CA2680472A1 - High temperature depressurization for naphtha mercaptan removal - Google Patents

High temperature depressurization for naphtha mercaptan removal Download PDF

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Publication number
CA2680472A1
CA2680472A1 CA002680472A CA2680472A CA2680472A1 CA 2680472 A1 CA2680472 A1 CA 2680472A1 CA 002680472 A CA002680472 A CA 002680472A CA 2680472 A CA2680472 A CA 2680472A CA 2680472 A1 CA2680472 A1 CA 2680472A1
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Prior art keywords
naphtha
sulfur
hydrodesulfurization
process according
hydrodesulfurizing
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Granted
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CA002680472A
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French (fr)
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CA2680472C (en
Inventor
Bruce Randall Cook
Richard Harry Ernst
Richard Alan Demmin
John Peter Greeley
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ExxonMobil Technology and Engineering Co
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Individual
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Priority claimed from CA2393753A external-priority patent/CA2393753C/en
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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
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
    • C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
    • 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
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
    • C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
    • C10G45/06—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
    • C10G45/08—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum, or tungsten metals, or compounds thereof
    • 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
    • C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
    • C10G67/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only
    • 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
    • C10G69/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process
    • C10G69/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only
    • 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
    • C10G69/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process
    • C10G69/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only
    • C10G69/06—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only including at least one step of thermal cracking in the absence of hydrogen
    • 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
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1037—Hydrocarbon fractions
    • C10G2300/1044—Heavy gasoline or naphtha having a boiling range of about 100 - 180 °C
    • 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
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/20—Characteristics of the feedstock or the products
    • C10G2300/201—Impurities
    • C10G2300/202—Heteroatoms content, i.e. S, N, O, P
    • 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
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/20—Characteristics of the feedstock or the products
    • C10G2300/201—Impurities
    • C10G2300/207—Acid gases, e.g. H2S, COS, SO2, HCN
    • 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
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/40—Characteristics of the process deviating from typical ways of processing
    • C10G2300/4018—Spatial velocity, e.g. LHSV, WHSV
    • 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

Abstract

The invention relates to naphtha hydrodesulfurization incorporating either high temperature depressurization or controlled heating for mercaptan removal. 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 condensed to a liquid, separated (16) from the gaseous H2S, stripped and sent to a mogas pool.

Claims (10)

1. 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.
2. The process of claim 1, further comprising separating the H2S from the treated naphtha.
3. A process according to claim 2, 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.
4. A process according to claim 3, wherein the catalytic metal component contains at least one Group VIII metal and at least one Group VI metal.
5. A process according to claim 1, 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.
6. A process according to claim 1, 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.
7. A process according to claim 5, 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.
8. The process of any one of claims 1 to 7, 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.
9. The process of claim 8, wherein the second catalyst comprises at least one neutral or alkaline metal oxide.
10. The process of claim 3, 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.
CA2680472A 1999-12-22 2000-12-05 High temperature depressurization for naphtha mercaptan removal Expired - Lifetime CA2680472C (en)

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 2000-10-10
US09/685,709 US6387249B1 (en) 1999-12-22 2000-10-10 High temperature depressurization for naphtha mercaptan removal
CA2393753A CA2393753C (en) 1999-12-22 2000-12-05 High temperature depressurization for naphtha mercaptan removal

Related Parent Applications (1)

Application Number Title Priority Date Filing Date
CA2393753A Division CA2393753C (en) 1999-12-22 2000-12-05 High temperature depressurization for naphtha mercaptan removal

Publications (2)

Publication Number Publication Date
CA2680472A1 true CA2680472A1 (en) 2001-12-31
CA2680472C CA2680472C (en) 2012-07-03

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CA2680472A Expired - Lifetime CA2680472C (en) 1999-12-22 2000-12-05 High temperature depressurization for naphtha mercaptan removal

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US (1) US6387249B1 (en)
EP (1) EP2031042B1 (en)
CA (1) CA2680472C (en)
ES (1) ES2655285T3 (en)

Families Citing this family (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7799210B2 (en) * 2004-05-14 2010-09-21 Exxonmobil Research And Engineering Company Process for removing sulfur from naphtha
US7507328B2 (en) * 2004-12-27 2009-03-24 Exxonmobile Research And Engineering Company Selective hydrodesulfurization and mercaptan decomposition process with interstage separation
US20060144757A1 (en) * 2004-12-30 2006-07-06 Steffens Todd R FCC feed injection for atomizing feed
US7670478B2 (en) * 2004-12-30 2010-03-02 Exxonmobil Research And Engineering Company FCC feed injection system
US20070114156A1 (en) * 2005-11-23 2007-05-24 Greeley John P Selective naphtha hydrodesulfurization with high temperature mercaptan decomposition
CN101130438B (en) * 2006-08-22 2010-05-12 中国科学院过程工程研究所 Combination device for adsorption desulfurization and biological reactivation adsorption agent, and operating method thereof
US7837861B2 (en) * 2006-10-18 2010-11-23 Exxonmobil Research & Engineering Co. Process for benzene reduction and sulfur removal from FCC naphthas
US20080093265A1 (en) * 2006-10-18 2008-04-24 Exxonmobil Research And Engineering Company Process for selective sulfur removal from FCC naphthas using zeolite catalysts
EP2816094B1 (en) 2013-06-19 2020-04-29 IFP Energies nouvelles Method for producing gasoline with low sulphur and mercaptan content
US10144883B2 (en) 2013-11-14 2018-12-04 Uop Llc Apparatuses and methods for desulfurization of naphtha
US9891011B2 (en) 2014-03-27 2018-02-13 Uop Llc Post treat reactor inlet temperature control process and temperature control device
US9850435B2 (en) 2014-08-26 2017-12-26 Exxonmobil Research And Engineering Company Hydroprocessing with drum blanketing gas compositional control
FR3049955B1 (en) 2016-04-08 2018-04-06 IFP Energies Nouvelles PROCESS FOR TREATING A GASOLINE
FR3057578B1 (en) 2016-10-19 2018-11-16 IFP Energies Nouvelles PROCESS FOR HYDRODESULFURING OLEFINIC ESSENCE
CA3049804A1 (en) 2017-02-21 2018-08-30 Exxonmobil Research And Engineering Company Desulfurization of a naphtha boiling range feed
FR3099173B1 (en) * 2019-07-23 2021-07-09 Ifp Energies Now PROCESS FOR THE PRODUCTION OF A GASOLINE WITH LOW SULFUR AND MERCAPTANS

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JP3387700B2 (en) 1995-07-26 2003-03-17 新日本石油株式会社 Desulfurization method of catalytic cracking gasoline

Also Published As

Publication number Publication date
ES2655285T3 (en) 2018-02-19
EP2031042A1 (en) 2009-03-04
EP2031042B1 (en) 2017-11-08
CA2680472C (en) 2012-07-03
US6387249B1 (en) 2002-05-14

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