Catalytic system and ethylene oligomerization process for the preparation of linear alpha-olefins
Patent Information
- Authority / Receiving Office
- JP · JP
- Patent Type
- Applications
- Current Assignee / Owner
- CHEVRON PHILLIPS CHEMICAL COMPANY LP
- Filing Date
- 2024-04-23
- Publication Date
- 2026-06-24
Smart Images
Figure 2026520648000001_ABST
Abstract
Claims
1. (A) Organoaluminum compounds and (B) Hydrocarbon diluent and (C) Heteroatomic ligand and, (D) A catalyst composition comprising a transition metal compound containing Fe, Co, or Ni.
2. (i) Contacting ethylene, an organic reaction medium, and a catalyst composition comprising an organoaluminum compound, a heteroatom ligand, and a transition metal compound including Fe, Co, or Ni in an oligomerization reactor, (ii) Forming an oligomer product in the oligomerization reactor, wherein the oligomer product comprises hexene and octene, (iii) an oligomerization process comprising discharging an effluent from the oligomerization reactor, wherein the effluent contains unreacted ethylene and the oligomer product.
3. The process according to claim 2, wherein the catalyst composition further comprises a hydrocarbon diluent.
4. The composition or process according to any one of claims 1 to 3, wherein the hydrocarbon diluent and the organic reaction medium are the same or different and independently comprise saturated aliphatic hydrocarbon, aromatic hydrocarbon, linear α-olefin, or any combination thereof.
5. The composition or process according to any one of claims 1 to 4, wherein the hydrocarbon diluent and the organic reaction medium are the same or different and independently comprise 1-butene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, or a combination thereof.
6. The composition or process according to any one of claims 1 to 5, wherein the transition metal compound is soluble in the hydrocarbon diluent, or the transition metal compound is soluble in the organic reaction medium, or both.
7. The composition or process according to any one of claims 1 to 6, wherein the heteroatom ligand is a compound having the following formula: 【Chemistry 1】 In the formula, X is either P or S, When X is S, y is equal to 1, and when X is P, y is equal to 2. R １ ~R １１ These are independently H, halogen, nitro group, and C １ ~C １８ Hydrocarbyl group, or C １ ~C １８ It is a halogenated hydrocarbyl group, R ５ and R ６ They can combine to form a ring or ring system. Each R １２ is, independently, a C １ to C １８ hydrocarbyl group or a C １ to C １８ halogenated hydrocarbyl group.
8. R １ ~R ６ However, independently, it is either an H or a methyl group. R ７ ~R １１ However, independently, these are H, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, adamantyl group, phenyl group, naphthyl group, benzyl group, nitro group, pentafluorophenyl group, or trifluoromethyl group. Each R １２ The compound or process according to claim 7, wherein the group is independently a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, an adamantyl group, a phenyl group, a methyl-substituted phenyl group, a naphthyl group, a benzyl group, a pentafluorophenyl group, or a trifluoromethyl group.
9. The composition or process according to any one of claims 1 to 6, wherein the heteroatom ligand is a compound having the following formula: 【Chemistry 2】 In the formula, X is either P or S, When X is S, y is equal to 1, and when X is P, y is equal to 2. Y is O, NH, or CH ２ And, B Ｂ ~R Ｊ These are independently H, halogen, nitro group, and C １ ~C １８ Hydrocarbyl group, or C １ ~C １８ It is a halogenated hydrocarbyl group, R Ｄ and R Ｅ They can combine to form a ring or ring system. Each R Ａ Independently, C １ ~C １８ Hydrocarbyl group or C １ ~C １８ It is a halogenated hydrocarbyl group.
10. R Ｂ ~R Ｅ However, independently, it is either an H or a methyl group. R Ｆ ~R Ｊ However, independently, these are H, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, adamantyl group, phenyl group, naphthyl group, benzyl group, nitro group, pentafluorophenyl group, or trifluoromethyl group. Each R Ａ The composition or process according to claim 9, wherein the group is independently a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, an adamantyl group, a phenyl group, a methyl-substituted phenyl group, a naphthyl group, a benzyl group, a pentafluorophenyl group, or a trifluoromethyl group.
11. The transition metal compound has the formula M(X １ ) ｐ It has, in the formula, M is Fe, Co, or Ni. p is the oxidation state of M, Each X １ The composition or process according to any one of claims 1 to 10, wherein is independently a monoanionic ligand.
12. The composition or process according to claim 11, wherein M is Fe.
13. Each X １ The composition or process according to claim 11 or 12, wherein the independent components are acetate, propionate, butyrate, pentanoate, hexanoate, heptanoate, octanoate, nonanoate, decanoate, undecanoate, dodecanoate, or acetylacetonate.
14. The composition or process according to any one of claims 1 to 13, wherein the molar ratio of ligand to transition metal in the catalyst composition is in the range of 20:1 to 1:
20.
15. (a) Organic aluminum compounds and (b) Hydrocarbon diluent and (c) A catalyst composition comprising a heteroatom ligand transition metal compound complex containing Fe, Co, or Ni.
16. (i) Contacting ethylene, an organic reaction medium, and a catalyst composition comprising an organoaluminum compound and a heteroatom ligand transition metal compound complex containing Fe, Co, or Ni in an oligomerization reactor, (ii) Forming an oligomer product in the oligomerization reactor, wherein the oligomer product comprises hexene and octene, (iii) an oligomerization process comprising discharging an effluent from the oligomerization reactor, wherein the effluent contains unreacted ethylene and the oligomer product.
17. The composition or process according to claim 15 or 16, wherein the heteroatom ligand transition metal compound complex has the following formula: 【Transformation 3】 In the formula, X is either P or S, When X is S, y is equal to 1, and when X is P, y is equal to 2. M is Fe, Co, or Cr. m is the oxidation state of M, Each Z independently corresponds to H, halogen, and C. １ ~C １８ Hydrocarbyl group or C １ ~C １８ It is a halogenated hydrocarbyl group, R １ ~R １１ These are independently H, halogen, nitro group, and C １ ~C １８ Hydrocarbyl group, or C １ ~C １８ It is a halogenated hydrocarbyl group, R ５ and R ６ They can combine to form a ring or ring system. Each R １２ Independently, C １ ~C １８ Hydrocarbyl group or C １ ~C １８ It is a halogenated hydrocarbyl group.
18. The composition or process according to claim 15 or 16, wherein the heteroatom ligand transition metal compound complex has the following formula: 【Chemistry 4】 In the formula, X is either P or S, When X is S, y is equal to 1, and when X is P, y is equal to 2. Y is O, NH, or CH ２ And, M is Fe, Co, or Cr. m is the oxidation state of M, Each Z independently corresponds to H, halogen, and C. １ ~C １８ Hydrocarbyl group or C １ ~C １８ It is a halogenated hydrocarbyl group, B Ｂ ~R Ｊ These are independently H, halogen, nitro group, and C １ ~C １８ Hydrocarbyl group, or C １ ~C １８ It is a halogenated hydrocarbyl group, R Ｄ and R Ｅ They can combine to form a ring or ring system. Each R Ａ Independently, C １ ~C １８ Hydrocarbyl group or C １ ~C １８ It is a halogenated hydrocarbyl group.
19. The composition or process according to any one of claims 1 to 18, wherein the organoaluminum compound comprises an aluminoxane, an alkylaluminum compound, or any combination thereof.
20. The composition or process according to any one of claims 1 to 19, wherein the organoaluminum compound comprises methylaluminoxane (MAO), ethylaluminoxane, modified methylaluminoxane (MMAO), n-propylaluminoxane, isopropylaluminoxane, n-butylaluminoxane, sec-butylaluminoxane, isobutylaluminoxane, t-butylaluminoxane, 1-pentylaluminoxane, 2-pentylaluminoxane, 3-pentylaluminoxane, isopentylaluminoxane, neopentylaluminoxane, or a combination thereof.
21. The aforementioned organoaluminum compound (I) an alkylaluminoxane having random repeating units of formula (A) and formula (B): 【Transformation 5】 In the formula, R is methyl, １ It is ethyl, and the molar ratio of methyl:ethyl is 5:95 to 80:20; (II) A hydrocarbon solvent and an alkylaluminoxane composition comprising The composition or process according to any one of claims 1 to 19, wherein the amount of aluminum in the composition is 0.1 to 20% by weight.
22. The aforementioned organoaluminum compound (a) Reacting trimethylaluminum (TMA), triethylaluminum (TEA), and water in a hydrocarbon solvent to form an alkylaluminoxane, The molar ratio of TMA:TEA is 5:95 to 80:
20. The formation is such that the molar ratio of water to Al is 0.2:1 to 1:
1. (b) The composition or process according to any one of claims 1 to 19, comprising the alkylaluminoxane composition produced by a process comprising: removing an insoluble aluminum-containing material from the solvent to form an alkylaluminoxane composition containing 0.1 to 20% by weight of aluminum.
23. The composition or process according to claim 22, wherein the molar ratio of water to Al is 0.3:1 to 0.8:
1.
24. The alkylaluminoxane composition contains 2 to 15% by weight of aluminum, The molar ratio of TMA:TEA or the molar ratio of methyl:ethyl is 15:85 to 30:
70. The composition or process according to any one of claims 21 to 23, wherein the hydrocarbon solvent comprises a saturated aliphatic hydrocarbon, an aromatic hydrocarbon, a linear α-olefin, or any combination thereof.
25. The composition or process according to any one of claims 1 to 24, wherein the molar ratio of Al:transition metal or Al:ligand in the catalyst composition is in the range of 10:1 to 5,000:
1.
26. The process according to any one of claims 2 to 14 or 16 to 25, wherein the oligomerization reactor includes a continuous stirred tank reactor, a loop reactor, or any combination thereof.
27. The process according to any one of claims 2 to 14 or 16 to 26, wherein hydrogen is present in step (i) of the oligomerization process.
28. The process according to any one of claims 2 to 14 or 16 to 27, wherein ethylene is introduced into the oligomerization reactor separately from the catalyst composition or catalyst system components.
29. The process according to any one of claims 2 to 14 or 16 to 28, wherein the catalyst composition is formed and then introduced into the oligomerization reactor.
30. The process according to any one of claims 2 to 14 or 16 to 28, wherein the catalyst composition is formed in the oligomerization reactor.
31. The process according to any one of claims 2 to 14 or 16 to 30, wherein at least a portion of the heteroatom ligand and at least a portion of the transition metal compound are combined to form at least a portion of the heteroatom ligand transition metal compound complex before being introduced into the oligomerization reactor.
32. The process according to any one of claims 2 to 14 or 16 to 31, wherein the organic reaction medium and the organoaluminum compound are combined and then introduced into the oligomerization reactor.