EP0462823B1 - Entschwefelung und Entmetallisierung von Rückständen - Google Patents

Entschwefelung und Entmetallisierung von Rückständen Download PDF

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Publication number
EP0462823B1
EP0462823B1 EP19910305552 EP91305552A EP0462823B1 EP 0462823 B1 EP0462823 B1 EP 0462823B1 EP 19910305552 EP19910305552 EP 19910305552 EP 91305552 A EP91305552 A EP 91305552A EP 0462823 B1 EP0462823 B1 EP 0462823B1
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EP
European Patent Office
Prior art keywords
resid
diluent
process according
blend
vacuum
Prior art date
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Expired - Lifetime
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EP19910305552
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English (en)
French (fr)
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EP0462823A1 (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
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Mobil Oil Corp
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Publication date
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    • 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.
  • German patent document DE-A- 1 034 302 discloses a process for treating an asphaltic hydrocarbon with a diluent comprising not less than 0.5 parts of gas oil-petroleum crude (as diluent) per part asphaltic hydrocarbon and treating the mixture with a desulphurization catalyst.
  • 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.
  • 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%.

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  • 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)

Claims (7)

  1. Verfahren zur Entschwefelung und Entmetallisierung eines Rückstandes, welches umfaßt:
    Mischen des Rückstandes mit einem Verdünnungsmittel mit einer Siedetemperatur im Bereich von 204°C bis zu weniger als die Siedetemperatur des Rückstands, um eine Mischung zu bilden, die bis zu 50 Vol.-% des Verdünnungsmittels enthält;
    Kontakt der Mischung mit einem Hydrotreating-Katalysator bei Bedingungen, die einen Wasserstoffdruck im Bereich 4270 bis 27700 kPa, erhöhte Temperaturen im Bereich von 316 bis 468°C und eine Raumgeschwindigkeit im Bereich von 0,05 bis 10 einschließen; und
    Gewinnung der behandelten Mischung.
  2. Verfahren nach Anspruch 1, worin das Verdünnungsmittel für den Rückstand aus atmosphärischem Gasöl, Vakuumgasöl und gecracktem Destillat, leichtem Rückführöl und hochsiedendem Öl besteht.
  3. Verfahren nach Anspruch 1 oder 2, worin der Katalysator für das Hydrotreating ein Katalysator ist, der aus Siliciumdioxid, Aluminiumoxid und Siliciumdioxid-Aluminiumoxid ausgewählt ist.
  4. Verfahren nach Anspruch 1, 2 oder 3, worin der Rückstand ein Vakuumrückstand ist.
  5. Verfahren nach einem der vorstehenden Ansprüche, worin der Rückstand eine wirksame Menge an Nickel oder Vanadium enthält, die bei der anschließenden stromabwärtigen Behandlung als Katalysatorgift wirkt.
  6. Verfahren nach einem der vorstehenden Ansprüche, worin die Menge an Nickel oder Vanadium in der gewonnen Mischung geringer als die wirksame Menge ist, die als Katalysatorgift wirkt.
  7. Verfahren nach einem der vorstehenden Ansprüche, worin die Mischung 10 bis 30 Vol.-% des Verdünnungsmittels enthält.
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
US54072190A 1990-06-21 1990-06-21
US540721 1990-06-21

Publications (2)

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

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

Country Status (5)

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

Families Citing this family (10)

* 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
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
US20100206770A1 (en) * 2007-07-24 2010-08-19 Idemitsu Kosan Co., Ltd. Hydrorefining method for hydrocarbon oil
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
US8932451B2 (en) 2011-08-31 2015-01-13 Exxonmobil Research And Engineering Company Integrated crude refining with reduced coke formation
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
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
BR112017024016A2 (pt) 2015-05-12 2018-07-17 Ergon Inc método para produção de óleos de processo naftênicos, óleo de processo naftênico, formulação de borracha, e, pneu
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

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB833705A (en) * 1956-03-14 1960-04-27 Exxon Research Engineering Co Destructive hydrogenation of asphaltic hydrocarbons
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

Also Published As

Publication number Publication date
CA2043403A1 (en) 1991-12-22
AU644166B2 (en) 1993-12-02
DE69101670D1 (de) 1994-05-19
JPH04239094A (ja) 1992-08-26
AU7727991A (en) 1992-01-02
DE69101670T2 (de) 1994-07-28
EP0462823A1 (de) 1991-12-27

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