EP0041588A1 - Procédé de production de coke supérieur à partir d'huile résiduaire - Google Patents

Procédé de production de coke supérieur à partir d'huile résiduaire Download PDF

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Publication number
EP0041588A1
EP0041588A1 EP19800301914 EP80301914A EP0041588A1 EP 0041588 A1 EP0041588 A1 EP 0041588A1 EP 19800301914 EP19800301914 EP 19800301914 EP 80301914 A EP80301914 A EP 80301914A EP 0041588 A1 EP0041588 A1 EP 0041588A1
Authority
EP
European Patent Office
Prior art keywords
residual oil
coke
premium
delayed
oil
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
EP19800301914
Other languages
German (de)
English (en)
Other versions
EP0041588B1 (fr
Inventor
William H. Kegler
James R. Mcconaghy
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.)
ConocoPhillips Co
Original Assignee
Conoco Inc
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 Conoco Inc filed Critical Conoco Inc
Priority to EP19800301914 priority Critical patent/EP0041588B1/fr
Priority to DE8080301914T priority patent/DE3070446D1/de
Publication of EP0041588A1 publication Critical patent/EP0041588A1/fr
Application granted granted Critical
Publication of EP0041588B1 publication Critical patent/EP0041588B1/fr
Expired legal-status Critical Current

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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
    • 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
    • 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

Definitions

  • This invention relates to delayed coking of a petroleum residuum, and more particularly to the production of premium delayed coke, suitable for formation of graphite electrodes for use in electric arc steel furnaces.
  • Delayed coking of residuum (residual oil) from a petroleum refinery vacuum distillation unit generally produces a coke having a longitudinal coefficient of thermal expansion (CTE) of about 20 x 10 -7 /°C or greater after graphitization.
  • CTE longitudinal coefficient of thermal expansion
  • the CTE of a graphitized coke is an important measure of its suitability for use in the manufacture of electrodes for electric arc steel furnaces. For example, the manufacture of 61 cm diameter electrodes requires a coke having, among other specified characteristics, a CTE of about 5 x 10 /°C or less, and the manufacture of 38 cm diameter electrodes requires a coke having a CTE of no more than about 8.0 x 10 -7 /°C.
  • Delayed premium coke is different in many respects from regular delayed coke, and is generally manufactured from specific feedstocks such as decant oil from a fluid catalytic cracker, tar from thermal cracking of regular coker gas oil, pyrolysis tars, or blends of these materials, sometimes with a minor amount of residual oil included in the feedstock.
  • Vacuum residual oil has, prior to this invention, always been considered in the industry as a material incapable of making premium coke when used as the principal ingredient of a delayed coker feedstock, even when coked at conditions which produce premium coke from conventional premium coke feedstocks.
  • Premium delayed coke is a different material from regular delayed coke, which is generally used only as a fuel.
  • Some better quality regular delayed cokes are suitable for use as anodes in aluminum smelting processes, and such cokes are sometimes referred to as metallurgical grade delayed cokes.
  • metallurgical grade delayed cokes are sometimes referred to as metallurgical grade delayed cokes.
  • even these better grade metallurgical delayed cokes are a different type of material than what is recognized by and referred to in the industry as premium delayed coke.
  • Premium coke is worth several times as much as regular coke, and yet the operating costs of a premium delayed coker, not considering the cost of the feedstock, are not greatly different from the costs for a regular coker. Accordingly, any process by which a low value material such as residual oil could be utilized as a premium coker feedstock is much to be desired.
  • Delayed coking is a routine petroleum refining step used in most cases to dispose of low value residual oils and to convert such residual oils into more valuable products.
  • the operating conditions and process steps of the delayed coking process, both for regular coke and premium coke, are well established and widely known.
  • a high sulfur and high metals content petroleum refinery vacuum residuum stream derived from a naphthenic crude oil is catalytically demetalized, then catalytically desulfurized, and then subjected to delayed coking under premium coking conditions to produce a premium coke suitable for manufacture of graphite electrodes.
  • the drawing is a schematic flowsheet illustrating the process of the invention.
  • Feedstocks for which the invention is applicable are residual oils derived from distillation of naphthenic crude oils having a UOP Characterization Factor (K factor) of 11.4 or lower.
  • K factor is defined as the cube root of the average boiling point in degrees Rankine divided by the specific gravity at 60°F.
  • Such residual oils have the particular molecular structure to produce premium coke when processed according to the invention.
  • the feedstocks also must have a 5 percent boiling point between 470 and 580°C when subjected to ASTM'Distillation Test D-1160.
  • the invention is particularly applicable to feedstocks which have the above-noted essential characteristics and additionally have a metals content, defined as total vanadium and nickel, of at least 25 parts per million by weight, and a sulfur content of more than 2 percent by weight.
  • the first step in the process of the invention involves subjecting an appropriate residual oil as defined above to a catalytic demetalation step, preferably over a vanadium promoted alumina catalyst, at rather severe conditions including a temperature of at least 400°C, a pressure of at least 75 kg/cm 2 , a liquid hourly space velocity of less than 0.25 and a hydrogen rate of 500 to 1000 standard cubic meters per cubic meter of residual oil.
  • the demetalation step protects the desulfurization catalyst from premature deactivation by reducing the amount of potentially damaging vanadium and nickel, and further serves to convert asphaltenes in the feedstock to components suitable for formation of premium delayed coke.
  • the demetalized residual oil is then subjected to catalytic desulfurization over a desulfurization catalyst, preferably a cobalt-molybdenum catalyst, at'a temperature of at least 370°C, a pressure of at least 50 kg/cm 2 , a liquid hourly space velocity of from 0.2 to 1.0 and a hydrogen rate of from 500 to 1000 standard cubic meters per cubic meter of residual oil.
  • a desulfurization catalyst preferably a cobalt-molybdenum catalyst
  • the demetalized and desulfurized residual oil is then subjected to delayed coking at premium coking conditions including a coker furnace outlet temperature of from 425 to 540°C, coke drum vapor outlet temperature of from 400 to 520°C and coke drum pressure of from 0.5 to 7 kg/cm .
  • a suitable residual oil is fed from line 10 to demetalizer 11, then to desulfurizer 12, then to coker furnace 13 and finally to coke drum 14.
  • conventional premium coker feedstock may be blended with the demetalized and desulfurized residual oil through line 15.
  • recycle gas oil from the coker fractionator (not shown) may be introduced in an amount of from 0.5 to 1.5 times the residual oil volume into line 15 to optimize the coking operation. In some cases, hydrotreating of the recycle gas oil will further improve the quality of the premium coke product.
  • the process is particularly useful for making premium coke from vacuum residual oil derived from a naphthenic crude such as Arabian Heavy having a K factor of less than 11.4, a sulfur content of more than 4.0 percent by weight and a metals content of more than 100 parts per million.
  • an Arabian Heavy residual oil having a sulfur content of 4.9 percent by weight and a vanadium and nickel content of 120 and 56 parts per million by weight respectively was coked in a pilot plant coker using a coke drum overhead vapor temperature of 510°C and a coke drum pressure of 1.75 kg/cm 2 .
  • the resulting green coke had a sulfur content of 6.9 percent by weight and a vanadium and nickel content of 510 and 277 parts per million by weight respectively.
  • Graphitized electrodes prepared from the green coke had an average coefficient of thermal expansion of 18.5 x 10 -7 /°C.
  • the same feedstock was then subjected to demetalation over a vanadium promoted alumina catalyst at a temperature of 425°C, a pressure of 126 kg/cm , a liquid hourly space velocity of 0.1 and a hydrogen rate of 900 standard cubic meters per cubic meter of residual oil, followed by desulfurization over a cobalt-molybdenum catalyst at a temperature of 370°C, a pressure of 84 kg/cm 2 , a liquid hourly space velocity of 0.5 and a hydrogen rate of 900 standard cubic meters per cubic meter of residual oil.
  • the demetalized and desulfurized residual oil was then coked at the same conditions as the untreated residual oil described above.
  • the resulting green coke had a sulfur content of 2.4 percent by weight and a vanadium and nickel content of 79 and 73 parts per million by weight respectively.
  • Graphitized electrodes prepared from this coke had an average coefficient of thermal expansion of 5.1 x 10 7/°C.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Coke Industry (AREA)
EP19800301914 1980-06-06 1980-06-06 Procédé de production de coke supérieur à partir d'huile résiduaire Expired EP0041588B1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
EP19800301914 EP0041588B1 (fr) 1980-06-06 1980-06-06 Procédé de production de coke supérieur à partir d'huile résiduaire
DE8080301914T DE3070446D1 (en) 1980-06-06 1980-06-06 Method for producing premium coke from residual oil

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP19800301914 EP0041588B1 (fr) 1980-06-06 1980-06-06 Procédé de production de coke supérieur à partir d'huile résiduaire

Publications (2)

Publication Number Publication Date
EP0041588A1 true EP0041588A1 (fr) 1981-12-16
EP0041588B1 EP0041588B1 (fr) 1985-04-10

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ID=8187186

Family Applications (1)

Application Number Title Priority Date Filing Date
EP19800301914 Expired EP0041588B1 (fr) 1980-06-06 1980-06-06 Procédé de production de coke supérieur à partir d'huile résiduaire

Country Status (2)

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EP (1) EP0041588B1 (fr)
DE (1) DE3070446D1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011005476A3 (fr) * 2009-06-22 2012-02-23 Saudi Arabian Oil Company Procédé de rechange pour le traitement de bruts lourds dans une raffinerie de cokéfaction
CN114426885A (zh) * 2020-09-25 2022-05-03 中国石油化工股份有限公司 一种加工渣油的方法和装置

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2871182A (en) * 1956-08-17 1959-01-27 Socony Mobil Oil Co Inc Hydrogenation and coking of heavy petroleum fractions
US3684688A (en) * 1971-01-21 1972-08-15 Chevron Res Heavy oil conversion
US3773653A (en) * 1971-03-15 1973-11-20 Hydrocarbon Research Inc Production of coker feedstocks
US3781198A (en) * 1972-02-02 1973-12-25 Sun Research Development Process for making electrode grade coke

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2871182A (en) * 1956-08-17 1959-01-27 Socony Mobil Oil Co Inc Hydrogenation and coking of heavy petroleum fractions
US3684688A (en) * 1971-01-21 1972-08-15 Chevron Res Heavy oil conversion
US3773653A (en) * 1971-03-15 1973-11-20 Hydrocarbon Research Inc Production of coker feedstocks
US3781198A (en) * 1972-02-02 1973-12-25 Sun Research Development Process for making electrode grade coke

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011005476A3 (fr) * 2009-06-22 2012-02-23 Saudi Arabian Oil Company Procédé de rechange pour le traitement de bruts lourds dans une raffinerie de cokéfaction
US8491779B2 (en) 2009-06-22 2013-07-23 Saudi Arabian Oil Company Alternative process for treatment of heavy crudes in a coking refinery
CN114426885A (zh) * 2020-09-25 2022-05-03 中国石油化工股份有限公司 一种加工渣油的方法和装置
CN114426885B (zh) * 2020-09-25 2023-09-05 中国石油化工股份有限公司 一种加工渣油的方法和装置

Also Published As

Publication number Publication date
DE3070446D1 (en) 1985-05-15
EP0041588B1 (fr) 1985-04-10

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