US2812289A - Staged calcining of fluid coke with falling, non-fluid bed - Google Patents

Staged calcining of fluid coke with falling, non-fluid bed Download PDF

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US2812289A
US2812289A US510698A US51069855A US2812289A US 2812289 A US2812289 A US 2812289A US 510698 A US510698 A US 510698A US 51069855 A US51069855 A US 51069855A US 2812289 A US2812289 A US 2812289A
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Jr Charles Newton Kimberlin
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ExxonMobil Technology and Engineering 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, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L9/00—Treating solid fuels to improve their combustion
    • C10L9/02—Treating solid fuels to improve their combustion by chemical means
    • C10L9/04—Treating solid fuels to improve their combustion by chemical means by hydrogenating

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  • This invention relates to improvements in the desulfurization, devolatilization and increase in electrical conductivity of fluid coke. More particularly it relates to a staged calcining treatment wherein the coke is treated While in the form of a falling, non-fluid bed. The coke is first contacted with a gaseous hydrocarbon at a lower temperature and the evolved hydrogen further treats the coke at a higher temperature.
  • the fluid coking unit consists basically of a reaction vessel or coker and a heater or burner vessel.
  • a reaction vessel or coker In a typi- .cal operation the heavy oil to be processed is injected into the reaction vessel containing a dense, turbulent, fluidized bed of hot inert solid particles, preferably coke particles.
  • a transfer line or staged reactors can be employed. Uniform temperature exists in the coking bed. Uniform mixing in the bed results in virtually isothermal conditions and effects instantaneous distribution of the feed stock. In the reaction zone the feed stock is partially vaporized and partially cracked. Product vapors are removed from 1.
  • the coking vessel and sent to a fractionator for the recovery of gas and light distillates therefrom. Any heavy bottoms is usually returned to the coking vessel.
  • the coke produced in the process remains in the bed coated on the solid particles. Stripping steam is injected into the stripper to remove oil from the coke particles prior to the passage of the coke to the burner.
  • the heat for carrying out the endothermic coking reaction is generated in the burner vessel, usually but not necessarily separate.
  • a stream of coke is thus transferred from the reactor to the burner vessel, such as a transfer line or fluid bed burner, employing a standpipe and riser system; air being supplied to the riser for conveying the solids to the burner.
  • Sufficient coke or added carbonaceous matter is burned in the burning vessel to bring the coke production, which represents the coke make less the coke burned, is withdrawn.
  • Heavy hydrocarbon oil feeds suitable for the coking process include heavy crudes, atmospheric and crude vacuum bottoms, pitch, asphalt, other heavy hydrocarbon petroleum residua or mixtures thereof. Typically such feeds can have an initial boiling point of about 700 F.
  • This invention provides an improved staged calcining operation for achieving this purpose.
  • the process comprises treating the coke in a unitary calcining zone while in the form ot a falling, non-flud bed.
  • a normally gaseous hydrocarbon countercurrently contacts the fluid coke in a lower portion of the calcination zone at a temperature in the range of l800 to 2200 F.
  • the hydrocarbon is cracked to hydrogen and carbon which latter deposits in the voids of the fluid coke.
  • the evolved hydrogen countercurrently contacts the falling fluid coke in an upper portion of the calcination zone at a temperature in the range of 2000 to 2.700" P.
  • the total holdup time in the calcination zone is in the range of about 30 minutes to 6 hours.
  • the temperature in the lower part of the bed is low because of the endothermic heat of the cracking reaction occurring therein. In passing form the bottom to the top of the bed there is first a fairly rapid increase in temperature and thereafter a less rapid increase.
  • the size of the zone of rapid temperature change (which is the zone Where most of the cracking is occurring) will depend upon the rate of flow of gas, i. e., for a high rate of flow this zone will be larger than for a low rate of flow.
  • This zone will ordinarily occupy one-t-entlrto one-half, preferably about onefourth, of the total bed volume.
  • the time of high temperature treating can thus be in the range of 20 minutes to four hours and the lower temperature in the range of 10 minutes to two hours.
  • the falling, non-fluid bed is that the same as a moving bed.
  • the particles are substantially not in motion with respect to each other, but the total mass slowly descends through the vessel.
  • the rate of descent is in the range of 1 to ft./ hr. depending upon the design of the vessel and upon the contact or residence time desired.
  • the density of the bed is about 55 to 62 lbs/cu. ft.
  • the velocity of the treating gases i. e., the evolved hydrogen and the normally gaseous hydrocarbon, is thus kept below that required to fluidize the coke.
  • the linear velocity is the critical one and should be kept below a maximum of about 0.2 ft./sec., preferably about 0.1 ft./ sec. or less. This does not depend upon vessel geometry.
  • the normally gaseous hydrocarbons that can be employed include C1 to C4 hydrocarbons such as methane, ethane, propane and butane. Unsaturates such as ethylene, propylene, butylene can also be employed. Methane is particularly preferred and effective.
  • the gas rate as expressed in volumes of gas per volume of coke per hour '2800 F. e. g. 2700 F. to supply the heat requirements further downstream in the process.
  • a transfer line burner can be used if desired. This heating is accomplished by burning part of the coke with preheated air from line 5. If desired an alternative fuel such as gas or oil from line 7 may be burned to supply the heat.
  • Flue gases are vented through cyclone 8 and line 10.
  • the heated coke is transferred by line 9 into an upper "portion of calcination zone 11, preferably conical shaped,
  • the falling, non-fluidized fluid coke .particles are treated with hydrogen at a temperature in the range of 2000 to 2700 F., e. g. 2600 F.
  • the temperature at the very top of zone 20 will be the same as that of the entering coke, i. e. 2700 F. in the example.
  • the temperature in the lower part of this zone will be considerably lower, say about 2200 to 2400 F.
  • Original green coke contained 7.5 wt. percent sulfur.
  • the hydrogen which has been evolved in a lower zone 22 and which thus countercurrently treats the fluid coke in upper zone 20 is at a linear velocity insufficient to fluidize the coke, less than about 0.2 ft./sec.', e. g. 0.1 ft./sec.
  • the hydrogen, hydrogen sulfide, carbon disulfide and other volatiles are removed through line 13.
  • the density and electrical conductivity of the coke is increased.
  • the residence time in the upper zone 20 is 1 /2 hours and in the lower zone 22 is /2 hour.
  • the desulfurized coke is with-drawn from a lower portion of the calciner through line 17.
  • EXAMPLE 1 Inone series of runs the temperature of calcination was varied from 1350 to 2700 F. while using a gas con- The temperature drop comes about in two ways: (1) heat Methane gives high coke yields for a givenreduction in sulfur content. Although yield values are now shown in Table II for air and steam, these gases are known to consume coke rapidly at these temperatures. This fact is more apparentat longer contact times.
  • the sulfur content of thecoke canbe reduced to be- CONDITIONS IN FLUID COKER REACTOR Broad Preferred Range Range Temperature, F 850-1. 200 900-1. 000 Pressure, Atmospheres -1- l-lO 1. 5-2 Superficial Velocity of Fluidizing Gas, cc. 0. 2-10 0. 5-4 Coke Circulation (Solids/Oil Ratio) 2-30 7-15 It is to be understood that this invention is not limited to the specific examples which have been otfered merely as illustrations and that modification may be made without departing from the spirit of the invention.
  • a process for desulfurizing, devolatilizing and increasing the density of fluid coke particles which comprises the steps of feeding heated coke particles to an upper portion of a calcination zone; maintaining the coke particles therein in the form of a falling, non-fluid bed; countercurrently contacting the coke particles under reducing conditions in an upper portion of the calcination zone at a temperature in the range of 2000 t0 2700 F. with hydrogen evolved in the lower portion of the calcination zone, the hydrogen velocity being less than that required to fiuidize the coke; countercurrently contacting the thus treated coke in a lower portion of the calcination zone at a temperature in the range of 1800 to 2200" E.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Description

Nov. 5, 1957 STAGED CALCINING c. N. KIMBERLIN, JR 2,812,289
0F FLUID COKE WITH FALLING, NON-FLUID BED Filed May 24, 1955 F ll 7 FALLING, NON-FLUID BED OF COKE COKE WITHDRAWAL Charles N. Kimberh'r Jr Invenfbr By C Attorney United States Patent STAGED CALCINING 0F FLUID COKE WITH FALLING, NON -FLUID BED Charles Newton Kimberlin, Jr., Baton Rouge, La., as-
signor to Esso Research and Engineering Company, a corporation of Delaware Application May 24, 1955, Serial No. 510,693
Claims. (Cl. 20231) This invention relates to improvements in the desulfurization, devolatilization and increase in electrical conductivity of fluid coke. More particularly it relates to a staged calcining treatment wherein the coke is treated While in the form of a falling, non-fluid bed. The coke is first contacted with a gaseous hydrocarbon at a lower temperature and the evolved hydrogen further treats the coke at a higher temperature.
There has recently been developed an improved process known as the fluid coking process for the production of fluid coke and the terminal conversion of heavy hydrocarbon oils to lighter fractions, e. g., see Serial No. 375,088, filed August 10, 1953. For completeness the process is described in further detail below although it should be understood that the fluid coking process itself is no part of this invention.
The fluid coking unit consists basically of a reaction vessel or coker and a heater or burner vessel. In a typi- .cal operation the heavy oil to be processed is injected into the reaction vessel containing a dense, turbulent, fluidized bed of hot inert solid particles, preferably coke particles. A transfer line or staged reactors can be employed. Uniform temperature exists in the coking bed. Uniform mixing in the bed results in virtually isothermal conditions and effects instantaneous distribution of the feed stock. In the reaction zone the feed stock is partially vaporized and partially cracked. Product vapors are removed from 1.
the coking vessel and sent to a fractionator for the recovery of gas and light distillates therefrom. Any heavy bottoms is usually returned to the coking vessel. The coke produced in the process remains in the bed coated on the solid particles. Stripping steam is injected into the stripper to remove oil from the coke particles prior to the passage of the coke to the burner.
The heat for carrying out the endothermic coking reaction is generated in the burner vessel, usually but not necessarily separate. A stream of coke is thus transferred from the reactor to the burner vessel, such as a transfer line or fluid bed burner, employing a standpipe and riser system; air being supplied to the riser for conveying the solids to the burner. Sufficient coke or added carbonaceous matter is burned in the burning vessel to bring the coke production, which represents the coke make less the coke burned, is withdrawn.
Heavy hydrocarbon oil feeds suitable for the coking process include heavy crudes, atmospheric and crude vacuum bottoms, pitch, asphalt, other heavy hydrocarbon petroleum residua or mixtures thereof. Typically such feeds can have an initial boiling point of about 700 F.
or higher, an A. .P. I. gravity of about 0 to 20, and a Conradson carbon residue content of about 5 to 40 wt.
2,812,289 Patented Nov. 5, 1957 above 6 wt. percent, and a volatile content of 2 to 10 wt.
percent. They have a real density of about 1.4 to 1.7 which is too low for use in the manufacture of carbon electrodes for making aluminum and other purposes. Increased density and lower sulfur and volatile content are particularly necessary before the fluid coke is suitable for manufacture into electrodes, one of the major uses of petroleum coke. The attainment of these properties can be accomplished by calcining the coke at high temperatures, e. g., minimum temperatures of 2100 F. or higher. These temperatures and the times required make the calcining operation relatively diflicult and expensive. It is therefore desirable to effect improvements in the calcination and conditioning of the fluid coke.
This invention provides an improved staged calcining operation for achieving this purpose. The process comprises treating the coke in a unitary calcining zone while in the form ot a falling, non-flud bed. A normally gaseous hydrocarbon countercurrently contacts the fluid coke in a lower portion of the calcination zone at a temperature in the range of l800 to 2200 F. The hydrocarbon is cracked to hydrogen and carbon which latter deposits in the voids of the fluid coke. The evolved hydrogen countercurrently contacts the falling fluid coke in an upper portion of the calcination zone at a temperature in the range of 2000 to 2.700" P.
The total holdup time in the calcination zone is in the range of about 30 minutes to 6 hours. The temperature in the lower part of the bed is low because of the endothermic heat of the cracking reaction occurring therein. In passing form the bottom to the top of the bed there is first a fairly rapid increase in temperature and thereafter a less rapid increase. The size of the zone of rapid temperature change (which is the zone Where most of the cracking is occurring) will depend upon the rate of flow of gas, i. e., for a high rate of flow this zone will be larger than for a low rate of flow. This zone will ordinarily occupy one-t-entlrto one-half, preferably about onefourth, of the total bed volume. The time of high temperature treating can thus be in the range of 20 minutes to four hours and the lower temperature in the range of 10 minutes to two hours.
The falling, non-fluid bed is that the same as a moving bed. The particles are substantially not in motion with respect to each other, but the total mass slowly descends through the vessel. The rate of descent is in the range of 1 to ft./ hr. depending upon the design of the vessel and upon the contact or residence time desired. The density of the bed is about 55 to 62 lbs/cu. ft.
The velocity of the treating gases, i. e., the evolved hydrogen and the normally gaseous hydrocarbon, is thus kept below that required to fluidize the coke. The linear velocity is the critical one and should be kept below a maximum of about 0.2 ft./sec., preferably about 0.1 ft./ sec. or less. This does not depend upon vessel geometry.
The normally gaseous hydrocarbons that can be employed include C1 to C4 hydrocarbons such as methane, ethane, propane and butane. Unsaturates such as ethylene, propylene, butylene can also be employed. Methane is particularly preferred and effective. The gas rate as expressed in volumes of gas per volume of coke per hour '2800 F. e. g. 2700 F. to supply the heat requirements further downstream in the process. A transfer line burner can be used if desired. This heating is accomplished by burning part of the coke with preheated air from line 5. If desired an alternative fuel such as gas or oil from line 7 may be burned to supply the heat.
Flue gases are vented through cyclone 8 and line 10.
Solids are returned to the bed through dipleg 12.
The heated coke is transferred by line 9 into an upper "portion of calcination zone 11, preferably conical shaped,
to provide easy passage of the dense bed. In the upper zone 20 of calciner 11 the falling, non-fluidized fluid coke .particles are treated with hydrogen at a temperature in the range of 2000 to 2700 F., e. g. 2600 F. The temperature at the very top of zone 20 will be the same as that of the entering coke, i. e. 2700 F. in the example.
However, the temperature in the lower part of this zone will be considerably lower, say about 2200 to 2400 F.
4 sisting essentially of hydrogen as the treating gas. The coke was treated for minutes with'hydrogen at each temperature as shown in Table I.
Table I HYDROGEN OALCINATION OF FLUID GOKE EFFEOT OF TEMPERATURE (30.-MINUTE TREATMENT) Coke Sulfur, Real Temp., F. Yield, Wt. Density,
Wt. Percent 25 0. Percent 1! Original green coke contained 7.5 wt. percent sulfur and had a density of 1.50 at 25 C It is apparent from the data in Table I that temperatures of 2000 F. and above are required to geta good rate of sulfur removal.
EXAMPLE 2 Direct comparisons were made between gases consisting essentially of hydrogen and several other common gases in fluid coke calcining at 2400 F. and 2700 F. The coke was treated for 30 minutes with the various gases, all at the same v./v./hr. Summary data are given in Table II.
Table II COMPARISON OF HYDROGEN WITH OTHER COMMON GASES IN'FLUID COKE OALCINING (30 Minute Treatment) Steam (75 vol.
Treating Gas Hg Hz N a N2 Air Air Steam C0 C02 CH percent), C0
(25 vol. percent) Temperature, F 2, 400 2, 700 2, 400 2, 700 2, 400 2, 700 2, 400 2, 400 2, 400 2, 400 2, 400 Coke Yield, Wt. Percent 89 83 92 85 90 80 97 1 80 Sulfur, Wt. Percent 4. 9 l. 8 7. 4 3. 7 6. 7 2. 8 a 5. 2' 6. 2 5. 8 n 5. 6 5. 7
Original green coke contained 7.5 wt. percent sulfur.
b Yields not available for these runs.
s Yield high because of carbon deposition from OH; cracking.
is needed to heat up the hydrogen from the cracked gases entering below, and (2) heat is consumed in vaporizing the volatile matter of the coke including the sulfur. The hydrogen which has been evolved in a lower zone 22 and which thus countercurrently treats the fluid coke in upper zone 20 is at a linear velocity insufficient to fluidize the coke, less than about 0.2 ft./sec.', e. g. 0.1 ft./sec. The hydrogen, hydrogen sulfide, carbon disulfide and other volatiles are removed through line 13.
-e. g. 2100 F. The density and electrical conductivity of the coke is increased. The residence time in the upper zone 20 is 1 /2 hours and in the lower zone 22 is /2 hour.
The desulfurized coke is with-drawn from a lower portion of the calciner through line 17.
The particular advantage of hydrogen at elevated temperature in the treatment of fluid'coke is demonstrated in'the following examples.
EXAMPLE 1 .Inone series of runs the temperature of calcination was varied from 1350 to 2700 F. while using a gas con- The temperature drop comes about in two ways: (1) heat Methane gives high coke yields for a givenreduction in sulfur content. Although yield values are now shown in Table II for air and steam, these gases are known to consume coke rapidly at these temperatures. This fact is more apparentat longer contact times.
Yields are lower for air and steam-because-both attack the carbon. Oxygen in the air burns the coke to give CO and steam gives CO+H2 by the water gas'reaction. As an illustration, one run made with air at 4500 v./v./hr. at 2400 F. and for a time of 20' minutes gave a yield of 82.5% as compared with 89% for hydrogen at a time of 30 minutes.
Another air run made at 2700 F. gave a yield of only 74.0% using a 20 minute'time of treating.
It is important to note the advantage for hydrogen over all the other gases shownin sulfur content. of the coke product. Thisholds for both 2400 F. and 2700 F, The superiority for hydrogen overnitrogen is significant in view of the fact that both are inert gases insofar as any reactionwith the carbon of the coke is concerned.
These runs were discontinued for the most part after 30 minutes because time intervals of that nature have been found to be valid and reliablein screening tests on different gaseous materials. Varying the tcrnperatureor time of treatment of both within the prescribed ranges can bring the sulfur content down to levels required.
The advantages of the process of this invention reside particularly in the fact that in addition to the desulfurization that is obtained, a coke product of high density, purity and good conductivity is provided without requiring an extraneous hydrogen supply.
The sulfur content of thecoke canbe reduced to be- CONDITIONS IN FLUID COKER REACTOR Broad Preferred Range Range Temperature, F 850-1. 200 900-1. 000 Pressure, Atmospheres -1- l-lO 1. 5-2 Superficial Velocity of Fluidizing Gas, cc. 0. 2-10 0. 5-4 Coke Circulation (Solids/Oil Ratio) 2-30 7-15 It is to be understood that this invention is not limited to the specific examples which have been otfered merely as illustrations and that modification may be made without departing from the spirit of the invention.
What is claimed is:
1. A process for desulfurizing, devolatilizing and increasing the density of fluid coke particles which comprises the steps of feeding heated coke particles to an upper portion of a calcination zone; maintaining the coke particles therein in the form of a falling, non-fluid bed; countercurrently contacting the coke particles under reducing conditions in an upper portion of the calcination zone at a temperature in the range of 2000 t0 2700 F. with hydrogen evolved in the lower portion of the calcination zone, the hydrogen velocity being less than that required to fiuidize the coke; countercurrently contacting the thus treated coke in a lower portion of the calcination zone at a temperature in the range of 1800 to 2200" E. with a normally gaseous hydrocarbon at a velocity less than that required to fiuidize the coke, the hydrocarbon being cracked to hydrogen and carbon which deposits on the voids of the fluid coke, said cracking cooling the coke to the required temperature and withdrawing calcined fluid coke product from the lower portion of the calcination zone, the total treating time in the calcination zone being in the range of minutes to 6 hours.
2. The process of claim 1 in which the treating time in the upper zone is in the range of 20 minutes to 4 hours, and the treating time in the lower .zone is in the range of 10 minutes to 2 hours.
3. The process of claim 1 in which the maximum linear velocity of the hydrogen and the normally gaseous hydrocarbon is 0.2 ft./sec.
4. The process of claim 3 in which the normally gaseous hydrocarbon is utilized in an amount of 20-150 v./v./hr. and the density of the falling, non-fluid bed is in the range of -62 lbs/cu. ft.
5. The process of claim 4 in which the normally gaseous hydrocarbon is methane.
References Cited in the file of this patent UNITED STATES PATENTS

Claims (1)

1. A PSROCESS FOR DESULFURIZING, DEVOLATILIZING AND INCREASING THE DENSITY OF FLUID COKE PARTICLES WHICH COMPRISES THE STEPS OF FEEDING HEATED COKE PARTICLES TO AN UPPER PORTION OF A CLACINATION ZONE; MAINTAINING THE COKE PARTICLES THEREIN IN THE FORM OF A FALLING, NON-FLUID BED; COUNTERCURRENTLY CONTACTING THE COKE PARTICLES UNDER REDUCING CONDITIONS IN AN UPPER PORTION OF THE CALCINATION ZONE AT A TEMPERATURE IN THE RANGE OF 2000* TO 2700* F. WITH HYDROGEN EVOLVED IN THE LOWER PORTION OF THE CALCINATION ZONE, THE HYDROGEN VELOCITY BEING LESS THAN THAT REQUIRED TO FLUIDIZE THE COKE; COUNTERCURENTLY CONTACTING THE THUS TREATED COKE IN A LOWER PORTION OF THE CALCINATION ZONE AT A TEMPERATURE IN THE RANGE OF 1800* TO 2200* F. WITH A NORMALLY GASEOUS HYDROCARBON AT A VELOCITY LES THAN THAT REQUIRED TO FLUIDIZE THE COKE, THE HYDROCARBON BEING CRACKED TO HYDROGEN AND CARBON WHICH DEPOSITS ON STHE VOIDS OF THE FLUID COKE, SAID CRACKING COOLING THE COKE TO THE REQUIRED TEMPERATURE AND WITHDRAWING CALCINED FLUID COKE PRODUCT FROM THE LOWER PORTION OF THE CALCINATION ZONE, THE TOTAL TREATING TIME IN THE CIRCINATION ZONE BEING IN THE RANGE OF 30 MINUTES TO 6 HOURS.
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3214346A (en) * 1962-01-16 1965-10-26 Exxon Research Engineering Co Removing ash components from coke by leaching
US3236745A (en) * 1966-02-22 Calcining coke
FR2215386A1 (en) * 1973-01-26 1974-08-23 Reis Thomas Desulphurisation of high-sulphur petroleum coke - by heat treatment in a rotary furnace
US4291008A (en) * 1980-06-27 1981-09-22 Great Lakes Carbon Corporation Process for calcining and desulfurizing petroleum coke

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2716628A (en) * 1950-11-13 1955-08-30 Exxon Research Engineering Co Desulfurization of petroleum coke
US2721169A (en) * 1954-05-21 1955-10-18 Exxon Research Engineering Co Desulfurization of fluid coke with oxygen and hydrogen

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2716628A (en) * 1950-11-13 1955-08-30 Exxon Research Engineering Co Desulfurization of petroleum coke
US2721169A (en) * 1954-05-21 1955-10-18 Exxon Research Engineering Co Desulfurization of fluid coke with oxygen and hydrogen

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3236745A (en) * 1966-02-22 Calcining coke
US3214346A (en) * 1962-01-16 1965-10-26 Exxon Research Engineering Co Removing ash components from coke by leaching
FR2215386A1 (en) * 1973-01-26 1974-08-23 Reis Thomas Desulphurisation of high-sulphur petroleum coke - by heat treatment in a rotary furnace
US4291008A (en) * 1980-06-27 1981-09-22 Great Lakes Carbon Corporation Process for calcining and desulfurizing petroleum coke

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