Wax isomerate yield enhancement by oxygenate pretreatment of feed
원문보기
IPC분류정보
국가/구분
United States(US) Patent
등록
국제특허분류(IPC7판)
C10G-069/08
C10G-069/00
C10G-073/02
C10G-073/00
출원번호
US-0678684
(2003-10-03)
발명자
/ 주소
Cody,Ian A.
Murphy,William J.
Hantzer,Sylvain
출원인 / 주소
ExxonMobil Research and Engineering Company
인용정보
피인용 횟수 :
4인용 특허 :
83
초록▼
A waxy hydrocarbon feed is catalytically dewaxed with a catalyst that has been selectively activated. The selective activation of the catalyst involves contacting the dewaxing catalyst with a feed mixture containing waxy hydrocarbon and at least one oxygenate. The process results in improved catalys
A waxy hydrocarbon feed is catalytically dewaxed with a catalyst that has been selectively activated. The selective activation of the catalyst involves contacting the dewaxing catalyst with a feed mixture containing waxy hydrocarbon and at least one oxygenate. The process results in improved catalyst performance resulting in improved yield of isomerate at equivalent pour.
대표청구항▼
The invention claimed is: 1. A process for catalytically dewaxing a waxy mineral hydrocarbon feed which comprises: (a) forming a mixture containing the waxy hydrocarbon feed and from 100 wppm to 10000 wppm of at least one oxygenate; and (b) contacting the mixture from step (a) with a dewaxing catal
The invention claimed is: 1. A process for catalytically dewaxing a waxy mineral hydrocarbon feed which comprises: (a) forming a mixture containing the waxy hydrocarbon feed and from 100 wppm to 10000 wppm of at least one oxygenate; and (b) contacting the mixture from step (a) with a dewaxing catalyst which functions by isomerizing waxy molecules under conditions effective to catalytically dewax the feed. 2. The process of claim 1 wherein the waxy hydrocarbon feed contains at least about 15 wt. % wax, based on feed. 3. The process of claim 1 wherein the oxygenate is at least one alcohol, carboxylic acid, ester, aldehyde, ketone or ether. 4. The process of claim 1 wherein the oxygenate is water. 5. The process of claim 1 wherein the amount of oxygenate in the mixture is at least about 100 wppm, measured as oxygen. 6. The process of claim 1 wherein the dewaxing catalyst contains at least one molecular sieve containing at least one 10 or 12 ring channel. 7. The process of claim 6 wherein the molecular sieve is at least one of ZSM-5, ZSM-11, ZSM-22, ZSM-23, ZSM-35, ZSM-48, ZSM-57, ferrierite, EU-1, NU-87, SAPO-11, SAPO-41, ITQ-13 or MCM-71. 8. The process of claim 6 wherein the molecular sieve is at least one of zeolite beta, ZSM-12, MCM-68, SAPO-5, SAPO-31, MAPO-36, ZSM-18, offretite, mordenite or faujasite. 9. The process of claim 6 wherein the molecular sieve is ZSM-48. 10. The process of claim 1 wherein the conditions effective to catalytically dewax the feed include a temperature of from 250 to 400째 C., a pressure of from 791 to 20786 kPa, a liquid hourly space velocity of from 0.1 to 10 hr-1 and a treat gas rate of from 45 to 1780 m3/m3. 11. The process of claim 1 wherein catalytic dewaxing of feed results in improved yield of isomerate boiling in the lube oil range at equivalent pour over the dewaxing catalyst without oxygenate treatment. 12. The process of claim 11 wherein the improved yield is at least 4 relative percent. 13. The process of claim 1 wherein the dewaxing catalyst is sulfided, reduced, or sulfided and reduced. 14. The process of claim 1 wherein the dewaxing catalyst bears a metal hydrogenation component. 15. The process of claim 14 wherein the metal hydrogenation component is at least one Group 9 or 10 noble metal. 16. A process for catalytically dewaxing a mineral hydrocarbon feed containing at least 15 wt. % wax, based on hydrocarbon feed, which comprises: (a) forming a mixture containing the hydrocarbon feed and at least one oxygenate wherein the amount of oxygenate in the mixture is at least about 100 wppm to 10000 wppm measured as oxygen, and (b) contacting the mixture from step (a) with a dewaxing catalyst which functions by isomerizing waxy molecules and contains at least one molecular sieve containing at least one 10 or 12 ring channel under conditions effective to catalytically dewax the feed. 17. The process of claim 16 wherein the oxygenate is at least one alcohol, carboxylic acid, ester, aldehyde, ketone or ether. 18. The process of claim 16 wherein the oxygenate is water. 19. The process of claim 16 wherein the molecular sieve is at least one of ZSM-5, ZSM-11, ZSM-22, ZSM-23, ZSM-35, ZSM-48, ZSM-57, ferrierite, EU-1, NU-7, SAPO-11, SAPO-41, ITQ-13 or MCM-71. 20. The process of claim 16 wherein the molecular sieve is at least one of zeolite beta, ZSM-12, MCM-68, SAPO-5, SAPO-31, MAPO-36, ZSM-18, offretite, mordenite or faujasite. 21. The process of claim 19 wherein the molecular sieve is ZSM-48. 22. The process of claim 16 wherein the conditions effective to catalytically dewax the feed include a temperature of from 250 to 400째 C., a pressure of from 791 to 20786 kPa, a liquid hourly space velocity of from 0.1 to 10 hr-1 and a treat gas rate of from 45 to 1780 m3/m3. 23. The process of claim 16 wherein catalytic dewaxing of feed results in improved yield of isomerate boiling in the lube oil range at equivalent pour over the dewaxing catalyst without oxygenate treatment. 24. The process of claim 23 wherein the improved yield is at least 4 relative percent. 25. The process of claim 16 wherein the dewaxing catalyst is sulfided, reduced, or sulfided and reduced. 26. The process of claim 16 wherein the dewaxing catalyst bears a metal hydrogenation component. 27. The process of claim 26 wherein the metal hydrogenation component is at least one Group 9 or 10 noble metal. 28. A process for catalytically dewaxing a mineral hydrocarbon feed containing at least about 15 wt. % wax, based on hydrocarbon feed, which comprises: (a) forming a mixture containing the hydrocarbon feed and at least one alcohol, carboxylic acid, ester, aldehyde, ketone or ether wherein the amount of oxygen in the mixture is at least about 100 wppm to 10000 wppm, measured as oxygen, and (b) contacting the mixture from step (a) with a dewaxing catalyst which functions by isomerizing waxy molecules and contains at least one molecular sieve containing at least one 10 or 12 ring channel under conditions effective to catalytically dewax the feed. 29. The process of claim 28 wherein the molecular sieve is at least one of ZSM-5, ZSM-11, ZSM-22, ZSM-23, ZSM-35, ZSM-48, ZSM-57, ferrierite, EU-1, NU-87, SAPO-11, SAPO-41, ITQ-13 or MCM-71. 30. The process of claim 28 wherein the molecular sieve is at least one of zeolite beta, ZSM-12, MCM-68 SAPO-5, SAPO-31, MAPO-36, ZSM-18, offretite, mordenite or faujasite. 31. The process of claim 29 wherein the molecular sieve is ZSM-48. 32. The process of claim 28 wherein the conditions effective to catalytically dewax the feed include a temperature of from 250 to 400째 C., a pressure of from 791 to 20786 kPa, a liquid hourly space velocity of from 0.1 to 10 hr-1 and a treat gas rate of from 45 to 1780 m3/m3. 33. The process of claim 28 wherein catalytic dewaxing of feed results in improved yield of isomerate boiling in the lube oil range at equivalent pour over the dewaxing catalyst without oxygenate treatment. 34. The process of claim 33 wherein the improved yield is at least 4 relative percent. 35. The process of claim 28 wherein the dewaxing catalyst is sulfided, reduced, or sulfided and reduced. 36. The process of claim 28 wherein the dewaxing catalyst bears a metal hydrogenation component. 37. The process of claim 36 wherein the metal hydrogenation component is at least one Group 9 or 10 noble metal. 38. A process for catalytically dewaxing a mineral hydrocarbon feed containing at least 15 wt. % wax, based on hydrocarbon, feed which comprises: (a) hydrotreating the hydrocarbon feed in the presence of a hydrotreating catalyst under hydrotreating conditions to produce a hydrotreated feed and sulfur-and nitrogen-containing contaminants; (b) separating the hydrotreated feed from the sulfur-and nitrogen-containing contaminants; (c) adding to the separated hydrotreated feed at least one alcohol, carboxylic acid, ester, aldehyde, ketone or ether wherein the amount of oxygen in the separated hydrotreated feed mixture is at least about 100 wppm to 10000 wppm measured as oxygen; and (d) contacting the mixture from step (c) with a dewaxing catalyst which functions by isomerizing waxy molecules and contains a molecular sieve containing at least one 10 or 12 ring channel under conditions effective to catalytically dewax the feed. 39. The process of claim 38 wherein the molecular sieve is at least one of ZSM-5, ZSM-11, ZSM-22, ZSM-23, ZSM-35, ZSM-48, ZSM-57, ferrierite, EU-1, NU-87, SAPO-11, SAPO-41, ITQ-13 or MCM-71. 40. The process of claim 38 wherein the molecular sieve is at least one of zeolite bets, ZSM-12, MCM-68 SAPO-5, SAPO-31, MAPO-36, ZSM-18, offretite, mordenite or faujasite. 41. The process of claim 39 wherein the molecular sieve is ZSM-48. 42. The process of claim 38 wherein the conditions effective to catalytically isomerize the feed include a temperature of from 250 to 400째 C., a pressure of from 791 to 20786 kPa, a liquid hourly space velocity of from 0.1 to 10 hr-1 and a treat gas rate of from 45 to 1780 m3/m3. 43. The process of claim 38 wherein catalytic dewaxing of feed results in improved yield of isomerate boiling in the lube oil range at equivalent pour over the dewaxing catalyst without oxygenate treatment. 44. The process of claim 43 wherein the improved yield is at least 4 relative percent. 45. The process of claim 38 wherein the dewaxing catalyst is sulfided, reduced, or sulfided and reduced. 46. The process of claim 38 wherein the dewaxing catalyst bears a metal hydrogenation component. 47. The process of claim 46 wherein the metal hydrogenation component is at least one Group 9 or 10 noble metal. 48. A process for catalytically dewaxing a mineral hydrocarbon feed containing at least about 15 wt % wax, based on hydrocarbon feed, which comprises: (a) forming a mixture containing the hydrocarbon feed and water wherein the amount of oxygen in the mixture is at least about 100 wppm to 10000 wppm, measured as oxygen, and (b) contacting the mixture from step (a) with a dewaxing catalyst which functions by isomerizing waxy molecules and contains at least one molecular sieve containing at least one 10 or 12 ring channel under conditions effective to catalytically dewax the feed. 49. A process for catalytically dewaxing a mineral hydrocarbon feed containing at least 15 wt. % wax, based on hydrocarbon feed which comprises: (a) forming a mixture containing the hydrocarbon feed and at least one alcohol, carboxylic acid, ester, aldehyde, ketone or ether wherein the amount of oxygen in the mixture is at least about 100 wppm to 1000 wppm, measured as oxygen, and (b) contacting the mixture from step (a) with a dewaxing catalyst which is ZSM-48 under conditions effective to catalytically dewax the feed. 50. The process of claim 49 wherein the conditions effective to catalytically dewax the feed include a temperature of from 250 to 400째 C., a pressure of from 791 to 20786 kPa, a liquid hourly space velocity of from 0.1 to 10 hr-1 and a treat gas rate of from 45 to 1780 m3/m3. 51. The process of claim 49 wherein catalytic dewaxing of feed results in improved yield of isomerate boiling in the lube oil range at equivalent pour over the dewaxing catalyst without oxygenate treatment. 52. The process of claim 49 wherein the improved yield is at least 4 relative percent. 53. The process of claim 52 wherein the dewaxing catalyst is sulfided, reduced, or sulfided and reduced. 54. The process of claim 49 wherein the dewaxing catalyst bears a metal hydrogenation component. 55. The process of claim 54 wherein the metal hydrogenation component is at least one Group 9 or 10 noble metal. 56. A process for catalytically dewaxing a Fischer-Tropsch wax containing greater than 0.5 wppm sulfur, based on Fischer-Tropsch wax, which comprises: (a) forming a mixture containing the hydrocarbon feed and at least one oxygenate wherein the amount of oxygenate in the mixture is at least about 100 wppm to 10000 wppm, measured as oxygen, and (b) contacting the mixture from step (a) with a dewaxing catalyst which functions by isomerizing waxy molecules and contains at least one molecular sieve containing at least one 10 or 12 ring under conditions effective to catalytically dewax the feed. 57. The process of claim 56 wherein the oxygenate is at least one alcohol, carboxylic acid, ester, aldehyde, ketone or ether. 58. The process of claim 56 wherein the oxygenate is water. 59. The process of claim 56 wherein the molecular sieve is at least one of ZSM-5, ZSM-11, ZSM-22, ZSM-23, ZSM-35, ZSM-48, ZSM-57, ferrierite, EU-1, NU-87, SAPO-11, SAPO-41, ITQ-13 or MCM-71. 60. The process of claim 56 wherein the molecular sieve is at least one of zeolite beta, ZSM-12, MCM-68, SAPO-5, SAPO-31, MAPO-36, ZSM-18, offretite, mordenite or faujasite. 61. The process of claim 59 wherein the molecular sieve is ZSM-48. 62. The process of claim 56 wherein the conditions effective to catalytically dewax the feed include a temperature of from 250 to 400째 C., a pressure of from 791 to 20786 kPa, a liquid hourly space velocity of from 0.1 to 10 hr-1 and a treat gas rate of from 45 to 1780 m3/m3. 63. The process of claim 56 wherein catalytic dewaxing of feed results in improved yield of isomerate boiling in the lube oil range at equivalent pour over the dewaxing catalyst without oxygenate treatment. 64. The process of claim 63 wherein the improved yield is at least 4 relative percent. 65. The process of claim 56 wherein the dewaxing catalyst is sulfided, reduced, or sulfided and reduced. 66. The process of claim 56 wherein the dewaxing catalyst bears a metal hydrogenation component. 67. The process of claim 56 wherein the metal hydrogenation component is at least one Group 9 or 10 noble metal. 68. The process of claim 56 wherein the Fischer-Tropsch wax is hydrotreated prior to step (a).
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이 특허에 인용된 특허 (83)
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