US3261878A - Autothermal cracking of liquid hydrocarbons - Google Patents

Autothermal cracking of liquid hydrocarbons Download PDF

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Publication number
US3261878A
US3261878A US3261878DA US3261878A US 3261878 A US3261878 A US 3261878A US 3261878D A US3261878D A US 3261878DA US 3261878 A US3261878 A US 3261878A
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United States
Prior art keywords
fluidized bed
oil coke
cracking
oil
liquid hydrocarbons
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
    • C10B55/00—Coking mineral oils, bitumen, tar, and the like or mixtures thereof with solid carbonaceous material
    • C10B55/02—Coking mineral oils, bitumen, tar, and the like or mixtures thereof with solid carbonaceous material with solid materials
    • C10B55/04—Coking mineral oils, bitumen, tar, and the like or mixtures thereof with solid carbonaceous material with solid materials with moving solid materials
    • C10B55/08—Coking mineral oils, bitumen, tar, and the like or mixtures thereof with solid carbonaceous material with solid materials with moving solid materials in dispersed form
    • C10B55/10—Coking mineral oils, bitumen, tar, and the like or mixtures thereof with solid carbonaceous material with solid materials with moving solid materials in dispersed form according to the "fluidised bed" technique
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C11/00—Aliphatic unsaturated hydrocarbons
    • C07C11/02—Alkenes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C4/00—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms
    • C07C4/02—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms by cracking a single hydrocarbon or a mixture of individually defined hydrocarbons or a normally gaseous hydrocarbon fraction
    • C07C4/025—Oxidative cracking, autothermal cracking or cracking by partial combustion

Definitions

  • This invention relates to a process for the production of gaseous olefines, especially ethylene, from liquid hydrocarbons, and especially to a process for the autothermal cracking of liquid hydrocarbons, for example crude petroleums, in a fluidized bed of oil coke formed by the cracking.
  • the said process is of special importance in processing liquid hydrocarbons with low Conradson carbon, for ex ample with more than 0% up to about 2.5% Conradson carbon, such as crude petroleums having this property, and in the processing of liquid hydrocarbons, especially crude petroleums, which contain water.
  • Conradson carbon such as crude petroleums having this property
  • the formation of oil coke during cracking is usually insuflicient to compensate for the loss by combustion and attrition.
  • a content of salts, especially alkali salts, such as sodium and potassium chloride often favors the combustion of oil coke. It has therefore always been necessary to separate the water by a special purification method prior to the use of such initial hydrocarbons.
  • Liquid hydrocarbons or certain fractions of petroleum 3,261,878 Patented July 19, 1966 distillation, gas oils and mineral oil residues, may be used as initial materials for the process.
  • the process is epecially suitable for processing crude petroleums.
  • the additions which inhibit burning of the oil coke may be substances which contain phosphoric and/ or boric acid or their salts, for example boric acid and phosphoric acid themselves and also the various salts of phosphoric and boric acids, such as sodium, potassium, ammonium, magnesium, calcium, strontium, barium, zinc and aluminum salts.
  • Primary, secondary and also tertiary phosphates i.e., alkali metal and ammonium salts, may be used as phosphates, and also mixed phosphates, for example sodium ammonium phosphate.
  • Ammonium phosphate (NH )H PO is especially suitable.
  • Compounds of boron and phosphorus may be used, as well as mixtures of boric acid and its salts with phosphoric acid and salts of phosphoric acid.
  • 0.05% by weight up to about 6% by weight, preferably 0.2 to 3% :by weight, of these compounds is added with reference to the weight of oil coke present in the fluidized 'bed.
  • the cracking of the liquid hydrocarbons is carried out at temperatures of 630 to 850 C., especially :at 680 to 780 C.
  • the flu-idizing agent may be steam and/ or carbon dioxide or another inert gas, and the oxygen necessary for autothermal cracking may be added thereto.
  • the oxygen necessary for partial combustion may be added in the form of an oxygen-containing gas, for example air. However, it is preferable to add the oxygen in pure form, i.e., a commercially pure oxygen such as is obtained for example by liquefaction of air.
  • Example 1 A fluidized bed of oil coke is supported above a metal grate provided with fine slots arranged in a shaft furnace having a cross-section of 1 sq. m.
  • a mixture of about 400 kg./h. of steam and about 200 m. (S.T.P.) per hour of oxygen is blown upwardly into the fluidized bed.
  • 800 kg. per hour of Sahara crude oil with 0.8% Conradson carbon is sprayed in above the grate.
  • Hydrocarbons boiling above 250 C. formed in the process are returned to the fluidized bed in an amount of 250 kg. per hour immediately above the grate.
  • 1 kg. of primary sodium phosphate is added to the fluidized bed.
  • the ratio of steam and oxygen supplied is regulated so that a reaction temperature of 720 C. prevails in the fluidized bed.
  • Solids entrained from the fluidized bed by the cracking gases and vapors formed are separated in a cyclone provided above the fluidized bed and flow back into the fluidized bed through the discharge pipe of the cyclone.
  • About 4 kg. per hour of excess oil coke is formed and is continuously removed.
  • the phosphorus content of the oil coke in the fluidized bed is 1.4% by weight.
  • Example 2 800 kg. per hour of a crude oil from Upper Alsace (France) with 2.3% Conradson carbon contaminated with 1% by weight of salt water is cracked in a fluidized bed of oil coke in the way described in Example 1. At the same time about 400 kg. per hour of steam and about 200 m. (S.T.P.) of oxygen is supplied. The hydrocarbons boiling above about 250 C. formed by the process are returned to the fluidized bed in an amount of 300 kg. per hour. 100 g. of calcium ammonium phosphate is introduced into the fluidized bed per hour. At a temperature of 730 C. in the fluidized bed, 190 kg. of ethylene, 120 kg.
  • S.T.P. 200 m.
  • An additive containing boron may be used instead of a phosphate as in Example 1.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Combustion & Propulsion (AREA)
  • Thermal Sciences (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
US3261878D 1961-02-09 Autothermal cracking of liquid hydrocarbons Expired - Lifetime US3261878A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DEB61194A DE1133362B (de) 1961-02-09 1961-02-09 Verfahren zur autothermen Spaltung von fluessigen Kohlenwasserstoffen

Publications (1)

Publication Number Publication Date
US3261878A true US3261878A (en) 1966-07-19

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US3261878D Expired - Lifetime US3261878A (en) 1961-02-09 Autothermal cracking of liquid hydrocarbons

Country Status (6)

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US (1) US3261878A (enExample)
CH (1) CH408903A (enExample)
DE (1) DE1133362B (enExample)
FR (1) FR1314261A (enExample)
GB (1) GB978576A (enExample)
NL (1) NL274559A (enExample)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4370223A (en) * 1980-12-31 1983-01-25 Chevron Research Company Coking hydrocarbonaceous oils with an aqueous liquid
US4504382A (en) * 1982-10-14 1985-03-12 Exxon Research And Engineering Co. Phosphorus-containing catalyst and catalytic cracking process utilizing the same
US4663018A (en) * 1985-06-27 1987-05-05 Betz Laboratories, Inc. Method for coke retardant during hydrocarbon processing
US20050126107A1 (en) * 2002-04-12 2005-06-16 Colman Derek A. Support grid

Families Citing this family (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4430199A (en) 1981-05-20 1984-02-07 Engelhard Corporation Passivation of contaminant metals on cracking catalysts by phosphorus addition
US10603657B2 (en) 2016-04-11 2020-03-31 Saudi Arabian Oil Company Nano-sized zeolite supported catalysts and methods for their production
US11084992B2 (en) 2016-06-02 2021-08-10 Saudi Arabian Oil Company Systems and methods for upgrading heavy oils
US10301556B2 (en) 2016-08-24 2019-05-28 Saudi Arabian Oil Company Systems and methods for the conversion of feedstock hydrocarbons to petrochemical products
US10689587B2 (en) 2017-04-26 2020-06-23 Saudi Arabian Oil Company Systems and processes for conversion of crude oil
US10870802B2 (en) 2017-05-31 2020-12-22 Saudi Arabian Oil Company High-severity fluidized catalytic cracking systems and processes having partial catalyst recycle
WO2019018223A1 (en) 2017-07-17 2019-01-24 Saudi Arabian Oil Company SYSTEMS AND METHODS FOR THE TREATMENT OF HEAVY OILS BY OIL RECOVERY FOLLOWED BY A DISTILLATION
US10889768B2 (en) 2018-01-25 2021-01-12 Saudi Arabian Oil Company High severity fluidized catalytic cracking systems and processes for producing olefins from petroleum feeds
US11505754B2 (en) 2020-09-01 2022-11-22 Saudi Arabian Oil Company Processes for producing petrochemical products from atmospheric residues
US11434432B2 (en) 2020-09-01 2022-09-06 Saudi Arabian Oil Company Processes for producing petrochemical products that utilize fluid catalytic cracking of a greater boiling point fraction with steam
US11332680B2 (en) 2020-09-01 2022-05-17 Saudi Arabian Oil Company Processes for producing petrochemical products that utilize fluid catalytic cracking of lesser and greater boiling point fractions with steam
US11230673B1 (en) 2020-09-01 2022-01-25 Saudi Arabian Oil Company Processes for producing petrochemical products that utilize fluid catalytic cracking of a lesser boiling point fraction with steam
US11352575B2 (en) 2020-09-01 2022-06-07 Saudi Arabian Oil Company Processes for producing petrochemical products that utilize hydrotreating of cycle oil
US11242493B1 (en) 2020-09-01 2022-02-08 Saudi Arabian Oil Company Methods for processing crude oils to form light olefins
US11230672B1 (en) 2020-09-01 2022-01-25 Saudi Arabian Oil Company Processes for producing petrochemical products that utilize fluid catalytic cracking

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2564268A (en) * 1947-11-10 1951-08-14 Phillips Petroleum Co Catalytic oil cracking
US2587703A (en) * 1948-02-18 1952-03-04 Universal Oil Prod Co Cracking heavy oils in presence of oxygen
US3027415A (en) * 1958-03-19 1962-03-27 Production of unsaturated hydrocarbons

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2564268A (en) * 1947-11-10 1951-08-14 Phillips Petroleum Co Catalytic oil cracking
US2587703A (en) * 1948-02-18 1952-03-04 Universal Oil Prod Co Cracking heavy oils in presence of oxygen
US3027415A (en) * 1958-03-19 1962-03-27 Production of unsaturated hydrocarbons

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4370223A (en) * 1980-12-31 1983-01-25 Chevron Research Company Coking hydrocarbonaceous oils with an aqueous liquid
US4504382A (en) * 1982-10-14 1985-03-12 Exxon Research And Engineering Co. Phosphorus-containing catalyst and catalytic cracking process utilizing the same
US4663018A (en) * 1985-06-27 1987-05-05 Betz Laboratories, Inc. Method for coke retardant during hydrocarbon processing
EP0207745A3 (en) * 1985-06-27 1988-02-10 Betz Europe, Inc. Composition and method for coke retardant during hydrocarbon processing
US20050126107A1 (en) * 2002-04-12 2005-06-16 Colman Derek A. Support grid

Also Published As

Publication number Publication date
FR1314261A (fr) 1963-01-04
CH408903A (de) 1966-03-15
GB978576A (en) 1964-12-23
DE1133362B (de) 1962-07-19
NL274559A (enExample)

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