EP0462823A1 - Entschwefelung und Entmetallisierung von Rückständen - Google Patents

Entschwefelung und Entmetallisierung von Rückständen Download PDF

Info

Publication number
EP0462823A1
EP0462823A1 EP91305552A EP91305552A EP0462823A1 EP 0462823 A1 EP0462823 A1 EP 0462823A1 EP 91305552 A EP91305552 A EP 91305552A EP 91305552 A EP91305552 A EP 91305552A EP 0462823 A1 EP0462823 A1 EP 0462823A1
Authority
EP
European Patent Office
Prior art keywords
resid
alumina
silica
diluent
blend
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
Application number
EP91305552A
Other languages
English (en)
French (fr)
Other versions
EP0462823B1 (de
Inventor
Byung Chang Choi
Philip Mobil Oil Singapore Pte Ltd. Varghese
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
ExxonMobil Oil Corp
Original Assignee
Mobil Oil Corp
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Mobil Oil Corp filed Critical Mobil Oil Corp
Publication of EP0462823A1 publication Critical patent/EP0462823A1/de
Application granted granted Critical
Publication of EP0462823B1 publication Critical patent/EP0462823B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

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
    • 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

Definitions

  • This invention relates to improved demetalation and desulfurization of resids, e.g. vacuum resids.
  • demetalation and/or desulfurization are undertaken to substantially reduce or remove contaminants from the resid.
  • the contaminants would interfere with catalysts, for example as poisons, in subsequent catalytic processing of the resid such as in the production of gasoline.
  • the invention relates to contacting a resid with gas oil, a distillate, or FCC cycle stock diluent, under conditions including hydrogen pressures ranging from 4240 to 27,700 kPa (600 to 4000 psig); space velocities (WHSV) from 0.05 to 10, and temperatures ranging from 316 to 468°C (600° to 875°F) over a catalyst comprising silica, alumina or silica-alumina.
  • WHSV space velocities
  • Figure 1 is a plot of the fraction of (nickel in the product)/(nickel in the feed) vs. WHSV and illustrates the effect of light cycle oil (LCO) on Nickel removal.
  • LCO light cycle oil
  • Figure 2 wherein the fraction of (vanadium in the product)/(vanadium in the feed) is plotted against WHSV illustrates the effect of LCO on vanadium removal.
  • Figure 3 illustrates the effect of LCO on resid desulfurization, wherein the change in sulfur in the resid is plotted against WHSV
  • Figure 4 is a plot of nickel vs. WHSV and shows the effect of diluent on demetalation of 850+ bottom.
  • Figure 5 is a plot of vanadium vs. WHSV and illustrates the effect of diluent on demetalation of 850+ bottom.
  • Figure 6 is a plot of sulfur vs. WHSV and illustrates the effect of diluent on desulfurization of 850+ bottom.
  • the objective of hydrotreating resids is to remove metals such as Ni and V, reduce product S, and reduce product CCR.
  • Kinetic limitations and catalyst fouling by carbonaceous deposits and metal deposits are two common problems encountered in such processing.
  • Atmospheric resids boil above 316 to 427°C (600° to 800°F), while vacuum resids boil above 482° up to 593°C (900° up to about 1100°F).
  • the resid which is subjected to demetalation and/or desulfurization, in accordance with the invention is a vacuum resid.
  • Resids are, by definition, the unevaporated liquid or solid bottoms from processes of distillation or cracking of petroleum crudes.
  • Vacuum resids result from vacuum distillation which is undertaken, under reduced pressure, to reduce the distillation temperature and the boiling temperature of the distilled material to prevent decomposition and cracking of the material being distilled. Accordingly, in preferred embodiments of the process the first stage is providing a vacuum resid; this involves previousl undertaking is a vacuum distillation of petroleum crude to provide the vacuum resid, by standard methods.
  • Lower boiling diluents for the resid include atmospheric and vacuum gas oils, or cracked distillates such as LCO (light cycle oil) and HCO (heavy cycle oil).
  • Gas oil is a petroleum distillate with a viscosity intermediate between kerosene and lubricating oil, boiling in the range of 204° to 427°C (about 400° to about 800°F).
  • Distillate includes gasoline, kerosene and light lubrication oil.
  • the diluent is an aromatic stream such as cracked FCC distillate. Cracked distillate, as an aromatic stream, includes LCO and HCO. Combination of the resid with the aromatic stream provided by cracked distillate, in the process of the invention, results in a beneficial impact on catalyst deactivation.
  • the resid is blended with the lower boiling diluent.
  • the resulting blend can contain up to 50 volume percent of the diluent. Practically, the blend will contain about 10 to 30 volume percent of the diluent.
  • Optimum levels of dilution are determined for each combination of vacuum resid and diluent; optimum levels of dilution are amounts of diluents lower boiling than the resid effective to increase the dematalation and desulfurization of the resid under the hydroprocessing conditions reported below.
  • rate enhancement of either or both demetalation and desulfurization, can be up to one hundred percent (100%). At one hundred percent rate enhancement with a specific diluent, rate enhancement will tend to be greater as the viscosity of the resid to be treated. The viscosity of the resid will vary with its source.
  • the blend of resid and diluent can be subjected to the following hydroprocessing conditions in fixed-, ebullated-, or moving-bed reactors that are well known in the art for dematalation and desulfurization of petroleum resids.
  • the hydroprocessing conditions include a catalyst.
  • hydroprocessing requires a hydrogen stream.
  • the hydrogen pressures in the process of the invention, range from 4240 to 27,700 kPa (600 to about 4000 psig). Elevated temperatures in the process of the invention range from about 316° to 468°C (600°F to about 875°F). Space velocities (WHSV) range from 0.05 to 10.
  • the catalyst for resid demetalation and/or desulfurization can be a conventional one.
  • compositions useful as catalysts include silica, alumina or silica-alumina.
  • the rate constants for dematalation and/or desulfurization of resid hydroprocessed in the presence of said lower boiling diluent is enhanced.
  • the extent of this enhancement allows a certain proportion of diluent to be hydrotreated in the same reactor with no negative consequence and even a positive effect on the treatment of the vacuum resid fraction.
  • the product of this process can be optionally fractionated and set to other conversion units or used directly as a finished product.
  • LCO was processed by itself for four days on an equilibrated catalyst at the same condition as in Example 1. Catalyst performance on resid hydrotreatment is compared before and after LCO runs. As shown below, metals removal from AL resid was increased from 43 to 46%, while sulfur removal was increased from 38 to 41%.

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)
EP19910305552 1990-06-21 1991-06-19 Entschwefelung und Entmetallisierung von Rückständen Expired - Lifetime EP0462823B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US540721 1983-10-11
US54072190A 1990-06-21 1990-06-21

Publications (2)

Publication Number Publication Date
EP0462823A1 true EP0462823A1 (de) 1991-12-27
EP0462823B1 EP0462823B1 (de) 1994-04-13

Family

ID=24156649

Family Applications (1)

Application Number Title Priority Date Filing Date
EP19910305552 Expired - Lifetime EP0462823B1 (de) 1990-06-21 1991-06-19 Entschwefelung und Entmetallisierung von Rückständen

Country Status (5)

Country Link
EP (1) EP0462823B1 (de)
JP (1) JPH04239094A (de)
AU (1) AU644166B2 (de)
CA (1) CA2043403A1 (de)
DE (1) DE69101670T2 (de)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100366709C (zh) * 2006-04-17 2008-02-06 中国石油化工集团公司 一种重油加工的组合工艺
EP2169031A1 (de) * 2007-07-24 2010-03-31 Idemitsu Kosan Co., Ltd. Hydroraffinationsverfahren für kohlenwasserstofföl
CN103102986A (zh) * 2011-11-10 2013-05-15 中国石油化工股份有限公司 一种渣油加氢处理–延迟焦化组合工艺方法
US8932451B2 (en) 2011-08-31 2015-01-13 Exxonmobil Research And Engineering Company Integrated crude refining with reduced coke formation
CN104927920A (zh) * 2014-03-21 2015-09-23 中国石油化工股份有限公司 一种渣油焦化方法
CN106367113A (zh) * 2015-07-23 2017-02-01 中国石化扬子石油化工有限公司 一种渣油加氢处理方法
EP3957705A1 (de) * 2015-05-12 2022-02-23 Ergon, Inc. Hochleistungsfähiges prozessöl
US11566187B2 (en) 2015-05-12 2023-01-31 Ergon, Inc. High performance process oil based on distilled aromatic extracts

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4711849B2 (ja) * 2006-02-21 2011-06-29 Ｊｘ日鉱日石エネルギー株式会社 燃料基材の製造方法
JP5563491B2 (ja) * 2011-01-14 2014-07-30 出光興産株式会社 重質炭化水素油の水素化処理方法

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1034302B (de) * 1956-03-14 1958-07-17 Exxon Research Engineering Co Verfahren zur Umwandlung asphaltischer Kohlenwasserstoffe

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4548709A (en) * 1983-04-29 1985-10-22 Mobil Oil Corporation Hydrotreating petroleum heavy ends in aromatic solvents with dual pore size distribution alumina catalyst
US4808289A (en) * 1987-07-09 1989-02-28 Amoco Corporation Resid hydrotreating with high temperature flash drum recycle oil

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1034302B (de) * 1956-03-14 1958-07-17 Exxon Research Engineering Co Verfahren zur Umwandlung asphaltischer Kohlenwasserstoffe

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100366709C (zh) * 2006-04-17 2008-02-06 中国石油化工集团公司 一种重油加工的组合工艺
EP2169031A1 (de) * 2007-07-24 2010-03-31 Idemitsu Kosan Co., Ltd. Hydroraffinationsverfahren für kohlenwasserstofföl
EP2169031A4 (de) * 2007-07-24 2012-10-10 Idemitsu Kosan Co Hydroraffinationsverfahren für kohlenwasserstofföl
US8932451B2 (en) 2011-08-31 2015-01-13 Exxonmobil Research And Engineering Company Integrated crude refining with reduced coke formation
CN103102986A (zh) * 2011-11-10 2013-05-15 中国石油化工股份有限公司 一种渣油加氢处理–延迟焦化组合工艺方法
CN103102986B (zh) * 2011-11-10 2015-05-13 中国石油化工股份有限公司 一种渣油加氢处理–延迟焦化组合工艺方法
CN104927920A (zh) * 2014-03-21 2015-09-23 中国石油化工股份有限公司 一种渣油焦化方法
CN104927920B (zh) * 2014-03-21 2017-03-15 中国石油化工股份有限公司 一种渣油焦化方法
EP3957705A1 (de) * 2015-05-12 2022-02-23 Ergon, Inc. Hochleistungsfähiges prozessöl
US11332679B2 (en) 2015-05-12 2022-05-17 Ergon, Inc. High performance process oil
US11560521B2 (en) 2015-05-12 2023-01-24 Ergon, Inc. High performance process oil
US11566187B2 (en) 2015-05-12 2023-01-31 Ergon, Inc. High performance process oil based on distilled aromatic extracts
CN106367113A (zh) * 2015-07-23 2017-02-01 中国石化扬子石油化工有限公司 一种渣油加氢处理方法

Also Published As

Publication number Publication date
AU644166B2 (en) 1993-12-02
AU7727991A (en) 1992-01-02
JPH04239094A (ja) 1992-08-26
CA2043403A1 (en) 1991-12-22
EP0462823B1 (de) 1994-04-13
DE69101670D1 (de) 1994-05-19
DE69101670T2 (de) 1994-07-28

Similar Documents

Publication Publication Date Title
US4626340A (en) Process for the conversion of heavy hydrocarbon feedstocks characterized by high molecular weight, low reactivity and high metal contents
EP0523679B2 (de) Verfahren zur Erzeugung von Diesel-Gasöl mit niedrigem Schwefelgehalt
US7938953B2 (en) Selective heavy gas oil recycle for optimal integration of heavy oil conversion and vacuum gas oil treating
US20050006279A1 (en) Method for the valorization of heavy charges by bubbling-bed deasphalting and hydrocracking
EP0462823B1 (de) Entschwefelung und Entmetallisierung von Rückständen
US4992163A (en) Cat cracking feed preparation
US4169040A (en) Staged process for the production of middle distillate from a heavy distillate
EP0433026B1 (de) Verfahren zur Entfernung von metallischen Verunreinigungen aus Kohlenwasserstoffölen
US5203987A (en) Method of upgrading residua
US3941680A (en) Lube oil hydrotreating process
US3948756A (en) Pentane insoluble asphaltene removal
AU2018329532A1 (en) Reactor staging for slurry hydroconversion of polycyclic aromatic hydrocarbon feeds
Scheuerman et al. Advances in Chevron RDS technology for heavy oil upgrading flexibility
JP3414861B2 (ja) 軽油留分の水素化精製処理方法
EP0159140B1 (de) Prozess zur Qualitätsverbesserung von schweren Rohölen
US3575844A (en) Hydrocracking process
US7332071B2 (en) Process for improving aromatic and naphtheno-aromatic gas oil fractions
US5135640A (en) High efficiency process for preparation of gasoline by catalytic cracking
RU2089596C1 (ru) Способ получения экологически чистого дизельного топлива
US6156189A (en) Operating method for fluid catalytic cracking involving alternating feed injection
US4537676A (en) Reducing metal content of oil feeds
US3291724A (en) Process for treating petroleum crude oil
JPH05112785A (ja) 重質炭化水素油の処理方法
JPH0413397B2 (de)
US11142704B2 (en) Methods and systems of steam stripping a hydrocracking feedstock

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): BE DE FR GB IT NL

17P Request for examination filed

Effective date: 19920624

17Q First examination report despatched

Effective date: 19930111

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): BE DE FR GB IT NL

REF Corresponds to:

Ref document number: 69101670

Country of ref document: DE

Date of ref document: 19940519

ET Fr: translation filed
ITF It: translation for a ep patent filed
PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed
PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 19970324

Year of fee payment: 7

Ref country code: FR

Payment date: 19970324

Year of fee payment: 7

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 19970331

Year of fee payment: 7

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 19970403

Year of fee payment: 7

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: BE

Payment date: 19970428

Year of fee payment: 7

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19980619

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19980630

BERE Be: lapsed

Owner name: MOBIL OIL CORP. (A NEW YORK CORP.)

Effective date: 19980630

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19990101

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 19980619

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19990226

NLV4 Nl: lapsed or anulled due to non-payment of the annual fee

Effective date: 19990101

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19990401

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

ITF It: translation for a ep patent filed
PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES;WARNING: LAPSES OF ITALIAN PATENTS WITH EFFECTIVE DATE BEFORE 2007 MAY HAVE OCCURRED AT ANY TIME BEFORE 2007. THE CORRECT EFFECTIVE DATE MAY BE DIFFERENT FROM THE ONE RECORDED.

Effective date: 20050619