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EP2578666A1 - Method for producing a coking additive by delayed coking - Google Patents

Method for producing a coking additive by delayed coking Download PDF

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Publication number
EP2578666A1
EP2578666A1 EP10852594.0A EP10852594A EP2578666A1 EP 2578666 A1 EP2578666 A1 EP 2578666A1 EP 10852594 A EP10852594 A EP 10852594A EP 2578666 A1 EP2578666 A1 EP 2578666A1
Authority
EP
European Patent Office
Prior art keywords
coking
coke
chamber
charge
additive
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.)
Granted
Application number
EP10852594.0A
Other languages
German (de)
French (fr)
Other versions
EP2578666B1 (en
EP2578666A4 (en
Inventor
Gennady Georgievich Valyavin
Nikolai Ivanovich Vetoshkin
Victor Pavlovich Zaporin
Sergei Vital'evich Sukhov
Mikhail Vladimirovich Mamaev
Igor Viktorovich Bidilo
Konstantin Gennad'evich Valyavin
Mikhail Ivanovich Stukov
Vladimir Semenovich Zagainov
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.)
Obshhestvo S Ogranichennoi Otvetstvennost'yu "Promintekh"
Original Assignee
Obshhestvo S Ogranichennoi Otvetstvennost'yu "Promintekh"
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Publication of EP2578666A1 publication Critical patent/EP2578666A1/en
Publication of EP2578666A4 publication Critical patent/EP2578666A4/en
Application granted granted Critical
Publication of EP2578666B1 publication Critical patent/EP2578666B1/en
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    • 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
    • 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
    • C10B57/00—Other carbonising or coking processes; Features of destructive distillation processes in general
    • C10B57/04—Other carbonising or coking processes; Features of destructive distillation processes in general using charges of special composition
    • C10B57/045—Other carbonising or coking processes; Features of destructive distillation processes in general using charges of special composition containing mineral oils, bitumen, tar or the like or mixtures thereof
    • 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
    • C10G9/00—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G9/005—Coking (in order to produce liquid products mainly)

Definitions

  • This invention relates to oil refining, in particular to delayed coking that produces coke containing 15-25% of volatiles substances, which can be used as a coking additive in a coal coking charge for metallurgical coke production.
  • Oil coke with more than 14% but less than 25% volatiles is capable not only of replacing the K-brand (coking) coal, which is in short supply, in coal coking charges, but also of improving the quality of metallurgical coke ( Russian Federation Patent 2355729 , C10B57/04, published on 20 May 2009).
  • This method includes slowly heating raw materials to 490-515°C in a tubular furnace, mixing the raw materials with a recirculant, presenting the coking distillate products formed inside the coking chamber, in a rectification column, which produces bottoms, supplying the bottoms as the secondary raw materials to the coking chamber at 485-495°C and carrying out coking, which results in the formation of coke ( Z. I. Syunyaev, "Forming, Refining and Using Petroleum Coke", Moscow: Khimiya: 1973, p. 95 ).
  • the drawback of this method is that the coke formed by its application has a high strength and low concentration of volatiles (up to 9% by mass).
  • a delayed coking method capable of guaranteeing that no direct contact would occur between the primary charge and the vapours reaching the rectification column from the coking chamber during the formation of the secondary charge, can prevent coke foam finding its way inside the reaction spiral tubes of the furnace, the coking up of the plant and thus lengthen the spans between overhauls.
  • the technology nearest to the proposed invention is the delayed coking of oil residues, which includes heating the original raw materials to 340-380°C, mixing them with a recirculant- heavy coking gasoil (pyrolisis resin, heavy catalytic cracking gasoil)- in a mixing tank where the secondary charge forms, heating the secondary charge, i.e. the heavy residues formed in the mixing tank, transferring this into the coking chamber at 485-505°C, and coking to form coke (Russian Federation Patent No. 2206595 , class C10B 55/00, published on 20 June 2003).
  • a recirculant- heavy coking gasoil pyrolisis resin, heavy catalytic cracking gasoil
  • the drawback of this invention is the low concentration of volatiles in the final product due to the high coking temperature (485-505°C) and the low efficiency due to extensive foaming, and consequently to not being able to use the coking chamber to its full capacity.
  • This invention aims at increasing the concentration of volatiles in the coke and improving the efficiency of the plant.
  • this method of delayed coking of a coking additive includes preheating of the primary raw materials at 270-350°C, mixing the primary raw materials with the recirculant in the tank for the production of secondary charge, heating the secondary charge, transporting it to the coking chamber, and coking to form the target product.
  • the secondary charge is heated at 455-470°C before it reaches the coking chamber.
  • an anti-foaming dope is introduced into the coking chamber 3-5 hours before the end of coking.
  • the anti-foaming dope is introduced in two to four areas around the perimeter of the coking chamber, so that it covers the entire surface of the foam.
  • Coking carried out at low temperatures because the raw material is charged into the coking chamber at a low temperature, produces coke with a concentration of volatiles of 15-25% to be used as a coking additive.
  • the diagram shows the main parts of the plant for carrying out the proposed method for production of a coking additive by the means of delayed coking.
  • the original raw materials such as tar, de-asphalting asphalt, oil production extracts, heavy gasoil of catalytic cracking or any mixtures of the above, are heated in a tubular furnace 1 to 270-350°C, then discharged into the mixing tank 2 connected in pairs to the rectification column 3.
  • the mixture of the primary raw materials and recirculant, which becomes the secondary charge, is heated to 455-470°C in the tubular furnace 4, then fed into the alternately working coking chambers 5 where a coking additive with 15-25% volatiles is gradually accumulated.
  • the distillate coking products, formed in the coking chamber 5, are discharged into the rectification column 3, where they are resolved into a gas, benzene, light and heavy coking gasoil and the bottoms.
  • Vapour-like products leave the plant through the top of the column 3, light and heavy gasoils are discharged from the middle part of the column, while the bottoms are removed from the bottom part.
  • the anti-foaming dope 6 is introduced in four areas around the perimeter of the coking chamber.
  • a mixture of raw materials, comprised of a vacuum visbreaking residue, tar oil and heavy gasoil of catalytic cracking in the ratio of 15:75:10 was coked, using an industrial delayed coking plant.
  • the mixture had the following characteristics: density 1.055 g/cm 3 , cokeability 25.8% and sulphur content 3.8%.
  • the primary charge was heated in a convection furnace to 320°C, then it was mixed with a recirculate: heavy coking gasoil, discharged from the rectification column as a side fraction.
  • the produced secondary charge was heated in a tubular furnace, then it was fed into the coking chamber to produce a coking additive. When coking was over, the coke was steamed out, water-cooled and discharged by hydraulic means.
  • an anti-foaming dope was introduced into the coking chamber 4 hours before the end of the process - to prevent foam formation.
  • the coking method suggested by this inventor produces coke that can be used as a coking additive, with a concentration of volatiles higher than 15%. Introducing it into the coking chamber at 456°C is not practicable because bitumen is likely to form, and it would make the steaming out and cooling down of coke difficult. On the other hand, a charge introduced at a temperature above 470°C, will produce coke that contains less than 15% of volatiles.

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Coke Industry (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

This invention relates to oil refining, in particular to delayed coking to produce coke with 15-25% of volatiles, to be used as a coking additive in a coal coking charge in metallurgical coke production. This invention aims at improving the concentration of volatiles in coke and the efficiency of the plant. The proposed method includes preheating the primary charge, mixing it with a recirculate in a tank, which produces a secondary charge, heating it at 455-470°°C and introducing it into the coking chamber, and coking, producing a coking additive. It is useful to add an anti-foaming dope into the coking chamber 3-5 hours before the end of coking. It is advisable to add the dope in 2-4 areas around the perimeter of the coking chamber.

Description

  • This invention relates to oil refining, in particular to delayed coking that produces coke containing 15-25% of volatiles substances, which can be used as a coking additive in a coal coking charge for metallurgical coke production.
  • Oil coke with more than 14% but less than 25% volatiles is capable not only of replacing the K-brand (coking) coal, which is in short supply, in coal coking charges, but also of improving the quality of metallurgical coke (Russian Federation Patent 2355729 , C10B57/04, published on 20 May 2009).
  • There exists technology for forming oil coke by delayed coking of oil residues. This method includes slowly heating raw materials to 490-515°C in a tubular furnace, mixing the raw materials with a recirculant, presenting the coking distillate products formed inside the coking chamber, in a rectification column, which produces bottoms, supplying the bottoms as the secondary raw materials to the coking chamber at 485-495°C and carrying out coking, which results in the formation of coke (Z. I. Syunyaev, "Forming, Refining and Using Petroleum Coke", Moscow: Khimiya: 1973, p. 95).
  • The drawback of this method is that the coke formed by its application has a high strength and low concentration of volatiles (up to 9% by mass).
  • It is possible to increase the concentration of volatiles in coke by reducing the temperature of the raw materials at the inlet into the coking chamber. However, reducing that temperature and coking at low temperatures results in excessive foaming and, consequently, it increases the probability of the foam getting into the rectification column, then into the furnace, which might result in the plant becoming coked up, shortening the spans between overhauls.
  • A delayed coking method, capable of guaranteeing that no direct contact would occur between the primary charge and the vapours reaching the rectification column from the coking chamber during the formation of the secondary charge, can prevent coke foam finding its way inside the reaction spiral tubes of the furnace, the coking up of the plant and thus lengthen the spans between overhauls.
  • The technology nearest to the proposed invention is the delayed coking of oil residues, which includes heating the original raw materials to 340-380°C, mixing them with a recirculant- heavy coking gasoil (pyrolisis resin, heavy catalytic cracking gasoil)- in a mixing tank where the secondary charge forms, heating the secondary charge, i.e. the heavy residues formed in the mixing tank, transferring this into the coking chamber at 485-505°C, and coking to form coke (Russian Federation Patent No. 2206595 , class C10B 55/00, published on 20 June 2003).
  • The drawback of this invention is the low concentration of volatiles in the final product due to the high coking temperature (485-505°C) and the low efficiency due to extensive foaming, and consequently to not being able to use the coking chamber to its full capacity.
  • This invention aims at increasing the concentration of volatiles in the coke and improving the efficiency of the plant.
  • This aim is achieved because this method of delayed coking of a coking additive includes preheating of the primary raw materials at 270-350°C, mixing the primary raw materials with the recirculant in the tank for the production of secondary charge, heating the secondary charge, transporting it to the coking chamber, and coking to form the target product. In this invention the secondary charge is heated at 455-470°C before it reaches the coking chamber.
  • Moreover, to prevent foaming, an anti-foaming dope is introduced into the coking chamber 3-5 hours before the end of coking.
  • Moreover, taking into consideration that the foam developed in low-temperature coking forms a thick layer, the anti-foaming dope is introduced in two to four areas around the perimeter of the coking chamber, so that it covers the entire surface of the foam.
  • Coking carried out at low temperatures, because the raw material is charged into the coking chamber at a low temperature, produces coke with a concentration of volatiles of 15-25% to be used as a coking additive.
  • Introducing the anti-foaming dope during the last 3-5 hours of the coking process not only reduces the amount of foam forming in the coking chamber but also makes the process more efficient with respect to the primary raw materials.
  • The diagram shows the main parts of the plant for carrying out the proposed method for production of a coking additive by the means of delayed coking.
  • The proposed method of production of a coking additive in delayed coking works as follows.
  • The original raw materials, such as tar, de-asphalting asphalt, oil production extracts, heavy gasoil of catalytic cracking or any mixtures of the above, are heated in a tubular furnace 1 to 270-350°C, then discharged into the mixing tank 2 connected in pairs to the rectification column 3. Heavy coking gasoil, used as the recirculant, is also charged into the rectification column 3. It is discharged from column 3 as a side fraction.
  • The mixture of the primary raw materials and recirculant, which becomes the secondary charge, is heated to 455-470°C in the tubular furnace 4, then fed into the alternately working coking chambers 5 where a coking additive with 15-25% volatiles is gradually accumulated. The distillate coking products, formed in the coking chamber 5, are discharged into the rectification column 3, where they are resolved into a gas, benzene, light and heavy coking gasoil and the bottoms.
  • Vapour-like products leave the plant through the top of the column 3, light and heavy gasoils are discharged from the middle part of the column, while the bottoms are removed from the bottom part. To reduce foam formation, the anti-foaming dope 6 is introduced in four areas around the perimeter of the coking chamber.
  • The suggested technology is illustrated with the following four examples: 1-4.
  • A mixture of raw materials, comprised of a vacuum visbreaking residue, tar oil and heavy gasoil of catalytic cracking in the ratio of 15:75:10 was coked, using an industrial delayed coking plant. The mixture had the following characteristics: density 1.055 g/cm3, cokeability 25.8% and sulphur content 3.8%. The primary charge was heated in a convection furnace to 320°C, then it was mixed with a recirculate: heavy coking gasoil, discharged from the rectification column as a side fraction. The produced secondary charge was heated in a tubular furnace, then it was fed into the coking chamber to produce a coking additive. When coking was over, the coke was steamed out, water-cooled and discharged by hydraulic means. In Examples 2 and 4, an anti-foaming dope was introduced into the coking chamber 4 hours before the end of the process - to prevent foam formation.
  • Coking conditions and results in Examples 1-4 are shown in the Table.
  • For comparison, the same charge as in 1-4 was coked, using the technology of the prototype of this invention. The temperature of the secondary charge at the inlet of the coking chamber was 485°C. No anti-foaming dope was used. The result was ordinary electrode coke with a concentration of volatiles of 10.8%. The conditions and results are also presented in the Table. Table
    Comparative Data on Coking of Raw Materials
    Characteristics Example
    Invention technology Prototype
    1 2 3 4 5
    Plant efficiency with respect to primary charge, m3/h 96 100 96 98 95
    Plant efficiency respective the secondary charge, m3/h 106 110 110 112 105
    Secondary charge temperature at the coking chamber inlet, °C 468 468 456 456 485
    Coking duration, h 16 16 16 16 16
    Coke level in the chamber, m 19.0 20,5 19.5 21.0 19.0
    Concentration of volatiles in coke, % 15.1 15.5 21.8 22.4 10.8
    Anti-foaming dope, yes/no No Yes No Yes No
  • As can be seen from the Table, the coking method suggested by this inventor produces coke that can be used as a coking additive, with a concentration of volatiles higher than 15%. Introducing it into the coking chamber at 456°C is not practicable because bitumen is likely to form, and it would make the steaming out and cooling down of coke difficult. On the other hand, a charge introduced at a temperature above 470°C, will produce coke that contains less than 15% of volatiles.
  • Introduction of the anti-foam dope into the top part of the coking chamber reduces the amount of foam that forms during coking, which improves the working efficiency of this technology with respect to the original raw material.

Claims (3)

  1. A method of producing a coking additive in delayed coking, which includes heating the primary charge to 270-330°C, mixing the primary charge with a recirculate in a tank, which makes a secondary charge, heating the secondary charge and introducing it into the coking chamber, coking to form the target product, different in that the secondary charge is introduced into the coking chamber at 455-470°C.
  2. A method as in 1, different in that an anti-foaming dope is introduced into the coke chamber 3-5 hours before the end of coking.
  3. A method as in 1, different in that the anti-foaming dope is introduced into 2-4 areas around the perimeter of the coking chamber.
EP10852594.0A 2010-06-01 2010-12-28 Method for producing a coking additive by delayed coking Not-in-force EP2578666B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
RU2010122135/05A RU2437915C1 (en) 2010-06-01 2010-06-01 Procedure for production of coke additive by delayed coking
PCT/RU2010/000795 WO2011152752A1 (en) 2010-06-01 2010-12-28 Method for producing a coking additive by delayed coking

Publications (3)

Publication Number Publication Date
EP2578666A1 true EP2578666A1 (en) 2013-04-10
EP2578666A4 EP2578666A4 (en) 2016-11-23
EP2578666B1 EP2578666B1 (en) 2017-11-15

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Family Applications (1)

Application Number Title Priority Date Filing Date
EP10852594.0A Not-in-force EP2578666B1 (en) 2010-06-01 2010-12-28 Method for producing a coking additive by delayed coking

Country Status (10)

Country Link
US (1) US20130276587A1 (en)
EP (1) EP2578666B1 (en)
JP (1) JP2013523942A (en)
KR (1) KR20130025875A (en)
CN (1) CN102892863B (en)
BR (1) BR112012030726A2 (en)
CA (1) CA2792300C (en)
RU (1) RU2437915C1 (en)
UA (1) UA104526C2 (en)
WO (1) WO2011152752A1 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2891697A4 (en) * 2012-08-29 2016-04-27 Obschestvo S Ogranichennoi Otvestvennostyu Promintekh Method for the retarded coking of petroleum residues

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2496852C1 (en) * 2012-05-11 2013-10-27 Общество С Ограниченной Ответственностью "Проминтех" Method for obtaining coking additive by delayed coking
RU2560442C2 (en) * 2013-11-18 2015-08-20 Государственное унитарное предприятие "Институт нефтехимпереработки Республики Башкортостан" (ГУП "ИНХП РБ") Method for obtaining of coking additive by slow coking
RU2576429C2 (en) * 2014-02-19 2016-03-10 Общество С Ограниченной Ответственностью "Проминтех" Method of coking additive production by delayed coking (versions)

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US4036736A (en) * 1972-12-22 1977-07-19 Nippon Mining Co., Ltd. Process for producing synthetic coking coal and treating cracked oil
JPS5341681B2 (en) * 1972-12-22 1978-11-06
JPS5519277B2 (en) * 1973-07-02 1980-05-24
JPS5736959B2 (en) * 1973-11-01 1982-08-06
JPH0639587B2 (en) * 1988-11-14 1994-05-25 新日鐵化学株式会社 Pitch coke manufacturing method
US4983272A (en) * 1988-11-21 1991-01-08 Lummus Crest, Inc. Process for delayed coking of coking feedstocks
US4961840A (en) * 1989-04-13 1990-10-09 Amoco Corporation Antifoam process for delayed coking
US5028311A (en) * 1990-04-12 1991-07-02 Conoco Inc. Delayed coking process
RU2067605C1 (en) * 1994-06-10 1996-10-10 Институт проблем нефтехимпереработки АН Республики Башкортостан Method for production of petroleum coke
RU2206595C1 (en) * 2001-10-30 2003-06-20 Институт проблем нефтехимпереработки АН Республики Башкортостан Method for delayed coking of petroleum residues
JP4865461B2 (en) * 2006-09-11 2012-02-01 Ｊｘ日鉱日石エネルギー株式会社 Delayed coker heating furnace operation method
CN103710042B (en) * 2006-11-17 2017-03-01 罗杰·G·埃特 Selective cracking and coking of undesirable components in coker recycle and diesel fuels
RU2355729C1 (en) 2008-02-26 2009-05-20 Закрытое акционерное общество научно-производственное объединение "Восточный научно-исследовательский углехимический институт" (ЗАО "НПО "ВУХИН") Coke addition

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2891697A4 (en) * 2012-08-29 2016-04-27 Obschestvo S Ogranichennoi Otvestvennostyu Promintekh Method for the retarded coking of petroleum residues

Also Published As

Publication number Publication date
RU2437915C1 (en) 2011-12-27
CN102892863A (en) 2013-01-23
KR20130025875A (en) 2013-03-12
EP2578666B1 (en) 2017-11-15
CN102892863B (en) 2014-07-09
JP2013523942A (en) 2013-06-17
BR112012030726A2 (en) 2019-05-07
US20130276587A1 (en) 2013-10-24
EP2578666A4 (en) 2016-11-23
UA104526C2 (en) 2014-02-10
CA2792300C (en) 2016-02-23
WO2011152752A1 (en) 2011-12-08
CA2792300A1 (en) 2011-12-08

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