CA2393753A1 - High temperature depressurization for naphtha mercaptan removal - Google Patents
High temperature depressurization for naphtha mercaptan removal Download PDFInfo
- Publication number
- CA2393753A1 CA2393753A1 CA002393753A CA2393753A CA2393753A1 CA 2393753 A1 CA2393753 A1 CA 2393753A1 CA 002393753 A CA002393753 A CA 002393753A CA 2393753 A CA2393753 A CA 2393753A CA 2393753 A1 CA2393753 A1 CA 2393753A1
- Authority
- CA
- Canada
- Prior art keywords
- naphtha
- process according
- catalyst
- sulfur
- hydrodesulfurizing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
- C10G65/02—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only
- C10G65/04—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including only refining steps
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/02—Gasoline
Landscapes
- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Catalysts (AREA)
Abstract
The invention relates to naphtha hydrodesulfurization incorporating either high temperature depressurization or controlled heating for mercaptan remova l. More particularly, the invention relates to a naphtha hydrodesulfurization process, wherein the hot naphtha exiting the desulfurization reactor (12) contains mercaptans, most of which are removed without olefin loss, by depressurizing the hot naphtha (14), thermally treating the hot naphtha, or some combination thereof. The desulfurized naphtha may be cooled and condens ed to a liquid, separated (16) from the gaseous H2S, stripped and sent to a mog as pool.
Claims (25)
1. A naphtha desulfurization process, comprising (a) hydrodesulfurizing a naphtha which contains olefins and sulfur in the form of organic sulfur compounds, to form a hydrodesulfurization effluent at an initial temperature, the hydrodesulfurization effluent comprising a hot mixture of sulfur reduced naphtha at an initial pressure, H2S and mercaptans, and then (b) rapidly depressurizing for a depressurization time at least a portion of the hydrodesulfurization effluent to destroy at least a portion of the mercaptans to form more H2S and a depressurized naphtha further reduced in sulfur.
2. A process according to claim 1 wherein the hydrodesulfurizing is conducted in the presence of a catalytically effective amount of a hydrodesulfurizing catalyst under catalytic hydrodesulfurization conditions, wherein the hydrodesulfurizing catalyst comprises at least one Group VIII
catalytic metal component and a support component, and wherein said naphtha feed contains at least 0.1 wt.% sulfur.
catalytic metal component and a support component, and wherein said naphtha feed contains at least 0.1 wt.% sulfur.
3. A process according to claim 1 wherein said hot mixture is depressurized to a final pressure of no more than 50% of the initial pressure, wherein said depressurization temperature is no less than the initial temperature, and wherein the depressurization time is sufficient for the effluent to reach thermodynamic equilibrium at the final pressure.
4. A process according to claim 2 wherein the catalytic metal component contains at least one Group VIII metal and at least one Group VI
metal.
metal.
5. A process according to clam 2 further comprising separating said H2S from said depressurized naphtha.
6. A process according to claim 5 wherein said hydrodesulfurizing catalyst comprises Co and Mo catalytic metal components and wherein said naphtha feed contains from 0.1 to 0.7 wt.% sulfur in the form of organic sulfur compounds, and from 5 to 60 vol.% olefins.
7. A process according to claim 4 wherein the final pressure ranges from about atmospheric pressure to about 300 psig, and the depressurization time ranges from 0.5 seconds to 10 minutes.
8. A process according to claim 3 wherein said depressurization temperature is greater than the initial temperature.
9. A process according to claim 8 wherein the total amount of said Co and Mo catalytic metal components, calculated as CoO and MoO3 is no greater than 12 wt.% of the total weight of said catalyst.
10. The process of claim 1, further comprising conducting the rapid depressurizing in the presence of a second catalyst in an amount effective to catalyze the decomposition of said mercaptans to H2S.
11. The process of claim 10 wherein the second catalyst comprises at least one neutral or alkaline metal oxide.
12. The process of claim 1 wherein the hydrodesulfurization conditions include a temperature of from 400-800°F and a pressure of from 60-2000 psig, a space velocity of about 0.1 to about 10, and a hydrogen treat gas rate of about 200 to about 5000 scf/b.
13. The process of claim 11 wherein hydrogen is present during the rapid depressurization.
14. The process of claim 11 wherein the second catalyst is alumina.
15. The process of claim 11 wherein the second catalyst does not have a hydrogenation function.
16. A naphtha desulfurization process, comprising:
(a) hydrodesulfurizing a naphtha, the naphtha containing olefins and sulfur in the form of organic sulfur compounds, to form a hydrodesulfurization effluent at an initial temperature, the effluent comprising a hot mixture of sulfur reduced naphtha, H2S and mercaptans; and then (b) heating at least a portion of the hydrodesulfurization effluent to a final temperature greater than the initial temperature at a substantially constant total pressure for a heating time to destroy at least a portion of the mercaptans to form more H2S and a treated naphtha further reduced in sulfur.
(a) hydrodesulfurizing a naphtha, the naphtha containing olefins and sulfur in the form of organic sulfur compounds, to form a hydrodesulfurization effluent at an initial temperature, the effluent comprising a hot mixture of sulfur reduced naphtha, H2S and mercaptans; and then (b) heating at least a portion of the hydrodesulfurization effluent to a final temperature greater than the initial temperature at a substantially constant total pressure for a heating time to destroy at least a portion of the mercaptans to form more H2S and a treated naphtha further reduced in sulfur.
17. The process of claim 16, further comprising separating the H2S
from the treated naphtha.
from the treated naphtha.
18. A process according to claim 17 wherein the hydrodesulfurizing is conducted in the presence of a catalytically effective amount of a hydrodesulfurizing catalyst under catalytic hydrodesulfurization conditions, wherein the hydrodesulfurizing catalyst comprises at least one Group VIII
catalytic metal component and a support component, and wherein said naphtha feed contains at least 0.1 wt.% sulfur.
catalytic metal component and a support component, and wherein said naphtha feed contains at least 0.1 wt.% sulfur.
19. A process according to claim 18 wherein the catalytic metal component contains at least one Group VIII metal and at least one Group VI
metal.
metal.
20. A process according to claim 16 wherein said hydrodesulfurization catalyst comprises Co and Mo catalytic metal components and wherein said naphtha feed contains from 0.1 to 0.7 wt.% sulfur in the form of organic sulfur compounds, and from 5 to 60 vol.% olefins.
21. A process according to claim 16 wherein the final temperature ranges from about 0°C to about 100°C above the initial temperature and wherein the heating time ranges from about 0.5 seconds to about 10 minutes.
22. A process according to claim 20 wherein the total amount of said Co and Mo catalytic metal components, calculated as CoO and MoO3 is no greater than 12 wt.% of the total weight of said catalyst.
23. The process of claim 16, further comprising conducting the heating in the presence of a second catalyst in an amount effective to catalyze the decomposition of said mercaptans to H2S.
24. The process of claim 23 wherein the second catalyst wherein the second catalyst comprises at least one neutral or alkaline metal oxide.
25. The process of claim 18 wherein the hydrodesulfurization conditions include a temperature of from 400-800°F and a pressure of from 60 2000 psig, a space velocity of about 0.1 to about 10, and a hydrogen treat gas rate of about 200 to about 5000 scf/b.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA2680472A CA2680472C (en) | 1999-12-22 | 2000-12-05 | High temperature depressurization for naphtha mercaptan removal |
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US47026799A | 1999-12-22 | 1999-12-22 | |
| US09/470,267 | 1999-12-22 | ||
| US09/685,709 US6387249B1 (en) | 1999-12-22 | 2000-10-10 | High temperature depressurization for naphtha mercaptan removal |
| US09/685,709 | 2000-10-10 | ||
| PCT/US2000/035701 WO2001094502A1 (en) | 1999-12-22 | 2000-12-05 | High temperature depressurization for naphtha mercaptan removal |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA2680472A Division CA2680472C (en) | 1999-12-22 | 2000-12-05 | High temperature depressurization for naphtha mercaptan removal |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2393753A1 true CA2393753A1 (en) | 2001-12-31 |
| CA2393753C CA2393753C (en) | 2010-07-20 |
Family
ID=27043031
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA2393753A Expired - Lifetime CA2393753C (en) | 1999-12-22 | 2000-12-05 | High temperature depressurization for naphtha mercaptan removal |
Country Status (6)
| Country | Link |
|---|---|
| EP (1) | EP1268711A4 (en) |
| JP (1) | JP4681794B2 (en) |
| AU (1) | AU769356B2 (en) |
| CA (1) | CA2393753C (en) |
| NO (1) | NO20023022L (en) |
| WO (1) | WO2001094502A1 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7419586B2 (en) * | 2004-12-27 | 2008-09-02 | Exxonmobil Research And Engineering Company | Two-stage hydrodesulfurization of cracked naphtha streams with light naphtha bypass or removal |
| FR2888583B1 (en) * | 2005-07-18 | 2007-09-28 | Inst Francais Du Petrole | NOVEL METHOD OF DESULFURIZING OLEFINIC ESSENCES FOR LIMITING THE MERCAPTAN CONTENT |
| US20070114156A1 (en) * | 2005-11-23 | 2007-05-24 | Greeley John P | Selective naphtha hydrodesulfurization with high temperature mercaptan decomposition |
Family Cites Families (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2206921A (en) * | 1936-10-06 | 1940-07-09 | Phillips Petroleum Co | Process for desulphurization of hydrocarbons |
| GB1174407A (en) * | 1966-12-05 | 1969-12-17 | British Petroleum Co | Preparation of Olefins. |
| BE758565A (en) * | 1969-11-18 | 1971-05-06 | Shell Int Research | PROCEDURE FOR THE CATALYTIC HYDROGENATING CONVERSION OF A RESIDUAL CARBON HYDROGEN OIL |
| US3720602A (en) * | 1971-02-26 | 1973-03-13 | Exxon Research Engineering Co | Water injection in a hydrodesulfurization process |
| US3732155A (en) * | 1971-03-31 | 1973-05-08 | Exxon Research Engineering Co | Two-stage hydrodesulfurization process with hydrogen addition in the first stage |
| US3801494A (en) * | 1972-09-15 | 1974-04-02 | Standard Oil Co | Combination hydrodesulfurization and reforming process |
| US4218309A (en) * | 1978-09-08 | 1980-08-19 | Occidental Research Corporation | Removal of sulfur from shale oil |
| EP0202772A3 (en) * | 1985-05-13 | 1988-07-27 | Mobil Oil Corporation | Oil upgrading by thermal processing |
| US5318690A (en) * | 1991-08-15 | 1994-06-07 | Mobil Oil Corporation | Gasoline upgrading process |
| US5525211A (en) * | 1994-10-06 | 1996-06-11 | Texaco Inc. | Selective hydrodesulfurization of naphtha using selectively poisoned hydroprocessing catalyst |
| JP3387700B2 (en) * | 1995-07-26 | 2003-03-17 | 新日本石油株式会社 | Desulfurization method of catalytic cracking gasoline |
-
2000
- 2000-12-05 CA CA2393753A patent/CA2393753C/en not_active Expired - Lifetime
- 2000-12-05 JP JP2002502047A patent/JP4681794B2/en not_active Expired - Fee Related
- 2000-12-05 WO PCT/US2000/035701 patent/WO2001094502A1/en active IP Right Grant
- 2000-12-05 AU AU26114/01A patent/AU769356B2/en not_active Ceased
- 2000-12-05 EP EP00989628A patent/EP1268711A4/en not_active Withdrawn
-
2002
- 2002-06-21 NO NO20023022A patent/NO20023022L/en not_active Application Discontinuation
Also Published As
| Publication number | Publication date |
|---|---|
| NO20023022D0 (en) | 2002-06-21 |
| JP4681794B2 (en) | 2011-05-11 |
| JP2003535955A (en) | 2003-12-02 |
| EP1268711A4 (en) | 2004-06-09 |
| NO20023022L (en) | 2002-08-21 |
| EP1268711A1 (en) | 2003-01-02 |
| CA2393753C (en) | 2010-07-20 |
| WO2001094502A1 (en) | 2001-12-13 |
| AU769356B2 (en) | 2004-01-22 |
| AU2611401A (en) | 2001-12-17 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EEER | Examination request | ||
| MKEX | Expiry |
Effective date: 20201207 |