Recovery of ethylene and propylene from a methanol to olefin reaction system

• US 7,074,971 B2
• Filed: 03/06/2003
• Issued: 07/11/2006
• Est. Priority Date: 03/06/2003
• Status: Active Grant

• Current Assignee: ExxonMobil Chemical Patents Inc. (Exxon Mobil Corporation)
• Original Assignee: ExxonMobil Chemical Patents Inc. (Exxon Mobil Corporation)
• Inventors: Brinen, Jeffrey L., Van Egmond, Cor F.
• Primary Examiner(s): KEYS, ROSALYND ANN
• Application Number:
  US10/383,204
• Publication Number:
  US 20040176646A1
• Time in Patent Office: 1,223 Days
• Field of Search: 585/639, 585/809, 585/259, 585/250, 585/264, 585/500, 203/38, 203/39, 203/75, 203/76, 203/77, 568/699, 526/77
• US Class Current: 568/699
• CPC Class Codes: C07C 11/04 Ethylene
• CPC Class Codes: C07C 11/06 Propene
• CPC Class Codes: C07C 7/04 by distillation

Abstract

The present invention provides new highly-efficient separation processes and systems for separating polymerization-grade ethylene and propylene from an initial effluent stream comprising ethane, ethylene, propylene, dimethyl ether, and one or more of propane, acetylene, methyl acetylene, propadiene, methane, hydrogen, carbon monoxide, carbon dioxide and C4+ components. In one embodiment, the initial effluent stream is provided from a methanol-to-olefin reaction system. It has been discovered that the best separation of these components is realized when DME is selectively removed in a first separation step, followed by separation of the remaining components in additional separation steps.

Claims

1. A process for separating components from an olefin-containing effluent stream, the process comprising the steps of:

(a) providing the effluent stream, wherein the effluent stream contains ethane, ethylene, propylene, and dimethyl ether;

(b) separating the effluent stream in a first separation unit into a first fraction and a second fraction, wherein the first fraction contains a majority of the ethane, ethylene and propylene present in the effluent stream, and wherein the second fraction contains a majority of the dimethyl ether present in the effluent stream;

(c) separating at least a portion of the first fraction into a third fraction and a fourth fraction, wherein the third fraction contains a majority of the ethylene and ethane present in the at least a portion of the first fraction, and wherein the fourth fraction contains a majority of the propylene present in the at least a portion of the first fraction, wherein the effluent stream, the first fraction, and the third fraction further contain methane and acetylene;

(d) separating at least a portion of the third fraction into a fifth fraction and a sixth fraction, wherein the fifth fraction contains a majority of the methane present in the at least a portion of the third fraction; and

the sixth fraction contains a majority of the acetylene, ethylene and ethane present in the at least a portion of the third fraction; and

(e) contacting the acetylene in at least a portion of the sixth fraction, or in a portion separated from the sixth fraction, with hydrogen and carbon monoxide under conditions effective to convert at least a portion of the acetylene to ethylene.

2. The process of claim 1, the process further comprising the step of contacting the acetylene in the at least a portion of the sixth fraction with hydrogen and carbon monoxide under conditions effective to convert at least a portion of the acetylene to ethylene, thereby forming an acetylene-depleted stream comprising ethylene and ethane.

3. The process of claim 2, wherein the process further comprises the step of separating at least a portion of the acetylene-depleted stream into a seventh fraction and an eighth fraction, wherein the seventh fraction contains a majority of the ethylene present in the at least a portion of the acetylene-depleted stream, and wherein the eighth fraction contains a majority of the ethane present in the at least a portion of the acetylene-depleted stream.

4. The process of claim 1 wherein the process further comprises the step of separating at least a portion of the sixth fraction into a seventh fraction and an eighth fraction, wherein the seventh fraction contains a majority of the ethylene present in the at least a portion of the sixth fraction, and wherein the eighth fraction contains a majority of the ethane present in the at least a portion of sixth fraction.

5. The process of claim 4, wherein the effluent stream, the first fraction and the fourth fraction further contain propane, the process further comprising the step of separating at least a portion of the fourth fraction into a ninth fraction and a tenth fraction, wherein the ninth fraction contains a majority of the propylene present in the at least a portion of the fourth fraction, and wherein the tenth fraction contains a majority of the propane present in the at least a portion of the fourth fraction.

6. The process of claim 1, wherein the effluent stream, the first fraction and the fourth fraction further contain propane, the process further comprising the step of separating at least a portion of the fourth fraction into a ninth fraction and a tenth fraction, wherein the ninth fraction contains a majority of the propylene present in the at least a portion of the fourth fraction, and wherein the tenth fraction contains a majority of the propane present in the at least a portion of the fourth fraction.

7. The process of claim 6, wherein at least a portion of the tenth fraction is recycled to the first separation unit.

8. The process of claim 1, wherein the effluent stream and the first fraction further contain carbon dioxide, the process further comprising the step of contacting the first fraction with a caustic medium under conditions effective to remove carbon dioxide from the first fraction.

9. The process of claim 1, wherein step (b) occurs at a pressure of at least 200 psig.

10. The process of claim 9, wherein the pressure is from 200 to 290 psig.

11. The process of claim 10, wherein the pressure is from 250 to 290 psig.

12. The process of claim 1, wherein the effluent stream further contains water in an amount not greater than 15,000 wppm.

13. The process of claim 12, wherein the water is present in an amount of from 10 to 15,000 wppm.

14. The process of claim 1, wherein the effluent stream further contains at least 500 wppm dimethyl ether.

15. The process of claim 1, wherein the effluent stream contains not greater than 50 weight percent dimethyl ether.

16. The process of claim 1, wherein the effluent stream further contains propane, and wherein the first fraction contains a majority of the propane present in the effluent stream.

17. The process of claim 1, wherein the effluent stream further contains propane, and wherein the second fraction contains a majority of the propane present in the effluent stream.

18. The process of claim 1, wherein the first fraction contains not greater than 100 wppm dimethyl ether.

19. The process of claim 1, wherein the first separation unit comprises a distillation column.

20. The process of claim 19, wherein a water absorbent is added to the distillation column.

21. The process of claim 20, wherein the water absorbent is added to the distillation column at a molar ratio or water absorbent to total effluent stream to be separated of from 4:

1 to 1;

5,000.

22. The process of claim 1, wherein the effluent stream contains from 50 to 95 combined weight percent ethylene and propylene, based on the total weight of the effluent stream.

23. The process of claim 1, wherein the effluent stream contains from 25 to 75 weight percent ethylene, based on the total weight of the effluent stream.

24. The process of claim 1, wherein the effluent stream contains from 25 to 75 weight percent propylene, based on the total weight of the effluent stream.

25. The process of claim 1, wherein the effluent stream further contains CO₂, and the first fraction further contains at least a majority of the CO₂ present in the effluent stream.

26. The process of claim 25, wherein the process further comprises the step of acid gas treating the first fraction.

27. The process of claim 1, wherein the effluent stream further contains C₄+ hydrocarbon components, and the second fraction further contains at least a majority of the C₄+ hydrocarbon components present in the effluent stream.

28. The process of claim 3, wherein the process further comprises the step of polymerizing the ethylene from the seventh fraction.

29. The process of claim 6, wherein the process further comprises the step of polymerizing the propylene from the ninth fraction.

30. The process of claim 20, wherein the process further comprises the step contacting the first fraction with water, acid gas treating the water contacted first fraction, and drying the acid gas treated first fraction.

31. The process of claim 1, wherein step (b) occurs at a pressure of less than 200 psig.

32. The process of claim 31, wherein the pressure is from 100 to 200 psig.

33. The process of claim 32, wherein the pressure is from 120 to 180 psig.

34. The process of claim 31, wherein the first separation unit comprises a distillation column.

35. The process of claim 34, wherein a water absorbent is added to the distillation column.

36. The process of claim 35, wherein the second fraction has an average temperature of not greater than 210°

F.

37. A process for separating components from an olefin-containing effluent stream, the process comprising the steps of:

(a) providing the effluent stream, wherein the effluent stream contains methane, ethane, ethylene, propane, propylene, and dimethyl ether;

(b) separating the effluent stream in a first separation unit into a first fraction and a second fraction, wherein the first fraction contains a majority of the methane, ethane, ethylene, propane and propylene present in the effluent stream, and wherein the second fraction contains a majority of the dimethyl ether present in the effluent stream;

(c) separating at least a portion of the first fraction into a third fraction and a fourth fraction, wherein the third fraction contains a majority of the methane that was present in the at least a portion of the first fraction, and wherein the fourth fraction contains a majority of the ethylene, ethane, propylene and propane that was present in the at least a portion of the first fraction, wherein the effluent stream, the first fraction, and the fourth fraction further contain acetylene; and

(d) contacting acetylene in the fourth fraction, or in an acetylene-containing fraction separated from the fourth fraction, with hydrogen and carbon monoxide under conditions effective to convert at least a portion of the acetylene to ethylene.

38. The process of claim 37, wherein the process further comprises the step of separating at least a portion of the fourth fraction into a fifth fraction and a sixth fraction, wherein the fifth fraction contains a majority of the ethylene and ethane that was present in the at least a portion of the fourth fraction, and wherein the sixth fraction contains majority of the propylene and propane that was present in the at least a portion of the fourth fraction.

39. The process of claim 38, wherein the fifth fraction contains acetylene, and wherein the process comprises the step of contacting the acetylene in at least a portion of the fifth fraction with hydrogen and carbon monoxide under conditions effective to convert at least a portion of the acetylene to ethylene, thereby forming an acetylene-depleted stream comprising ethylene and ethane.

40. The process of claim 39, wherein the process further comprises the step of separating at least a portion of the acetylene-depleted stream into a seventh fraction and an eighth fraction, wherein the seventh fraction contains a majority of the ethylene present in the at least a portion of the acetylene-depleted stream, and wherein the eighth fraction contains a majority of the ethane present in the at least a portion of acetylene-depleted stream.

41. The process of claim 40, the process further comprising the step of separating at least a portion of the sixth fraction into a ninth fraction and a tenth fraction, wherein the ninth fraction contains a majority of the propylene present in the at least a portion of the sixth fraction, and wherein the tenth fraction contains a majority of the propane present in the at least a portion of the sixth fraction.

42. The process of claim 41, wherein at least a portion of the tenth fraction is recycled to the first separation unit.

43. The process of claim 38, wherein the process further comprises the step of separating at least a portion of the fifth fraction into a seventh fraction and an eighth fraction, wherein the seventh fraction contains a majority of the ethylene present in the at least a portion of the fifth fraction, and wherein the eighth fraction contains a majority of the ethane present in the at least a portion of fifth fraction.

44. The process of claim 43, the process further comprising the step of separating at least a portion of the sixth fraction into a ninth fraction and a tenth fraction, wherein the ninth fraction contains a majority of the propylene present in the at least a portion of the sixth fraction, and wherein the tenth fraction contains a majority of the propane present in the at least a portion of the sixth fraction.

45. The process of claim 38, the process further comprising the step of separating at least a portion of the sixth fraction into a ninth fraction and a tenth fraction, wherein the ninth fraction contains a majority of the propylene present in the at least a portion of the sixth fraction, and wherein the tenth fraction contains a majority of the propane present in the at least a portion of the sixth fraction.

46. The process of claim 45, wherein at least a portion of the tenth fraction is recycled to the first separation unit.

47. The process of claim 37, wherein the effluent stream and the first fraction further contain carbon dioxide, the process further comprising the step of contacting the first fraction with a caustic medium under conditions effective to remove carbon dioxide from the first fraction.

48. The process of claim 37, wherein step (b) occurs at a pressure of at least 200 psig.

49. The process of claim 48, wherein the pressure is from 200 to 290 psig.

50. The process of claim 49, wherein the pressure is from 250 to 290 psig.

51. The process of claim 37, wherein the effluent stream further contains water in an amount not greater than 15,000 wppm.

52. The process of claim 51, wherein the water is present in an amount of from 10 to 15,000 wppm.

53. The process of claim 37, wherein the effluent stream further contains at least 500 wppm dimethyl ether.

54. The process of claim 37, wherein the effluent stream contains not greater than 50 weight percent dimethyl ether.

55. The process of claim 37, wherein the first fraction contains not greater than 100 wppm dimethyl ether.

56. The process of claim 37, wherein the first separation unit comprises a distillation column.

57. The process of claim 56, wherein a water absorbent is added to the distillation column.

58. The process of claim 57, wherein the water absorbent is added to the distillation column at a molar ratio of water absorbent to total effluent steam to be separated of from 4:

1 to 1;

5,000.

59. The process of claim 37, wherein the effluent stream contains from 50 to 95 combined weight percent ethylene and propylene, based on the total weight of the effluent stream.

60. The process of claim 37, wherein the effluent stream contains from 25 to 75 weight percent ethylene, based on the total weight of the effluent stream.

61. The process of claim 37, wherein the effluent stream contains from 25 to 75 weight percent propylene, based on the total weight of the effluent stream.

62. The process of claim 37, wherein the effluent stream further contains CO₂, and the first fraction further contains at least a majority of the CO₂ in the effluent stream.

63. The process of claim 62, wherein the process further comprises the step of acid gas treating the first fraction.

64. The process of claim 37, wherein the effluent stream further contains C₄+ hydrocarbon components, and the second fraction further contains at least a majority of the C₄+ hydrocarbon components present in the effluent stream.

65. The process of claim 40, wherein the process further comprises the step of polymerizing the ethylene from the seventh fraction.

66. The process of claim 45, wherein the process further comprises the step of polymerizing the propylene from the ninth fraction.

67. The process of claim 50, wherein the process further comprises the step of contacting the first fraction with water, acid gas treating the water contacted first fraction, and drying the acid gas treated first fraction.

68. The process of claim 37, wherein step (b) occurs at a pressure of less than 200 psig.

69. The process of claim 68, wherein the pressure is from 100 to 200 psig.

70. The process of claim 69, wherein the pressure is from 120 to 180 psig.

71. The process of claim 68, wherein the first separation unit comprises a distillation column.

72. The process of claim 71, wherein a water absorbent is added to the distillation column.

73. The process of claim 72, wherein the second fraction has an average temperature of not greater than 210°

F.

74. The process of claim 44, wherein at least a portion of the tenth fraction is recycled to the first separation unit.

75. A process for selectively hydrogenating acetylene, the process comprising the steps of:

(a) providing an effluent stream containing methane, acetylene, ethylene, ethane, propylene, propane and dimethyl ether;

(b) separating the effluent stream in a first separation unit into a first fraction and a second fraction, wherein the first fraction contains a first portion of the propane and a majority of the methane, ethane, ethylene and propylene present in the effluent stream, and wherein the second fraction contains a second portion of the propane and a majority of the dimethyl ether present in the effluent stream;

(c) separating at least a portion of the first fraction into a third fraction and a fourth fraction, wherein the third fraction contains a majority of the methane, ethylene and ethane present in the at least a portion of the first fraction, and wherein the fourth fraction contains a majority of the propylene and propane present in the at least a portion of the first fraction;

(d) separating at least a portion of the third fraction into a fifth fraction and a sixth fraction, wherein the fifth fraction contains a majority of the methane present in the at least a portion of the third fraction, and wherein the sixth fraction contains a majority of the ethylene and ethane present in the at least a portion of the third fraction;

(e) separating at least a portion of the sixth fraction into a seventh fraction and an eight fraction, wherein the seventh fraction contains a majority of the ethylene present in the at least a portion of the sixth fraction, and wherein the eighth fraction contains a majority of the ethane present in the at least a portion of the sixth fraction; and

(f) contacting acetylene in an acetylene-containing stream with hydrogen and carbon monoxide in a conversion unit under conditions effective to at least partially hydrogenate at least a portion of the acetylene in the acetylene-containing stream, wherein the acetylene-containing stream is selected from the group consisting of the sixth fraction and the seventh fraction.

76. The process of claim 75, wherein the acetylene-containing stream is the sixth fraction.

77. The process of claim 75, wherein the acetylene-containing stream is the seventh fraction.

78. A process for separating components from an olefin-containing effluent stream, the process comprising the steps of:

(a) providing the effluent stream, wherein the effluent stream contains ethane, ethylene, dimethyl ether, and propylene;

(b) separating the effluent stream into a first fraction and a second fraction, wherein the first fraction contains at least 5 weight percent of the dimethyl ether and a majority of the ethane, ethylene and propylene present in the effluent stream, and wherein the second fraction contains at least 5 weight percent of the dimethyl ether and a majority of the C4+ components present in the effluent stream; and

(c) separating at least a portion of the first fraction into a third fraction and a fourth fraction, wherein the fourth fraction contains a majority of the dimethyl ether present in the at least a portion of the first fraction.

79. The process of claim 78, wherein the third fraction contains a majority of the ethylene and ethane that was present in the first fraction, and wherein the fourth fraction further contains a majority of the propylene that was present in the first fraction.

80. The process of claim 79, wherein the process further comprises the step of separating at least a portion of the fourth fraction into a ninth fraction and a tenth fraction, wherein the ninth fraction contains a majority of the propylene present in the at least a portion of the fourth fraction, and wherein the tenth fraction contains a majority of the dimethyl ether present in the at least a portion of the fourth fraction.

81. The process of claim 80, wherein the tenth fraction further contains a majority of the propane that was present in the at least a portion of the fourth fraction.

82. The process of claim 78, wherein the effluent stream, the first fraction and the third fraction further contains methane, the process further comprising the step of separating at least a portion of the fourth fraction into a fifth fraction and a sixth fraction, wherein the fifth fraction contains a majority of the methane present in the at least a portion of the fourth fraction, and wherein the fifth fraction contains a majority of the ethane and ethylene present in the at least a portion of the fourth fraction.

83. The process of claim 82, wherein the process further comprises the step of separating at least a portion of the sixth fraction into a seventh fraction and an eighth fraction, wherein the seventh fraction contains a majority of the ethylene present in the at least a portion of the sixth fraction, and wherein the eighth fraction contains a majority of the ethane present in the at least a portion of the sixth fraction.

84. The process of claim 78, wherein the first fraction contains at least 10 weight percent of the dimethyl ether present in the effluent stream.

85. The process of claim 84, wherein the first fraction contains at least 20 weight percent of the dimethyl ether present in the effluent stream.

86. The process of claim 85, wherein the first fraction contains at least 60 weight percent of the dimethyl ether present in the effluent stream.

87. The process of claim 78, wherein the second fraction contains at least 10 weight percent of the dimethyl ether present in the effluent stream.

88. The process of claim 87, wherein the second fraction contains at least 20 weight percent of the dimethyl ether present in the effluent stream.

89. The process of claim 88, wherein the second fraction contains at least 30 weight percent of the dimethyl ether present in the effluent stream.

90. The process of claim 78, wherein the effluent stream and the first fraction further comprise methane and the third fraction contains a majority of the methane present in the at least a portion of the first fraction, and wherein the fourth fraction further contains a majority of the ethane, ethylene and propylene present in the first fraction.

91. The process of claim 90, wherein the process further comprises the step of separating at least a portion of the fourth fraction into a fifth fraction and a sixth fraction, wherein the fifth fraction contains a majority of the ethane and ethylene present in the at least a portion of the fourth fraction, and wherein the fifth fraction contains a majority of the dimethyl ether and propylene present in the at least a portion of the fourth fraction.

92. The process of claim 91, wherein the process further comprises the step of separating at least a portion of the fifth fraction into a seventh fraction and an eighth fraction, wherein the seventh fraction contains a majority of the ethylene present in the at least a portion of the fifth fraction, and wherein the eighth fraction contains a majority of the ethane present in the at least a portion of the sixth fraction.

93. The process of claim 91, wherein the process further comprises the step of separating at least a portion of the sixth fraction into a ninth fraction and a tenth fraction, wherein the ninth fraction contains a majority of the propylene present in the at least a portion of the sixth fraction, and wherein the tenth fraction contains a majority of the dimethyl ether present in the at least a portion of the sixth fraction.

94. The process of claim 93, wherein the effluent stream, the first fraction, the forth fraction and the sixth fraction further contain propane and wherein the tenth fraction further contains a majority of the propane that was present in the at least a portion of the sixth fraction.