US3712855A - Control of calcined petroleum coke particle size - Google Patents

Control of calcined petroleum coke particle size Download PDF

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Publication number
US3712855A
US3712855A US00034965A US3712855DA US3712855A US 3712855 A US3712855 A US 3712855A US 00034965 A US00034965 A US 00034965A US 3712855D A US3712855D A US 3712855DA US 3712855 A US3712855 A US 3712855A
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coke
particle size
petroleum coke
calcining
calcined
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US00034965A
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V Allred
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Marathon Oil Co
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Marathon Oil Co
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L9/00—Treating solid fuels to improve their combustion
    • C10L9/02—Treating solid fuels to improve their combustion by chemical means
    • C10L9/06—Treating solid fuels to improve their combustion by chemical means by oxidation
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L9/00—Treating solid fuels to improve their combustion
    • C10L9/08—Treating solid fuels to improve their combustion by heat treatments, e.g. calcining

Definitions

  • calcined petroleum coke product can be controlled by either 1) contacting coke with 2-21 mole percent oxygen atmosphere at about 450-600 F. for /a16 hours to prevent an increase in particle size during later calcining, or (2) high volatile petroleum coke fines can be consolidated by calcining them at from about 1800 to about 3000 F. for about /2 to about 2 hours under an atmosphere substantially free from oxygen.
  • Field of the invention pertains to the field of petroleum coke, and to the calcining thereof and might be classified under Class 201, distillation: processes, thermolytic, subclass 9 and surface treating material to reduce or prevent agglomerating or foaming or swelling during distillation or in Class 201, subclass 42, Particle Size.
  • Control of particle size and the corresponding particle density is of particular importance where petroleum coke is to be used for electrodes, resistors, and carbon shapes.
  • the present invention embodies the discovery that, by treating petroleum coke, preferably delayed petroleum coke having selected volatile content, with gases which contain specific levels of oxygen content at temperatures in the range of from about 450 to about 600 F., the coke may be prevented from consolidating during subsequent calcination.
  • finer coke particles can be caused to consolidate, yielding a calcined product which has a higher average particle size than the raw coke being fed.
  • consolidation or agglomeration can be controlled by varying the degree of oxygenation of the coke.
  • FIG. 1 is a vector diagram showing relationship be tween pretreatment temperature, volatile matter, and oxygen content.
  • FIG. 2 is a graph of the relationship between pretreatment time and oxygen uptake on the agglomerating properties of coke.
  • FIG. 3 is a graph showing the relationship between average particle size of the initial and final materials after oxygen pretreatment and before calcining.
  • FIG. 4 is a schematic diagram of laboratory apparatus used for the invention.
  • the starting materials for the present invention are petroleum cokes, e.g. those made by either the delayed or the fluid coking processes as described in Chapter 3 of the aforementioned Petroleum Processing handbook. Delayed petroleum coke is particularly preferred. Volatile content of the dry coke used in practicing the invention should be 10 to 20, more preferably 12 to 15, and most preferably 13 to 14 weight percent.
  • the coke may be contacted with the gas stream in any convenient solid-liquid contactor, e.g. those shown in Perry, Chemical Engineers Handbook 4th ed. (1963), e.g. static-bed systems, such as various dryers where the solids rest on a perforate surface with the gases moving perpendicular to the bed, tunnel dryers, continuous through-circulation conveyor dryers; moving bed systems, e.g. rotary kilns, the Roto-Louvre dryer manufactured by Link Belt Company, various shaft type dryers and coolers in which moving bed systems flow by gravity, the multilouvre dryer of Link Belt Company, various conveyor systems in which the material is contacted with cocurrent, countercurrent or perpendicular gas flow, e.g.
  • any convenient solid-liquid contactor e.g. those shown in Perry, Chemical Engineers Handbook 4th ed. (1963), e.g. static-bed systems, such as various dryers where the solids rest on a perforate surface with the gases moving perpendicular to the bed, tunnel dryer
  • FIG. 4 shows a simple laboratory-type contactor in which the gas stream is preheated in a coil and fed through a bed of carbon lying in a container having a gas-tight lid. This apparatus is convenient for laboratory pretreatment.
  • composition of the pretreatment gas stream to prevent agglomeration the carbonaceous materials is contacted with an oxygencontaining gas stream consisting primarily of air or free oxygen in inert gases, e.g. N C0, C Ar, He, and H 0 vapor prior to calcination.
  • an oxygencontaining gas stream consisting primarily of air or free oxygen in inert gases, e.g. N C0, C Ar, He, and H 0 vapor prior to calcination.
  • inert gases e.g. N C0, C Ar, He, and H 0 vapor
  • the contact time between the coke and the gas stream will be from about 0.3 to about 20, more preferably from 0.4 to about 2, and most preferably from 0.5 to about 1.0 hours. If the carbonaceous material is not spread sufficiently thin to provide good gas-solid contact, longer times will be required.
  • Pretreatment temperature The temperature of the gases contacting the carbonaceous material to prevent agglomeration will be from 350 to about 700, more preferably from 450 to about 650, and more preferably from 450 to about 500 F. In general, it is preferred that the carbonaceous material be at approximately the same temperature and this can readily be accomplished by conventional preheating. However, if necessary, the coke can be brought into contact with the gases at lower coke temperatures with the coke being gradually heated by contact with the hot gas stream.
  • Pretreatment oxygen content In cases where the particle size of the product is to be approximately that of the feed (that is, Where agglomeration is to be avoided), the oxygen content during pretreatment will be from about 2 to about 30, more preferably from 4 to about 25, and most preferably about 21% by volume of the gas stream with care being taken to avoid spontaneous ignition by too high a percent oxygen.
  • FIG. 1 shows the oxygen content versus pretreatment at various temperatures for a typical delayed coke.
  • FIG. 2 shows the eeffct of various intervals of pretreatment with oxygen-containing gas on the degree of oxygen percent and indicates the difference between agglomerating and non-agglomerating characteristics for a typical high volatile delayed coke.
  • FIG. 3 shows the results of treatment of reasonably typical high volatile petroleum coke in air for periods of 1 to 16 hours at a temperature of 500 F.
  • FIGS. 1 through 3 were obtained by techniques similar to those employed in the examples which follow.
  • Calcining apparatus and conditions The apparatus used for calcining according to the present invention can generally be that taught by the references discussed under the description of the prior art, above, except that where the desired particle size is the same as or larger than that of the raw coke being fed to the calciner, apparatus which minimizes the amount of agitation will be preferred. Especially preferred for such purposes will be the apparatus of the aforementioned US. Pat. 3,227,627.
  • this patent teaches oxidizing the volatile material in an upper portion of the devolatilizing chamber to radiate heat onto the material on the hearth.
  • lines -16 it describes a bed of coal 7 being coked upon the substantially imperforate hearth 2 wherein the particles on the hearth are in contacting support with each other.
  • this bed may be formed of materials other than coal, e.g., the petroleum coke of the present application (see also col. 1, line 27 of US. 3,227,- 627).
  • the oxygen content during calcination will be from 0.00 to about 0.10, most preefrably 0.00.
  • the oxygen content during calcination is not narrowly critical but will probably range from about 0. to about 5%, more preferably from 0. to about 4%, and most preferably as low as possible.
  • EXAMPLE I Preventing agglomeration according to the invention
  • delayed petroleum coke produced from vacuum residuum type hydro-carbon feed stock by the method as discussed in Mantel, Carbon and Graphite Handbook, pp. 149-151, crushed to a particle size of minus 20 mesh Tyler Sieve Size is contacted with the air stream containing 21% 05 in a tray-type dryer in which the coke is spread onto trays and the gas stream flows across the stacked trays.
  • the temperature of the gas stream is held at about 500 F. and the contact is maintained for approximately minutes.
  • the coke is removed from the trays of the dryer and is calcined in a 50 ml. crucible for about 30 minutes at about 1800 F.
  • Example II Agglomeration according to the invention
  • the finished volatile content is as stated in Example 1.
  • the product particle size is essentially that of the 50 ml. crucible in which the coke was calcined, indicating that substantial agglomeration has taken place, fusing all the coke into a cohesive mass.
  • EXAMPLE III Preventing agglomeration according to the invention
  • delayed petroleum coke having a particle size distribution and volatile content similar to that of Example II, above is pretreated with the air stream of Example I in a Linkbelt Roto louver Dryer and calcined in the apparatus shown in US. 3,475,286 according to the techniques of Example I, the particle size distribution of the product is approximately the same or smaller than before treatment due to thermal shrinkage, and no substantial agglomeration occurs.
  • calcined petroleum coke having an average particle size of from to about 15,000 microns and a volatile content of from 1 to about 0.01% by weight based on the weight of the calcined coke
  • the improvement comprising intimately contacting coke of the normally agglomerating variety having an average particle size of from about 10 to about 50,000 microns and a volatile content of from 10 to about 25% by weight based on the weight of the dry coke with a gas stream containing from 2 to about 30% by volume free oxygen, the remainder of said gas stream being gases substantially non-reactive with said coke, at a tempera ture of from about 450 to about 600 F.
  • calcined petroleum coke having an average particle size of. from 100 to about 50,000 microns and a volatile content of from 1 to about 0.01 percent by weight based on the weight of the calcined coke
  • the improvement comprising calcining and simultaneously agglomerating coke having an average particle size of from about 10 to about 3,000 microns and a volatile content of from 10 to about 25% by weight based on the weight of the carbon in said coke in contact with gases containing from 0.00 to about 0 .10% by volume free oxygen, the remainder of said gases being substantially non-reactive with said coke, at a temperature of from about 1800 to about 3000 F.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Carbon And Carbon Compounds (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
US00034965A 1970-05-06 1970-05-06 Control of calcined petroleum coke particle size Expired - Lifetime US3712855A (en)

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US (1) US3712855A (OSRAM)
CA (1) CA947683A (OSRAM)
DE (1) DE2114116A1 (OSRAM)
ES (1) ES390030A1 (OSRAM)
FR (1) FR2091165A5 (OSRAM)
GB (2) GB1353461A (OSRAM)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4002533A (en) * 1972-07-06 1977-01-11 Westvaco Corporation Two-step process for conditioning sized coal and resulting product
US4100265A (en) * 1976-08-02 1978-07-11 Koa Oil Co., Ltd. Process for preparation of high quality coke
US4146434A (en) * 1974-11-15 1979-03-27 Standard Oil Company (Indiana) Process for the desulfurization of petroleum coke

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0032520A1 (en) * 1980-01-21 1981-07-29 Great Lakes Carbon Corporation Process and apparatus for calcining coke
CN101779313B (zh) 2007-08-10 2012-11-28 昭和电工株式会社 锂系二次电池用负极、碳系负极活性物质的制造方法、和锂系二次电池及其用途
CN112877086B (zh) * 2021-01-25 2022-11-25 山东平阴丰源炭素有限责任公司 一种石油焦煅烧控制方法

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4002533A (en) * 1972-07-06 1977-01-11 Westvaco Corporation Two-step process for conditioning sized coal and resulting product
US4146434A (en) * 1974-11-15 1979-03-27 Standard Oil Company (Indiana) Process for the desulfurization of petroleum coke
US4100265A (en) * 1976-08-02 1978-07-11 Koa Oil Co., Ltd. Process for preparation of high quality coke

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Publication number Publication date
FR2091165A5 (OSRAM) 1972-01-14
ES390030A1 (es) 1973-06-01
GB1353461A (en) 1974-05-15
GB1354205A (en) 1974-06-05
CA947683A (en) 1974-05-21
DE2114116A1 (de) 1971-11-18

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AS Assignment

Owner name: MARATHON OIL COMPANY, AN OH CORP

Free format text: ASSIGNS THE ENTIRE INTEREST IN ALL PATENTS AS OF JULY 10,1982 EXCEPT PATENT NOS. 3,783,944 AND 4,260,291. ASSIGNOR ASSIGNS A FIFTY PERCENT INTEREST IN SAID TWO PATENTS AS OF JULY 10,1982;ASSIGNOR:MARATHON PETROLEUM COMPANY;REEL/FRAME:004172/0421

Effective date: 19830420