EP0090897B1 - Delayed coking of a heat-treated ethylene tar - Google Patents

Delayed coking of a heat-treated ethylene tar Download PDF

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Publication number
EP0090897B1
EP0090897B1 EP82305707A EP82305707A EP0090897B1 EP 0090897 B1 EP0090897 B1 EP 0090897B1 EP 82305707 A EP82305707 A EP 82305707A EP 82305707 A EP82305707 A EP 82305707A EP 0090897 B1 EP0090897 B1 EP 0090897B1
Authority
EP
European Patent Office
Prior art keywords
ethylene tar
tar
coking
hydrogen donor
ethylene
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
EP82305707A
Other languages
German (de)
English (en)
French (fr)
Other versions
EP0090897A3 (en
EP0090897A2 (en
Inventor
Hugh E. Romine
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
Publication of EP0090897A2 publication Critical patent/EP0090897A2/en
Publication of EP0090897A3 publication Critical patent/EP0090897A3/en
Application granted granted Critical
Publication of EP0090897B1 publication Critical patent/EP0090897B1/en
Expired legal-status Critical Current

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Classifications

    • 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, and more particularly to delayed coking of premium coking feedstocks at conditions under which premium coke suitable for graphitization is formed.
  • ethylene -fars from the steam pyrolysis ethylene process may be used as a feedstock component in a premium coking process.
  • ethylene tars have lowered the quality of premiun ⁇ coke proportionately with their ratio in the feedstock. The reasons for this are not clear, and the extent of lowering varies with the source of the ethylene tar and probably with many other variables.
  • One theory is that ethylene tars contain heavy asphaltenes which not only lower coke quality but also tend to produce furnace coil coking, which in turn neces- .. sitates costly shutdowns for furnace cleaning.
  • a delayed coking process in which a premium coking feedstock including ethylene tar is introduced to the lower portion of a coker fractionator, transferred from said coker fractionator, to a coking furnace and then to a coking drum, and wherein said ethylene tar is heat soaked in the presence of a hydrogen donor at a temperature of from 260 to 430°C and for a time sufficient to substantially reduce the toluene insolubles content thereof prior to introduction to said coker fractionator.
  • the described embodiment of the invention involves heat soaking ethylene tar in the presence of a hydrogen donor solvent and then utilizing the treated ethylene tar as feedstock to a premium coking operation.
  • Ethylene tar has been used as a feedstock component in premium coking operations.
  • the use of ethylene tar has generally led to coke formation on the furnace coils and to a deterioration of the quality of the coke product, particularly in the area of the coefficient of thermal expansion of the graphitized coke. It is believed that both of these problems are the result of the presence of heavy asphaltenes in the ethylene tar.
  • This invention is primarily directed to a process of treating ethylene tar to reduce the amount of heavy asphaltenes therein, with a resultant elimination of or reduction of the problems normally associated with coking material containing ethylene tar.
  • Coker feedstock enters coker fractionator 10 from line 12, and passes to coker furnace 14 where it is heated to coking temperature.
  • the heated feedstock then passes into one of the two coke drums 16 and 18 which are filled alternatively while the other is being cooled and emptied. Vapors from the coke drum being filled are returned to the coker fractionator through line 20, and products are recovered from the coker fractionator in a conventional manner.
  • Ethylene tar is added through line 24 as a feedstock component, and prior to being introduce to the coker fractionator it is heat soaked in a vessel 22 in the presence of a hydrogen donor added through line 26.
  • the feedstock to the coker fractionator may be made up entirely of donor soaked ethylene tar, but preferably would comprise from 5 to 20 volume percent ethylene tar with the balance being thermal tar, decant oil from a fluid catalytic cracking operation (sometimes referred to as cycle oil or gas oil).
  • Coal tars are sometimes utilized as premium coker feedstocks when they are available.
  • premium coking feedstocks are highly aromatic hydrocarbon streams having relatively high boiling ranges.
  • the hydrogen donor material is generally a hydrocarbon which has the ability to take up hydrogen in a hydrogenation zone and readily release it in a thermal treating zone. It is believed that the hydrogen donor operates by yielding hydrogen atoms, thereby upgrading the ethylene tar and preventing condensation and/or polymerization of the ethylene tar.
  • Hydrogen donor materials may be relatively pure chemicals such as tetralin or decalin or they may be a partially hydrogenated catalytic cycle oil, a partially hydrogenated lubricating oil extract or other partially hydrogenated aromatic material. Hydrogen donors usually contain condensed ring aromatics in sufficient qualities to serve as a hydrogen carrier. These aromatics are partially hydrogenated by addition of easily removable hydrogen atoms. After use in the heat soaking vessel 22, the hydrogen donor may be recovered from fractionator 10, rehydrogenated, and reused as hydrogen donor solvent in the process.
  • the amount of hydrogen donor in relation to the amount of ethylene tar may vary considerably, but practical limitations suggest a ring of from 0.2 to 5.0 times the volume of ethylene tar.
  • a preferred amount of hydrogen donor is a volume of from 0.5 to 2.0 times the volume of ethylene tar.
  • the temperature in the heat soaking step may also vary considerably, but generally should be above 260°C to provide a reasonable rate of hydrogen transfer, and the maximum temperature is a temperature where thermal cracking becomes significant. Thermal cracking may occur to a significant amount at temperatures above about 450°C, and that should be considered an upper limit in the process.
  • the residence time in the heat soaking step varies inversely with the soaking temperature. At lower temperatures, such as 260°C or slightly greater, a time of many hours may be required to effect a substantial reduction in the amount of heavy asphaltenes in the ethylene tar. At temperatures near the upper limit, such as from 425-450°C, the time required is much shorter, such as a fraction of an hour.
  • a soaking temperature of from 300°C to 380°C for a time of from one to three hours is preferred. However, there are situations in which a very long residence time is desirable or expedient, and in such cases a similar result can be obtained by maintaining the lower soaking temperature for a longer period of time.
  • the toluene insoluble material in an ethylene tar was determined to be 15.4 weight percent.
  • the tar was then heat soaked at a temperature of 357°C for a time of 40 minutes, and the toluene insoluble material increased to 16.0 percent by weight.
  • the same ethylene tar was then mixed with hydrogen donor material. The mixture was heat soaked at a temperature of 357°C for a time of 40 minutes, and the toluene insoluble material in the donor soaked tar was determined to be 10.5 percent by weight.
  • the pentane insoluble fraction of an ethylene tar was run straight, diluted with a cutter solvent, and blended in varying proportions with cutter solvent and hydrogen donor.
  • Each of the blends was soaked at a temperature of 357°C for a time of two hours, and the toluene insoluble fraction and the tetrahydrofuran insoluble fraction of each blend was determined.
  • Table I the amount of insoluble material was dramatically reduced for the case where one volume of hydrogen donor was heat soaked with one volume of asphaltenes from the ethylene tar. In the absence of the hydrogen donor material, the toluene insolubles and the THF insolubles increased significantly.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Coke Industry (AREA)
  • Cookers (AREA)
  • Bakery Products And Manufacturing Methods Therefor (AREA)
EP82305707A 1982-04-05 1982-10-27 Delayed coking of a heat-treated ethylene tar Expired EP0090897B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US36572382A 1982-04-05 1982-04-05
US365723 1982-04-05

Publications (3)

Publication Number Publication Date
EP0090897A2 EP0090897A2 (en) 1983-10-12
EP0090897A3 EP0090897A3 (en) 1984-06-20
EP0090897B1 true EP0090897B1 (en) 1986-05-28

Family

ID=23440074

Family Applications (1)

Application Number Title Priority Date Filing Date
EP82305707A Expired EP0090897B1 (en) 1982-04-05 1982-10-27 Delayed coking of a heat-treated ethylene tar

Country Status (7)

Country Link
EP (1) EP0090897B1 (es)
JP (1) JPS58173186A (es)
CA (1) CA1205408A (es)
DE (1) DE3271430D1 (es)
ES (1) ES516692A0 (es)
NO (1) NO830160L (es)
ZA (1) ZA827996B (es)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4624775A (en) * 1984-10-22 1986-11-25 Union Carbide Corporation Process for the production of premium coke from pyrolysis tar
US4740291A (en) * 1984-12-20 1988-04-26 Union Carbide Corporation Upgrading of pyrolysis tar using acidic catalysts
NZ217510A (en) * 1985-09-12 1989-09-27 Comalco Alu Process for producing high purity coke by flash pyrolysis-delayed coking method
JP2009102477A (ja) * 2007-10-22 2009-05-14 Japan Energy Corp 高純度石油コークスの製造方法
CN102234539B (zh) * 2010-04-23 2014-01-01 中国石油化工股份有限公司 一种乙烯焦油的加工方法
CN105038852B (zh) * 2015-08-14 2016-08-31 北京宝塔三聚能源科技有限公司 一种乙烯焦油的加氢工艺
CN106609145B (zh) * 2017-01-02 2019-02-15 深圳市科拉达精细化工有限公司 乙烯裂解焦油作延迟焦化原料的预处理工艺

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5014644B1 (es) * 1969-11-07 1975-05-29
US3687840A (en) * 1970-04-28 1972-08-29 Lummus Co Delayed coking of pyrolysis fuel oils
GB1351295A (en) * 1971-04-19 1974-04-24 Ruetgerswerke Ag Process for producing coke
US3736249A (en) * 1972-02-22 1973-05-29 Atlantic Richfield Co Hydrocarbonaceous feed treatment

Also Published As

Publication number Publication date
JPS58173186A (ja) 1983-10-12
EP0090897A3 (en) 1984-06-20
ES8308915A1 (es) 1983-10-01
CA1205408A (en) 1986-06-03
ES516692A0 (es) 1983-10-01
ZA827996B (en) 1983-08-31
NO830160L (no) 1983-10-06
DE3271430D1 (en) 1986-07-03
EP0090897A2 (en) 1983-10-12

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