CA1260868A - Process for calcining green coke - Google Patents

Process for calcining green coke

Info

Publication number
CA1260868A
CA1260868A CA000476282A CA476282A CA1260868A CA 1260868 A CA1260868 A CA 1260868A CA 000476282 A CA000476282 A CA 000476282A CA 476282 A CA476282 A CA 476282A CA 1260868 A CA1260868 A CA 1260868A
Authority
CA
Canada
Prior art keywords
stage
coke
volatile matter
temperature
furnace
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
CA000476282A
Other languages
French (fr)
Inventor
Izaak Lindhout
Ferdinand J.A. Geiger
Barend Alberts
Roger S. Downing
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.)
Shell Canada Ltd
Original Assignee
Shell Canada Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Shell Canada Ltd filed Critical Shell Canada Ltd
Application granted granted Critical
Publication of CA1260868A publication Critical patent/CA1260868A/en
Expired legal-status Critical Current

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10LFUELS 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
    • C10L9/00Treating solid fuels to improve their combustion
    • C10L9/08Treating solid fuels to improve their combustion by heat treatments, e.g. calcining

Landscapes

  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Coke Industry (AREA)
  • Carbon And Carbon Compounds (AREA)
  • Inorganic Insulating Materials (AREA)
  • Compositions Of Oxide Ceramics (AREA)
  • Processing Of Solid Wastes (AREA)
  • Manufacture And Refinement Of Metals (AREA)
  • Control And Other Processes For Unpacking Of Materials (AREA)
  • Fertilizers (AREA)
  • Mold Materials And Core Materials (AREA)
  • Solid Fuels And Fuel-Associated Substances (AREA)

Abstract

A B S T R A C T

A PROCESS FOR CALCINING GREEN COKE

A process for calcining green coke containing combustible volatile matter in at least two stages, whereby in a first stage the green coke is heated in a furnace to a temperature of between 750 °C and 1000 °C and in a second stage in a second furnace to a temperature of between 1200 °C and 1600 °C, characterized in that the heating in the first stage is carried out with a controlled heat-up rate of less than 60 °C/min in the temperature range of between 600 °C and 800 °C, whereby said heating up is achieved by hot combusted volatile matter, which is obtained by withdrawing the released volatile matter from the first stage, burning said volatile matter outside the first stage and recycling the burnt volatile matter to the first stage.

Description

fi~

. I

A PROCESS FOR CALCINING GREEN COKE

The invention relates to a process for calcining green coke containing combustible volatile matter in at least two stagesj whereby in a first stage the green coke is heated in a furnace to a temperature of between 750 C and 1000 C and in a second stage in a second furnace to a temperature of between 1200 C and 1600 C.
It is generally known that green coke made from a suitable hydrocarbon feedstock may be converted to high quality needle coke for use in high performance graphite electrodes which are applied in electric ore furnaces, or other purposes, like in baked carbon anodes in aluminium cells. For this purpose the green coke, after the water being removed at relatively low ~emperatures, is heated (precalcinated) in a furnace to a temperature which necessary to release at least a part of the combustible volatile matter, generally around 800 ~C. In a further stage the coke is calcined in a second furnace to a temperature in the range between 1200 C
and 1600 ~C. In principle in each of the stages either a shaft kiln, a rotary kiln or a rotary hearth furnace may be used, depending on the specific circumstances. After the precalcination cooling of the product may optionally take place, before the second stage calcination is carried out. The patent literature describes a number of processes for calcining coke, for example UK
patent specification 1,603,924, UK patent applications 2,093,061 and 2,016,512, German patent specification 2,931,475 and US patent specification 4,291,008.
In UK patent specification 1,603,924 is disclosed a process for calcining green coke in three stages of heating furnaces which are connected in series and in which process in a first step the water is evaporated from the green coke, in a second step the volatile matter is distilled off and burnt from the dried coke and
- 2 -in a third step the coke is calcined. In the precalcination stage preheated air is introduced into the burning kiln in order to burn the released volatile matter. Disadvantages are the degradation in particle siæe distribution upon calcination, the high friability of the product obtained by such a process and the lower product yield resulting from coke combustion.
Applicant has now found a process in which these disadvantages may be avoided.
The invention relates to a process for calcining green coke containing combustible volatile matter in at least two stages, whereby in a first stage the green coke is heated in a furnace to a temperature of between 750 C and 1000 C and in a second stage in a second furnace to a temperature of between 1200 C and 1600 C, characterized in that the heating in the first stage is carried out with a controlled heat-up rate of less than 60 C/min in the temperature range of between 600 C and 800 C, whereby said heating up is achieved by hot combusted volatile matter, which is obtained by withdrawing the released volatile-matter from the first stage, burning said volatile matter outside the first stage and recycling the burnt volatile matter to the first stage.
Part of the hot combusted gases may be obtained by burning an additional combustible gas outside the first stage and introducing the burnt gas into the first stage.
A major advantage of the process according to the invention is that the calcined coke contains sufficient coarse material, which makes it especially suitable for the manufacture of ultra high power electrodes.
It is advantageous to carry out the first stage, namely the precalcination in a non-oxidiæing atmosphere, this means that except from some oxygen leaked into the kiln because it works below atmospheric pressure, there is no more or hardly any free oxygen present in the recycled gases. The atmosphere in the precalcination stage could also be described as reducing.

In principle in the first stage any type of furnace is suitable, a rotary kiln is preferred. In the second stage any type of kiln may be suitable. Preference is given to the com-bination of a rotary kiln with a rotary hearth furnace in the first and second stage respectively.
The heat-up rate control in the first stage is regulated by the temperature and the amount of combusted gases, which prefer-ably flow countercurrently with the direction in which the green coke flows. In a rotary kiln the direction in which the green coke flows, has a small angle with the horizontal surface. The incli-nation of said rotary kiln is generally below 5. Depending upon the total length and the rotational speed of the kiln the retent-ion time of the coke in the first kiln may be so chosen that the heat-up rate does not exceed 60 C per minute, preferably the heat-up rate is less than 40 C per minute. At the upper part of the rotary kiln the green coke is introduced and due to the rotation of the kiln and the gravity the green coke moves to the lower end of the kiln. The combustible volatile matter released from the grsen coke in the first stage, leaves the upper end and is recycled via a burner to the first stage furnace. Additional combustible gas if necessary, and air are added, so that combustion takes place in the burner. The combusted gases entering the lower part of the kiln have a temperature of between 900 C
and 1300 C. A part of the combustible volatile matter is withdrawn from the recycling system before entering ths burner.
The right temperature and the amount of burnt gas necessary to achieve the controlled release of the combustible gases from the green coke is in this way secured. The amount of oxygen in the air introduced into the burner, is generally completely used for com-bustion of the gases, before these are recycled to the furnace inthe first stage. The precalcined coke leaving the lower part of the kiln is transported to a rotary hearth furnace or other kiln.
The kilns of the first and the second stage may be so arranged that the transport takes place by gravity. The inlet of the calciner may be positioned immediately below the outlet of the precalciner and thc precalcined coke is directly dropped into the coke feeding device of the calciner. Transportation may also take place by means of a conveyor. After the green coke has been subjected to precalcination, the obtained product may preferably be cooled to a temperature below 100 C, or even to room temperature. As already stated hereinbefore the second stage (calcination) may take place in any kind of furnace, in which the presence of free oxygen may be tolerated. Preference is given to a rotary hearth furnace, which is well known in industry.
The process as applicable to any type of green coke, produced by delayed coking from heavy oils of petroleum or coal origin, such as residue oils of catalytic cracking, thermal cracking or steam cracking, stralght run oils and tars resulting from thermal cracking or coal tar pitch or any suitable blend of two or more of the above-mentioned oils before or after any additional treatment as thermal treatment, solvent extraction or hydrotreatment and the like.
Furthermore the process according to the invention may be carried out in such a way that only one furnace is used with two different stages: the precalcination and the calcination, wherein the temperatures and gas compositions are controlled.
EXAMPLE
Green coke with a water content of 9% weight was introduced at the upper end into a rotary kiln (with a length of 12 metres and an internal diameter of 0.5 metre) and precalcined to a temperature of 826 C. The 8reen coke was introduced at a rate of 250 kg/h, while the kiln was operated at 2 rpm (rotations per minute), the inclination being 2.5 degrees. The green coke was obtained as residue in the steam cracking process of naphtha and gas oil.
The green coke was heated-up with a flue gas which had a temperature of 950 C and which gas flowed in the direction countercurrently with the direction in which the coke was moving.
The outlet temperature of the flue gas was 480 C. The flue gas which contained no free oxygen, was produced by external stoichio-metric combustion in a burner chamber of 16 kg/h natural gas with 206 kg/h air of ambient temperature and quenching the adiabatic flame temperature with a recycle of 730 kg/h of the total amount of 1081 kg/h of kiln-off gas. 357 kg/h of the kiln-off gas is withdrawn from the recycle stream. 218 kg/h of precalcined coke was obtained at the lower end of the rotary kiln.
The heat-up rate of the coke in the temperature range of from 600 C to 800 C was 24 C/min.
After cooling to 20 C precalcined coke was introduced at a rate of 100 kg/h at the upper end into a second rotary kiln with a final temperature of 1380 C. This rotary kiln was operated at
3.6 rpm and had the same length and diameter as the first kiln.
The inclination was 2.5 degrees. The coke was heated up by once through countercurrent heat exchange in an oxidizing atmosphere with a flue gas which had an inlet temperature of 1480 C. The flue gas was obtained by combustion of natural gas with air and additional air was added to maintain an oxidi~ing atmosphere in the kiln. Starting from 100 kg/h of precalcined coke 94 kg/h of calcined coke was obtained. Real density was 2.13 g/ml.
Comparative example A comparative experiment was carried out in the s~me rotary kilns, in which the precalcination and the final calcination took place.
250 kg/h of green coke was in~roduced at the upper end into a rotary kiln and precalcinated, while the kiln was operated at 2 rpm.
The green coke was heated-up with a flue gas which had a temperature of 950 C and which gas flowed in the same direction as the coke was moving in the kiln. The flue gas was obtained by burning 17 kg of natural gas with 221 kg/h air of ambient tem-perature and was quenched with 312 kg/h additional air of ambient temperature. Burning of the released combustible gases took place in the rotary kiln. No recycle of the flue gas took place. 214 kg/h of precalcined coke was obtainedO

~6~

The heat-up rate of the coke in the temperature range of from 600 to 800 C could not be controlled, when additional air was used.
The precalcined coke was calcined in the second rotary kiln under exactly the same conditions as described in the example.
Starting from 100 kg/h of precalcined coke 94 kg/h of calcined coke was obtained. Real density was 2.13 g/ml.
The calcined cokes obtained by the process according to the invention (example) and the process according to the comparatlve example differed considerably in physical characteristics.
Hereinafter the friability of the calcined cokes will be compared.

~Zi~ 3~

__ ; I Calcined coke I IGreen coke obtained by I obtained by ¦ ~ process acc. I process acc.
coke particle size to invention ~to comparative distribution I exper-lment _ ~ _ fraction ~ 1 mm 22%w 25%w 27%w fraction ~ 5. 6 mm 40%w 42%w 52%w fraction ~ 10 mm 55%w 59%w 697OW .

Breakdown of coke Green coke Calcined coke fraction 8 to 9. 5 mm in friability test _ obtained by obtained by process acc. process. acc.
to invention to comparative experiment __ . ! _, I
fraction < 1 mm (forl led) 20%w 20%w 1 23/ow fraction ~ 5~6 mm (formed) 26%w 28%w 1 48/ow fraction < 8 mm (unchanged) 35%w 31%w ! 12%w . !

In the friability test the coke fraction of 8 to 9.5 mm is subjected during one hour to mechanical action of 2400 rotations (40 rpm) in a rotating drum provided at the inner side with one baffle.

3~i~

Calcined coke Coefficient of thermal expansion obtained by obtained by for 20 mm 0 artefact. Artefact process acc. process acc.
made by mixing and extrusion of to invention to comparative calcined coke flour with coal tar Xlo~6 K-l example binder pitch, baking of rod at Xlo~6 K-850 C and graphitization of 0.54 0.58 baked rod at 3000 C
Artefacts tested over a temperature range of 35 C
to 235 C.
__ _ _ ... _.

From table 1 it is evident that the friability of the cal-cined coke produced by the process according to the invention has been decreased, the coke has thus become less friable. Starting from a green coke with a given size distribution, it is observed that the obtained coke has hardly undergone any changes in size distribution in the process according to the invention.
From table 2 it is evideat that the calcined coke obtained by the process according to the invention is better proof against deterioration than the calcined coke not produced according to the invention.
From table 3 it is evident that the calcined coke, when graphitized, and prepared by the method according to our invention, has a coefficient of thermal expansion which is less than that of calcined and graphitized coke not prepared according to the invention.

Claims (11)

-THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A process for calcining green coke containing combust-ible volatile matter in at least two stages, whereby in a first stage the green coke is heated in a furnace to a temperature of between 750 °C and 1000 °C and in a second stage in a second furnace to a temperature of between 1200 °C and 1600 °C, charac-terized in that the heating in the first stage is carried out with a controlled heat-up rate of less than 60 °C/min in the temper-ature range of between 600 °C and 800 °C, whereby said heating up is achieved by hot combusted volatile matter, which is obtained by withdrawing the released volatile matter from the first stage, burning said volatile matter outside the first stage and recycling the burnt volatile matter to the first stage.
2. A process as claimed in claim 1, characterized in that part of the hot combusted volatile matter is obtained by burning an additional combustible gas outside the first stage and intro-ducing the burnt gas into the first stage.
3. A process as claimed in claim 1, characterized in that in the first stage furnace a non-oxidizing atmosphere is upheld.
4. A process as claimed in claim 1, characterized in that in the first stage a rotary kiln is used.
5. A process as claimed in claim 1, characterized in that in the second stage a rotary hearth furnace is used.
6. A process as claimed in claim 1, characterized in that in the first stage the hot combusted volatile matter is recycled countercurrently with the direction in which the green coke, being precalcined, flows.
7. A process as claimed in claim 1, characterized in that the hot combusted volatile matter has a temperature of between 900 °C and 1300 °C.
8. A process as claimed in claim 1, characterized in that the amount of oxygen is completely used for combustion of the combustible volatile matter derived from the coke and the additional combustible gas, before they are recycled to rotary kiln.
9. A process as claimed in claim 4 and 5, characterized in that the rotary kiln is situated above the rotary hearth furnace, enabling the coke transport to take place by gravity.
10. A process as claimed in claim 1, characterized in that in the first stage the heating is carried out with a controlled heat-up rate of less than 40 °C/min.
11. A process as claimed in claim 1, characterized in that the precalcinated coke is cooled to a temperature below 100 °C, before it is subjected to the calcination in the second stage.
CA000476282A 1984-04-11 1985-03-12 Process for calcining green coke Expired CA1260868A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB8409402 1984-04-11
GB8409402 1984-04-11

Publications (1)

Publication Number Publication Date
CA1260868A true CA1260868A (en) 1989-09-26

Family

ID=10559530

Family Applications (1)

Application Number Title Priority Date Filing Date
CA000476282A Expired CA1260868A (en) 1984-04-11 1985-03-12 Process for calcining green coke

Country Status (8)

Country Link
EP (1) EP0158387B1 (en)
JP (1) JPH064857B2 (en)
AT (1) ATE49017T1 (en)
BR (1) BR8501688A (en)
CA (1) CA1260868A (en)
DE (1) DE3574988D1 (en)
ES (1) ES8603553A1 (en)
NO (1) NO167301C (en)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3609348A1 (en) * 1986-03-20 1987-09-24 Ruetgerswerke Ag METHOD FOR CONTINUOUS COOKING OF PECHES AND USE OF THE COOK RECOVED
US7480988B2 (en) * 2001-03-30 2009-01-27 Second Sight Medical Products, Inc. Method and apparatus for providing hermetic electrical feedthrough
WO2013187960A1 (en) 2012-06-15 2013-12-19 Fluor Technologies Corporation Carbon baking oxygen preheat and heat recovery firing system
CA2876837C (en) 2012-06-15 2020-06-30 Fluor Technologies Corporation Carbon baking heat recovery ring furnace
KR101405480B1 (en) * 2012-12-21 2014-06-11 주식회사 포스코 Method for manufacturinfg coal briquettes

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3448012A (en) * 1967-02-01 1969-06-03 Marathon Oil Co Rotary concentric partition in a coke oven hearth
US3677533A (en) * 1971-02-08 1972-07-18 Union Oil Co Method of using a coke preheater
US4100265A (en) * 1976-08-02 1978-07-11 Koa Oil Co., Ltd. Process for preparation of high quality coke
JPS5410301A (en) * 1977-06-27 1979-01-25 Koa Oil Co Ltd Method of calcining coke
US4160814A (en) * 1978-03-01 1979-07-10 Great Lakes Carbon Corporation Thermal desulfurization and calcination of petroleum coke
JPS5825392B2 (en) * 1979-03-08 1983-05-27 興亜石油株式会社 Coke firing method
DE3129244A1 (en) * 1981-07-24 1983-02-10 Hoechst Ag, 6000 Frankfurt WATER-SOLUBLE LUBRICANTS

Also Published As

Publication number Publication date
ES542105A0 (en) 1985-12-16
EP0158387A3 (en) 1987-04-01
DE3574988D1 (en) 1990-02-01
JPH064857B2 (en) 1994-01-19
NO167301B (en) 1991-07-15
NO167301C (en) 1991-10-23
NO851426L (en) 1985-10-14
BR8501688A (en) 1985-12-10
EP0158387A2 (en) 1985-10-16
EP0158387B1 (en) 1989-12-27
ATE49017T1 (en) 1990-01-15
ES8603553A1 (en) 1985-12-16
JPS60231791A (en) 1985-11-18

Similar Documents

Publication Publication Date Title
NO155838B (en) PROCEDURE FOR CONTINUOUS PREPARATION OF A PREPARED PRODUCT FOR THE PRODUCTION OF SILICON OR SILICON CARBID.
EP0020057B1 (en) Method and apparatus for producing char and gases from coal
US4169767A (en) Process for calcining coke
CA1260868A (en) Process for calcining green coke
US2209255A (en) Coke production
US4265710A (en) Process for calcining coke
CA1137433A (en) Method and apparatus for calcining delayed coke
CN85106835A (en) Produce the apparatus and method for of white cement clinker
GB723455A (en) Improvements in preparation of a charge for a calcium carbide furnace
RU2553116C1 (en) Method of metallurgical coke production
US4670054A (en) Heat processing of particulate material
GB2158088A (en) Process and apparatus for the production of calcined coke
NO157459B (en) KOKSKALSINERINGSANLEGG.
JPH05202362A (en) Production of acicular coke
CN111961483B (en) Needle coke, process for producing the same, and apparatus for producing the same
GB2085915A (en) Method for producing coke and a high calorific gas from coal
JP2006124561A (en) Silica brick for coke oven
RU1811210C (en) Coke calcination method
GB870730A (en) Improvements in thermal processing of green carbon articles
US256607A (en) tucker
SU737387A1 (en) Charge for producing refractory articles
SU255103A1 (en) METHOD OF MANUFACTURING LIGHTWEIGHT CHAMBER PRODUCTS
SU1458374A1 (en) Method of producing coke and reducing gas
JPH115983A (en) Preparation of coke
IE41468B1 (en) Process for continuous coking of peat bovey coal and wood in particle form

Legal Events

Date Code Title Description
MKEX Expiry