrocarbon flows into the oligomerization reactor via the annular space separately from the flow of the ethylene into the oligomerization reactor via the end of the oligomerization reactor inlet.
11. The process of claim 10 , wherein the end of the oligomerization reactor inlet extends outside of the inlet sleeve, wherein the end of the oligomerization reactor inlet is contained within the inlet sleeve, or wherein the end of the oligomerization reactor inlet and an end of the inlet sleeve terminate in a common plane.
12. The process of claim 1 , wherein flowing the saturated hydrocarbon into the oligomerization reactor provides a turbulent region at an injection point.
13. A system for introducing reactants into an oligomerization reactor inlet, the system comprising:
an oligomerization reactor;
an oligomerization reactor inlet coupled with the oligomerization reactor such that an end of the oligomerization reactor inlet extends into an interior of the oligomerization reactor;
an inlet sleeve coupled with the oligomerization reactor such that an end of the inlet sleeve extends into the interior of the oligomerization reactor;
a reactant source coupled to the oligomerization reactor;
an inert material source coupled to the oligomerization reactor;
wherein the inlet sleeve is placed coaxially around at least a portion of the oligomerization reactor inlet such that an annular space is formed between an outer surface of the oligomerization reactor inlet and an inner surface of the inlet sleeve,
wherein the reactant source provides reactant or a mixture of the reactant and diluent to the oligomerization reactor via the oligomerization reactor inlet,
wherein the inert material source provides an inert material to the oligomerization reactor via the annular space,
wherein the reactant is ethylene, and
wherein the inert material and diluent are independently a saturated hydrocarbon.
14. The system of claim 13 , further comprising:
a catalyst system source coupled to the oligomerization reactor; and
wherein the catalyst system source provides a catalyst system to the oligomerization reactor via the oligomerization reactor inlet or via a catalyst inlet.
15. The system of claim 14 , wherein the catalyst system comprises
1) a chromium component comprising a chromium compound, a heteroatomic ligand, and an aluminoxane; or
2) a chromium component comprising a heteroatomic ligand chromium compound complex, and an aluminoxane.
16. The system of claim 15 , wherein the catalyst system comprises
1) i) a chromium component comprising an N 2 -phosphinyl formamidine chromium compound complex, an N 2 -phosphinyl amidine chromium compound complex, an N 2 -phosphinyl guanidine chromium compound complex, or any combination thereof, and
ii) an aluminoxane;
2) i) a chromium component comprising a chromium compound having the formula CrX p ,
ii) a heteroatomic ligand, and
iii) an aluminoxane; or
3) i) a chromium component comprising a heteroatomic ligand chromium compound complex, and
ii) an aluminoxane;
where the heteroatomic ligand has the formula
(R 1s ) m X 1s (L 1s )X 2s (R 2s ) n or
where the heteroatomic ligand chromium compound complex has the formula
wherein each X 1s and each X 2s is independently selected from the group consisting of N, P, O, and S,
wherein each L 1s is an independent linking group between the respective X 1s s and X 2s s and independently are an organylene group, an amin-di-yl group, or a phospbin-di-yl group,
wherein each R 1s and each R 2s are independently hydrogen, an organyl group or a heterohydrocarbyl group, where when there are two or more R 1s s and/or two R 2s s, each R 1s can be the same or different and/or each R 2s can be the same or different,
wherein each m and each n are independently 1 or 2, and
wherein X represents a monoanionic ligand selected from a halide, a carboxylate, a β-diketonate, a hydrocarboxide, a nitrate, or a chlorate, and p can be from 2 to 4.
17. The system of claim 16 , wherein the catalyst system comprises
i) an N 2 -phosphinyl formamidine chromium compound complex having structure
an N 2 -phosphinyl amidine chromium compound complex having structure or
or
an N 2 -phosphinyl guanidine chromium compound complex having the structure
and
wherein
R 1 is a C 1 to C 20 alkyl group, a C 1 to C 20 substituted alkyl group, a C 4 to C 20 cycloalkyl group, a C 4 to C 20 substituted cycloalkyl group, a C 6 to C 20 aryl group, a C 6 to C 20 substituted aryl group, a C 7 to C 20 aralkyl group, or a C 7 to C 20 substituted aralkyl group,
R 2 is a C 1 to C 20 alkyl group, a C 1 to C 20 substituted alkyl group, a C 4 to C 20 cycloalkyl group, a C 4 to C 20 substituted cycloalkyl group, a C 6 to C 20 aryl group, a C 6 to C 20 substituted aryl group, a C 7 to C 20 aralkyl group, or a C 7 to C 20 substituted aralkyl group,
R 2a and R 2b independently are C 1 to C 20 alkyl group, a C 1 to C 20 substituted alkyl group, a C 4 to C 20 cycloalkyl group, a C 4 to C 20 substituted cycloalkyl group, a C 6 to C 20 aryl group, a C 6 to C 20 substituted aryl group, a C 7 to C 20 aralkyl group, or a C 7 to C 20 substituted aralkyl group,
L 12 and L 23 independently are a C 2 to C 20 organylene group consisting of inert functional groups,
L 22 is a C 3 to C 20 organylene group consisting of inert functional groups,
R 3 is hydrogen, a C 1 to C 20 alkyl group, a phenyl group, or a C 6 to C 20 substituted phenyl group,
R 4 and R 5 are each independently a C 1 to C 20 alkyl group, a C 1 to C 20 substituted alkyl group, a C 4 to C 20 cycloalkyl group, a C 4 to C 20 substituted cycloalkyl group, a C 6 to C 20 aryl group, a C 6 to C 20 substituted aryl group, a C 7 to C 20 aralkyl group, or a C 7 to C 20 substituted aralkyl group,
CrX p represents the chromium salt where X is a C 1 to C 20 carboxylate, a C 1 to C 20 β-diketonate, or a halide, and p ranges from 2 to 3,
Q is a neutral ligand and each neutral ligand independently is a C 2 to C 20 nitrile or a C 2 to C 40 ether,
a ranges from 0 to 6, and
wherein each substituent independently can be a halide, a hydrocarbyl group, or a hydrocarboxy group, and
ii) an aluminoxane comprising methylaluminoxane, modified methylaluminoxane, ethylaluminoxane, n-propylaluminoxane, iso-propyl aluminoxane, n-butylaluminoxane, sec-butylaluminoxane, iso-butylaluminoxane, t-butyl aluminoxane, 1-pentylaluminoxane, 2-pentylaluminoxane, 3-pentylaluminoxane, iso-pentylaluminoxane, neopentylaluminoxane, and mixtures thereof.
18. The system of claim 17 , wherein
R 1 is a phenyl group or a C 6 to C 10 substituted phenyl group,
R 2 is a C 6 to C 10 aryl group, a C 6 to C 10 substituted aryl group, a C 7 to C 10 aralkyl group, or a C 7 to C 10 substituted aralkyl group,
R 2a and R 2b independently are a C 1 to C 5 alkyl group, a C 4 to C 10 cycloalkyl group, a phenyl group, or a C 4 to C 10 substituted phenyl group,
L 12 and L 23 independently are C 2 to C 10 hydrocarbylene group,
L 22 is a C 4 to C 10 hydrocarbylene group,
R 3 is hydrogen, and
R 4 and R 5 are each independently a C 1 to C 10 alkyl group, a C 4 to C 10 cycloalkyl group, a phenyl group, or a C 6 to C 20 substituted phenyl group.
19. The system of claim 16 , wherein the catalyst system comprises
1) i) a chromium component comprising a chromium compound having the formula CrX p ,
ii) a heteroatomic ligand having the formula R 1s S(L 1s )SR 2s , (R 1s ) 2 P(L 1s )P(R 2s ) 2 , or (R 1s ) 2 N(L 1s )N(R 2s ) 2 , and
iii) an aluminoxane; or
2) i) a chromium component comprising a heteroatomic ligand chromium compound complex having the formula
and
ii) an aluminoxane;
wherein L 1s has the -(L 3s )NR 5s (L 4s )-, -(L 3s )PR 5s (L 4s )-, —N(R 5s )—, or —P(R 5s )— where L 3s and L 4s independently are a C 1 to C 20 organylene group consisting of inert functional groups and R 5s is a C 1 to C 20 alkyl group, a substituted C 1 to C 20 alkyl group, a C 4 to C 20 cycloalkyl group, a substituted C 4 to C 20 cycloalkyl group, a C 6 to C 20 aryl group, a substituted C 6 to C 20 aryl group, a C 7 to C 20 aralkyl group, or a C 7 to C 20 substituted aralkyl group,
wherein each R 1s and each R 2s independently are a C 1 to C 20 alkyl group, a substituted C 1 to C 20 alkyl group, a C 4 to C 20 cycloalkyl group, a substituted C 4 to C 20 cycloalkyl group, a C 6 to C 20 aryl group, a substituted C 6 to C 20 aryl group, a C 7 to C 20 aralkyl group, or a C 7 to C 20 substituted aralkyl group,
wherein each substituent is a halogen, hydrocarbyl group, or a hydrocarboxyl group,
wherein X is a halide, a C 4 to C 20 carboxylate, a C 1 to C 20 β-diketonate, or a halide, and p ranges from 2 to 3, and
wherein the aluminoxane comprises methylaluminoxane, modified methylaluminoxane, ethylaluminoxane, n-propylaluminoxane, iso-propylaluminoxane, n-butylaluminoxane, sec-butylaluminoxane, iso-butylaluminoxane, t-butyl aluminoxane, 1-pentylaluminoxane, 2-pentylaluminoxane, 3-pentylaluminoxane, iso-pentylaluminoxane, neopentylaluminoxane, and mixtures thereof.
20. The system of claim 19 , wherein
L 3s and L 4s independently are a C 1 to C 10 hydrocarbylene group;
R 5s is a C 1 to C 10 alkyl group, a C 5 to C 10 cycloalkyl group, a substituted C 5 to C 10 cycloalkyl group, a phenyl group or a C 6 to C 10 substituted phenyl group, or a C 7 to C 10 aralkyl group, where each substituent independently is an alkyl group; and
wherein each R 1s and each R 2s are independently C 1 to C 10 alkyl group, a C 4 to C 10 cycloalkyl group, a C 6 to C 10 aryl group, or a C 7 to C 10 aralkyl group where each substituent independently is an alkyl group.
21. The system of claim 13 , wherein the end of the oligomerization reactor inlet extends outside of the inlet sleeve, the end of the oligomerization reactor inlet is contained within the inlet sleeve, or the end of the oligomerization reactor inlet and the end of the inlet sleeve terminate in a common plane in the interior of the reactor.
22. The system of claim 13 , wherein the annular space is formed both inside and outside of the oligomerization reactor.