US3475323A - Process for the preparation of low sulfur fuel oil - Google Patents

Process for the preparation of low sulfur fuel oil Download PDF

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Publication number
US3475323A
US3475323A US635036A US3475323DA US3475323A US 3475323 A US3475323 A US 3475323A US 635036 A US635036 A US 635036A US 3475323D A US3475323D A US 3475323DA US 3475323 A US3475323 A US 3475323A
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Prior art keywords
coke
metals
percent
fuel oil
hydrodesulfurization
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Expired - Lifetime
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US635036A
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English (en)
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Alto N Stuckey Jr
Noah E Blackwell
Ignacio G Del Valle
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ExxonMobil Technology and Engineering Co
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Exxon Research and Engineering Co
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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
    • 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
    • C10G49/00—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00
    • C10G49/007—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00 in the presence of hydrogen from a special source or of a special composition or having been purified by a special treatment

Definitions

  • This invention relates to a process for the preparation of fuel oil of the type burned in industrial furnaces, particularly furnaces located at plants in or near metropolitan areas. More particularly, the invention relates to a process for upgrading high sulfur, high metals content petoleum crude or residual fractions for use as industrial Very large quantities of industrial fuel oils are burned daily in areas such as the eastern seaboard of the United States. Recently, statutes limiting the sulfur content of residual fuel have been enacted in eastern metropolitan areas. Sulfur contents of less than 3 wt. percent, preferably less than 1 wt. percent are being required to reduce air pollution.
  • a number of Latin American crude oils are favorably located for processing and shipping to the large eastern markets.
  • these oils are characterized by a high content of metals such as iron, nickel and vanadium.
  • metals such as iron, nickel and vanadium.
  • These metals have an adverse effect upon the catalysts used in hydrodesulfurization of the resduum.
  • the metals are present in the fuel, they -attack the refractories used to line boilers and combustion chambers; cause slagging and buildup of deposits upon boiler tops, combustion chamber walls and the blades of gas turbines and they severely corrode high temperature metallic surfaces with which they come into contact.
  • the feedstocks of the present invention are also characterized by a high content of high molecular Weight hydrocarbons having complicated ring structures and a high carbon-to-hydrogen ratio. Asphaltenes and resins are representative of this type of hydrocarbon. These materials are the source of carbonaceous deposits laid down on the catalyst surfaces during the hydrodesulfurization reaction.
  • the objects of the invention are accomplished by subjecting a high sulfur, high metals content fuel oil feedstock to mild coking, taking the total coker overhead product boiling above about 600 F. or separating a fraction boiling in the gas oil boiling range from the coker overhead and subjecting either of the latter stocks to hydrodesulfurization.
  • coke from the coking step is treated to produce hydrogen and a high metals coke concentrate is recovered.
  • Feed A is a heavy Arabian (Safaniya) atmospheric residuum
  • Feed B is a topped Venezuelan (Ba mangoro) crude.
  • Feed A has 4.0% sulfur by weight and 84 p.p.m. V, 32 p.p.m. Ni, and 11 p.p.m. Fe by weight;
  • Feed B has 2.65% sulfur by Weight and 316 p.p.m. V, 58 p.p.m. Ni, and 9 p.p.m. Fe by Weight.
  • Processing conditions in the comparative desulfurization tests were 1500 p.s.i.g. pressure, 725 F.
  • catalyst life is substantially shorter with the high metals Venezuelan feed (Feed B) as operations above 780-800 F. lead to substantial cracking and product degradation.
  • the process of this invention is specifically designed to prepare fuel oils from stocks having a high total content of sulfur compounds, metals compounds and coke formers.
  • Typical feeds include heavy whole crude oils, atmospheric residuums, vacuum residuums, visbreaker bottoms, and crude oils topped by flashing or any other means. Generally speaking the from 30 to 90 wt. percent of the feed boils above 900 F.
  • the preferred feedstocks are atmospheric residual bottoms having an initial boiling point ranging from 500 to 800 F.
  • the characteristics of the feedstocks of the process are set forth below in Table Il.
  • Coker products are removed from the coker in the vapor phase by line 8 and passed to any suitable separation means such as a flash distillation tower 9.
  • Any suitable separation means such as a flash distillation tower 9.
  • Gas and light Tia Juana Medium At- Bacliaquero Bucliaquero mosplieric Vaccuuin Crude Rcsiduuni R esid Gravity, API 16.5 10.4 G. 7 Sulfur, wt. percent 2. 23 2. 16 3. 3 Carbon, Conradson, ⁇ vt pe1ce1 0. 8 10.9 18. 4 Metals, p.p.m.:
  • Ni, and 22 wt. percent Conradson carbon is passed by line 1 to fluid coker 2.
  • Steam at a temperature of 900 to 1050 F. is passed by line 3 to the coker.
  • the coke is maintained in a uidized state.
  • Coking is carried out at a temperature in the range of 900 to 1100 F., a pressure ranging from atmospheric pressure to 70 p.s.i.a., in the presence of 5 to 100 wt. percent steam based on the feed.
  • Small particles of petroleum coke, formed in the process itself circulate in a fluidized state between the coker 2 and the coke burner 4 and they serve as the heat transfer medium.
  • Coke is passed by line 5 to the coke burner 4.
  • a portion of the coke, i.e., 5 to 50 wt. percent is continuously burned in the presence of air supplied by line 6. Hot coke is returned to coker 2 by line 7. If the hydrogen production step described subsequently in this description is not employed part ofthe coke can be recovered from burner 4 as a cokemetals concentrate.
  • the equipment and technology of fluid coking is available in the prior art and constitutes no part of the invention.
  • the coking Step of the invention differs ends and liquids boiling up to 600 F. are removed overhead from the tower by line 10. In the preferred embodiment, all of the 600 F. plus material is passed by line 11 to the hydrodesulfurization reactor.
  • a vacuum distillation tower replaces the ash tower and a side cut boiling in the range of 600-1150 F. is recovered as the hydrodesulfurization feed and the bottoms from the vacuum tower, i.e., the 1150 R+ fraction is blended with desulfurized oil.
  • the 1150 F. can be recycled to the coker.
  • the coked hydrodesulfurization feedstock in line 11 has been reduced in metals content at least 50 wt. percent and more commonly iat least 75 wt. percent. Furthermore, the asphaltene content has also been reduced at least S0 wt. percent and more commonly at least 75 wt. percent. Similarly the Conradson carbon content of the oil ⁇ has been reduced at least The fraction is passed into hydrodesulfurization reactor 12.
  • the reaction is carried out infa conventional reactor of the fixed bed, moving bed, or uidized bed type.
  • the oil is preferably contacted in the liquid phase. Typical conditions are as follows:
  • catalysts include salts of metals of Groups VI and VIII of the Periodic Table supported on a suitable porous support material such as alumina, silica alumina, bauxite, magnesia and the like. Catalysts containing oxides or sulfides of cobalt, nickel, molybdenum and tungsten are preferred. Oxide catalysts are preferably sulfided prior to use or in situ. The most preferred catalyst is one containing 2 5 wt. percent cobalt oxide, 10i-25 wt. percent molybdenum oxide and the balance silica stabilized alumina. 'I'he preferred silica content of the base is 1.5 to 5 wt. percent. l
  • Hydrogen is fed to the reactor by lines 13l and 14. Hydrodesulfurization efiiuent is removed from the reactor by line 15 Iand passes to separator 16. Recycle gas passes overhead :by line 17 from the separator to gas purification system 18. Low sulfur fuel oil is recovered by line 19. If desired tHe oil in line 19 can be fractionated by any suitable means into a plurality of fuel oil cuts.
  • gas purification system 18 hydrogen is separated from H28, NH3, CO, CO2 and other gases and light ends by known means such as cooling,water washing, amine scrubbers, the hot carbonate process or a combination of these gas purification techniques-Hydrogen is recycled by line 14. Gas impurities are purged by line 20.
  • all or part of the hydrogen for hydrodesulfurization is prepared in the process.
  • coke burner 4 in the drawing coke is removed by line 21 from the burner at a temperature of 1300 to l500 F. after burning with air. The burning step tends to concentrate the metals in the coke.
  • Coke is passed from line 21 into a water gas shift convertor 22 where it is contacted with steam from line 23. The hot coke and steam undergo the Well known water gas shift reaction, i.e.,
  • the CO and H2 product mixture may be further processed over a nickel catalyst to produce additional H2, i.e.,
  • the hydrogen containing gas from convertor 22 is passed by line 24 to gas purification system 18 for removal of impurities by known means.
  • Alternate processes for making H2 from coke include the partial oxidation process (Hydrocarbon Processing, September 1966, vol. 45, No. 9).
  • a part of the coke is recycled by line 25 from con vertor 22 to burner 4 for reheating and the remainder of the coke is recovered by line 26 iin the form of a cokemetals concentrate.
  • the concentrate will contain from to 90 wt. percent vanadium, nickel and iron.
  • the coking, coke burning and hydrogen making steps all serve to raise the metals concentration ofthe concentrate recovered by line 26.
  • the metals can be recovered from coke by known means. A typical method is shown in U.S. Patent 3,226,316 issued Dec. 28, 1965.
  • a process for the preparation of low sulfur fuel oil by catalytic hydrodesulfurization comprising the steps of (a) pretreating a fuel oil feed containing at least 1.0 wt. percent sulfur, at least p.p.m. metals, and at least 5 wt. percent asphaltenes in a fluid coking step at a temperature in the range of 900 to 1100 F. in the presence of 5 to 100 wt. percent steam and proportionally reducing the quantity of steam employed in said liuid coking stop as the temperature is increased over said range whereby the effective distillation cut point is controlled;
  • a process for making an improved low sulfur content fuel oil from a high sulfur content, high metals content residual petroleum oil fraction comprising the steps of:
US635036A 1967-05-01 1967-05-01 Process for the preparation of low sulfur fuel oil Expired - Lifetime US3475323A (en)

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US (1) US3475323A (xx)
BE (1) BE714468A (xx)
DE (1) DE1770308A1 (xx)
FR (1) FR1561772A (xx)
GB (1) GB1218117A (xx)
NL (1) NL158840B (xx)

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3617481A (en) * 1969-12-11 1971-11-02 Exxon Research Engineering Co Combination deasphalting-coking-hydrotreating process
US3617513A (en) * 1969-01-03 1971-11-02 Exxon Research Engineering Co Coking of heavy feedstocks
US4007092A (en) * 1975-03-18 1977-02-08 Exxon Research And Engineering Company Process for producing low sulfur coke
US4036736A (en) * 1972-12-22 1977-07-19 Nippon Mining Co., Ltd. Process for producing synthetic coking coal and treating cracked oil
US4058451A (en) * 1976-08-23 1977-11-15 Uop Inc. Combination process for producing high quality metallurgical coke
US4062760A (en) * 1976-04-20 1977-12-13 Exxon Research And Engineering Company Dry fines recycle in a coking process
US4213848A (en) * 1978-07-27 1980-07-22 Exxon Research & Engineering Co. Fluid coking and gasification process
US4269696A (en) * 1979-11-08 1981-05-26 Exxon Research & Engineering Company Fluid coking and gasification process with the addition of cracking catalysts
US4325810A (en) * 1979-10-01 1982-04-20 The Standard Oil Company Distillate yields by catalytically co-coking shale oil and petroleum residua
US4358366A (en) * 1979-10-01 1982-11-09 Standard Oil Company (Ohio) Catalytic hydrocoking of residua
US4394250A (en) * 1982-01-21 1983-07-19 Chevron Research Company Delayed coking process
US5853570A (en) * 1995-08-25 1998-12-29 Mitsubishi Oil Co., Ltd. Process for desulfurizing catalytically cracked gasoline

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* Cited by examiner, † Cited by third party
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US7306713B2 (en) 2003-05-16 2007-12-11 Exxonmobil Research And Engineering Company Delayed coking process for producing free-flowing coke using a substantially metals-free additive
US7645375B2 (en) 2003-05-16 2010-01-12 Exxonmobil Research And Engineering Company Delayed coking process for producing free-flowing coke using low molecular weight aromatic additives
US7658838B2 (en) 2003-05-16 2010-02-09 Exxonmobil Research And Engineering Company Delayed coking process for producing free-flowing coke using polymeric additives
WO2005113707A1 (en) 2004-05-14 2005-12-01 Exxonmobil Research And Engineering Company Viscoelastic upgrading of heavy oil by altering its elastic modulus
ES2550260T3 (es) * 2004-05-14 2015-11-05 Exxonmobil Research And Engineering Company Proceso de coquización retardada para la producción de coque en esencia libremente fluyente de un corte profundo de un aceite residual de vacío
EP1751256A1 (en) 2004-05-14 2007-02-14 Exxonmobil Research And Engineering Company Fouling inhibition of thermal treatment of heavy oils
MXPA06012949A (es) 2004-05-14 2007-02-12 Exxonmobil Res & Eng Co Combinacion de materias primas de residuos para producir un coque que sea mas facil de remover de un tambor de coquizacion.
CN101010415B (zh) 2004-05-14 2012-07-04 埃克森美孚研究工程公司 生产及从延迟焦化鼓中去除自由流动的焦炭
US7871510B2 (en) 2007-08-28 2011-01-18 Exxonmobil Research & Engineering Co. Production of an enhanced resid coker feed using ultrafiltration
US7794587B2 (en) 2008-01-22 2010-09-14 Exxonmobil Research And Engineering Company Method to alter coke morphology using metal salts of aromatic sulfonic acids and/or polysulfonic acids

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2606144A (en) * 1949-12-10 1952-08-05 Universal Oil Prod Co Fluidized conversion and coking of heavy petroleums
US2885350A (en) * 1954-01-20 1959-05-05 Exxon Research Engineering Co Hydrocoking of residual oils
US2894897A (en) * 1954-05-28 1959-07-14 Universal Oil Prod Co Hydrocarbon conversion process in the presence of added hydrogen
US2901417A (en) * 1954-05-17 1959-08-25 Exxon Research Engineering Co Hydrodesulfurization of a coked hydrocarbon stream comprising gasoline constituents and gas oil constituents
US2916438A (en) * 1955-11-25 1959-12-08 Exxon Research Engineering Co Prevention of disperse phase coking in fluid coking apparatus
US3226316A (en) * 1962-06-05 1965-12-28 Exxon Research Engineering Co Coking of hydrocarbons with the removal of metallic contaminants from the coke

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2606144A (en) * 1949-12-10 1952-08-05 Universal Oil Prod Co Fluidized conversion and coking of heavy petroleums
US2885350A (en) * 1954-01-20 1959-05-05 Exxon Research Engineering Co Hydrocoking of residual oils
US2901417A (en) * 1954-05-17 1959-08-25 Exxon Research Engineering Co Hydrodesulfurization of a coked hydrocarbon stream comprising gasoline constituents and gas oil constituents
US2894897A (en) * 1954-05-28 1959-07-14 Universal Oil Prod Co Hydrocarbon conversion process in the presence of added hydrogen
US2916438A (en) * 1955-11-25 1959-12-08 Exxon Research Engineering Co Prevention of disperse phase coking in fluid coking apparatus
US3226316A (en) * 1962-06-05 1965-12-28 Exxon Research Engineering Co Coking of hydrocarbons with the removal of metallic contaminants from the coke

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3617513A (en) * 1969-01-03 1971-11-02 Exxon Research Engineering Co Coking of heavy feedstocks
US3617481A (en) * 1969-12-11 1971-11-02 Exxon Research Engineering Co Combination deasphalting-coking-hydrotreating process
US4036736A (en) * 1972-12-22 1977-07-19 Nippon Mining Co., Ltd. Process for producing synthetic coking coal and treating cracked oil
US4007092A (en) * 1975-03-18 1977-02-08 Exxon Research And Engineering Company Process for producing low sulfur coke
US4062760A (en) * 1976-04-20 1977-12-13 Exxon Research And Engineering Company Dry fines recycle in a coking process
US4058451A (en) * 1976-08-23 1977-11-15 Uop Inc. Combination process for producing high quality metallurgical coke
US4213848A (en) * 1978-07-27 1980-07-22 Exxon Research & Engineering Co. Fluid coking and gasification process
US4325810A (en) * 1979-10-01 1982-04-20 The Standard Oil Company Distillate yields by catalytically co-coking shale oil and petroleum residua
US4358366A (en) * 1979-10-01 1982-11-09 Standard Oil Company (Ohio) Catalytic hydrocoking of residua
US4269696A (en) * 1979-11-08 1981-05-26 Exxon Research & Engineering Company Fluid coking and gasification process with the addition of cracking catalysts
US4394250A (en) * 1982-01-21 1983-07-19 Chevron Research Company Delayed coking process
US5853570A (en) * 1995-08-25 1998-12-29 Mitsubishi Oil Co., Ltd. Process for desulfurizing catalytically cracked gasoline

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NL158840B (nl) 1978-12-15
FR1561772A (xx) 1969-03-28
BE714468A (xx) 1968-10-30
GB1218117A (en) 1971-01-06
NL6806146A (xx) 1968-11-04
DE1770308A1 (de) 1971-10-07

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