EP0454425B1 - Procédé pour la fabrication de coke à faible teneur en matières carbonées volatiles - Google Patents

Procédé pour la fabrication de coke à faible teneur en matières carbonées volatiles Download PDF

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Publication number
EP0454425B1
EP0454425B1 EP91303657A EP91303657A EP0454425B1 EP 0454425 B1 EP0454425 B1 EP 0454425B1 EP 91303657 A EP91303657 A EP 91303657A EP 91303657 A EP91303657 A EP 91303657A EP 0454425 B1 EP0454425 B1 EP 0454425B1
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EP
European Patent Office
Prior art keywords
coke
light hydrocarbon
hydrocarbon stream
drum
steam
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 - Lifetime
Application number
EP91303657A
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German (de)
English (en)
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EP0454425A1 (fr
Inventor
Harry A. Adams
Stephen C. Paspek
Jeffrey B. Hauser
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.)
Standard Oil Co
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Standard Oil Co
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Publication date
Application filed by Standard Oil Co filed Critical Standard Oil Co
Priority to AT91303657T priority Critical patent/ATE100486T1/de
Publication of EP0454425A1 publication Critical patent/EP0454425A1/fr
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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
    • C10B57/00—Other carbonising or coking processes; Features of destructive distillation processes in general
    • C10B57/005—After-treatment of coke, e.g. calcination desulfurization
    • 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

  • the present invention relates to an improved process for forming coke with a low volatile carbonaceous matter (VCM) content.
  • VCM volatile carbonaceous matter
  • Processes for forming coke from petroleum hydrocarbons are well-known. See, for example, U.S. Patent Nos. 3,745,110 and 3,836,434; the disclosures of which are incorporated herein by reference. Such processes involve heating certain petroleum hydrocarbon streams to elevated temperatures, for example 496°C (925°)-524°C 975°F), and rapidly running the hot hydrocarbons into the bottom of a relatively quiescent chamber known as a coking drum. As the hydrocarbons are charged into the coking drum, they undergo coking, i.e., they undergo a chemical change from a liquid to a solid.
  • steam stripping drives off non-coked hydrocarbons, i.e., portions of the hydrocarbon feed which have not become a carbonaceous solid.
  • steam stripping provides initial cooling of the very hot mass of coke in the coking drum. After steam stripping, the coke is further cooled to a relatively low temperature of about 93°C (200°F) or less so that it can be safely removed from the coking drum. The cooling is accomplished by charging steam and water into the bottom of the coking drum. Care must be taken to adjust the water flow rate during water cooling to prevent high pressures from developing at the coke drum inlet.
  • the coking drum is ready for emptying. This is accomplished by removing covering plates called heads, located at the top and bottom of the coking drum and breaking the hardened coke into chunks. Break-up of the coke is normally accomplished by means of high pressure water drills which direct jets of high pressure water into the coke. The chunks of coke so formed fall through the bottom of the coking drum to railcars or other suitable means of transportation.
  • U.S. Pat. No. 4,547,284 discloses that a portion of the VCM can be converted to coke by passing a heated non-coking vapor through the contents of the drum after the coker drum has been taken off stream, i.e., the residuum feed has been switched to the other coke drum.
  • the non-coking vapor is introduced at a temperature above the coke temperature to increase the coke temperature and facilitate reacting of the VCM. This requires additional energy input and increases cycle time, thereby decreasing the productivity of the coker.
  • VCM volatile carbonaceous matter
  • the foregoing objective is accomplished by carrying out the coking of a petroleum hydrocarbon stream in a coking drum.
  • the hydrocarbon is a high boiling petroleum residuum.
  • the high boiling petroleum hydrocarbon residuum is heated and introduced as a feedstock to a coke drum to form coke and overhead vapors.
  • the overhead vapors escape through the top of the coke drum and are passed to a bubble tower.
  • a liquid light hydrocarbon stream is introduced into the bottom of the coking drum at a temperature below that of the coke in the drum.
  • the light hydrocarbon stream functions to reduce the volatile carbonaceous material in the coke as it passes through the drum.
  • the light hydrocarbon stream extracts a portion of the VCM and the mixture passes through the coking drum to an overhead outlet and subsequently to the bubble tower.
  • the coke can be optionally steam stripped or stripped with an inert stream.
  • the coke is water quenched and cut as is known in the art.
  • a superior grade coke is obtained because the VCM content of the coke is reduced below the level typically achieved with steam stripping alone.
  • the VCM remaining in the coke is more uniformly dispersed throughout the coke, i.e., the coke at the top of the drum is more similar in VCM content to the coke at the bottom of the drum.
  • the light hydrocarbon stream also functions to reduce the coke temperature, therefore cycle time is not increased.
  • a feed which is generally a petroleum residuum, e.g., crude oil vacuum bottoms, is fed through line 1 to bubble tower 3 where it is stripped.
  • the coke drum overhead vapors entering through line 11 provide the heat for fractionation.
  • the resultant tower bottoms consisting of condensed recycle from the coking operation and all but the low boiling fractions of the regular coker feed is passed through line 5 to the fired heater 7.
  • the coker charge is heated to a temperature sufficient to produce the coking reaction and is passed through line 8 into one of the coke drums 9A or 9B.
  • One of the coking drums is "on-line” being filled while the second drum is “off-line” being stripped, cooled, and emptied. Access to the drums is controlled by valves 12A and 12B. Overhead vapors from the coke drums exit via line 11 and return to the bubble tower 3.
  • the bottom of the coke drum is much hotter than the top of the drum, for example about 482°C (900°F), and about 441°C (825°F) respectively.
  • steam is introduced into the bottom of the drum at about 177°C (350°F). The steam cools the hot coke bed and sweeps some VCM out of the bed through an overhead vapor outlet leading to a bubble tower.
  • a second drum is placed "on-line" to receive the coker feedstock. Since the second coke drum is relatively cool and empty, the quantity of vapors exiting the top is much lower than the steady state value. This decrease in the amount of hot vapor entering the bubble tower upsets the heat balance and decreases the effectiveness of the bubble tower.
  • a light hydrocarbon stream is introduced as an alternative, or in conjunction with steam.
  • the light hydrocarbon will be comprised of at least hydrogen and carbon.
  • the light hydrocarbon stream is comprised largely of C3 to C30 hydrocarbon molecules.
  • the stream consists largely of C5 to C20 hydrocarbon molecules. Due to its higher vapor density, greater weights per period of time of light hydrocarbon can be passed through the drum than steam, further facilitating VCM removal.
  • the light hydrocarbon stream should be introduced at a temperature lower than the coke temperature in the drum.
  • the light hydrocarbon stream should be introduced at a temperature below its boiling range, i.e., substantially as a liquid at coke drum inlet pressure. Any hydrocarbon stream with a boiling range below the coke temperature can be used.
  • the light hydrocarbon has a final boiling point less than about 482°C (900°F). More preferably, the final boiling point is less than about 316°C (600°F). Blends of light hydrocarbons and/or steam are also envisioned.
  • the light hydrocarbon stream has a limited coking potential.
  • the preferred light hydrocarbons are naphtha, kerosene, or light gas oil. More preferably, the light hydrocarbon is naptha or kerosene.
  • kerosene is introduced through line 13.
  • Valves 10A and 10B direct flow into the filled "off-line" drum.
  • the kerosene is introduced at a temperature below its boiling point.
  • the kerosene is below about 232°C (450°F). Therefore the kerosene serves to extract heat from the coke as did steam in the prior art process. Accordingly, cycle time is not increased.
  • better heat removal within the coke drum is achieved with light hydrocarbons rather than steam due to the energy necessary for the vaporization of the light hydrocarbon stream. Accordingly, the kerosene transfers more heat from the lower portion of the coke drum to the upper portion of the coke drum, thereby increasing the coking activity of the top portion which has been subjected to coking reaction temperatures for the shortest period of time.
  • the kerosene has a higher affinity for the tar-like VCM than steam and will effectively strip this material from the product coke by extracting the VCM into the gas phase.
  • the light hydrocarbons because they are very soluble in the VCM, cause swelling of the VCM resulting in VCM being pushed out of micro-pores and into the macro-pores and channels increasing the accessibility of the solvent flow.
  • the light hydrocarbon reduces the viscosity of the VCM, making it more mobile.
  • the hot light hydrocarbon routed back to the bubble tower through line 11, carrying the VCM will function to stabilize the thermal requirements of the column during the "on-line" swing from drum 9A to 9B.
  • the next "on-line” drum initially produces less overhead heat and vapor.
  • the light hydrocarbon is fully miscible with the bubble tower contents, in contrast to steam, therefore it does not negatively effect the bubble tower operation.
  • VCM solubilized by the kerosene can be collected from the bubble tower as usable hydrocarbons which is a significant economical advantage.
  • the kerosene can be recovered in the bubble tower and recycled through line 13 to maintain the process.
  • stripping of the coke bed with a light hydrocarbon can eliminate the need for steam stripping, it is possible to accompany the light hydrocarbon stripping with steam stripping or to subsequently steam strip.
  • Lines 15, 17, 19 and 21 are the recovery lines for various product fractions from the bubble tower.
  • the bubble tower aids recovery of products such as heavy coker gas oil (line 21), a light coker gas oil (line 19), kerosene (line 13), naphtha (line 17) and gas (line 15).
  • Example 1 Coke which had previously been steam stripped, resulting in a 13.1 weight percent VCM content, was treated in a 150 cc. microreactor at 454°C (850°F) and a pressure of 272.4 kPa (25 p.s.i.g.) with solvents consisting of nitrogen, coker naphtha, and coker kerosene.
  • solvents consisting of nitrogen, coker naphtha, and coker kerosene.
  • the light hydrocarbon solvents resulted in much greater reduction of coke VCM.

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  • 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)
  • Coke Industry (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Carbon And Carbon Compounds (AREA)

Claims (12)

  1. Procédé pour préparer du coke ayant une faible teneur en matière carbonée volatile à partir d'une charge d'alimentation de pétrole comprenant les opérations consistant:
    (a) à chauffer et à introduire la charge d'alimentation de pétrole à un réacteur de coke pour former du coke et des vapeurs de tête;
    (b) à faire passer un courant d'hydrocarbure léger à travers ledit coke, dans lequel ledit courant d'hydrocarbure léger pénètre dans ledit réacteur de coke en phase pratiquement liquide; et
    (c) à retirer ledit hydrocarbure léger contenant au moins une partie de la matière carbonée volatile dudit réacteur de coke;
  2. Procédé selon la revendication 1, dans lequel on fait passer les vapeurs de tête de l'étape (a) et le courant d'hydrocarbure léger de l'étape (c) dans une colonne à plateaux.
  3. Procédé selon la revendication 1, dans lequel on introduit ladite charge d'alimentation de pétrole à une température de 454°C (850°F) ou au-dessus.
  4. Procédé selon la revendication 4, dans lequel ledit courant d'hydrocarbure léger a un point d'ébullition final inférieur à la température dudit coke.
  5. Procédé selon la revendication 4, dans lequel ledit courant d'hydrocarbure léger possède un point d'ébullition final de 482°C (900°F).
  6. Procédé selon la revendication 5, dans lequel ledit courant d'hydrocarbure léger a un point d'ébullition final inférieur à environ 316°C (600°F).
  7. Procédé selon l'une quelconque des revendications précédentes, dans lequel on choisit ledit courant d'hydrocarbure léger dans le groupe constitué par le naphta, le kérosène, le gazole léger et leurs mélanges.
  8. Procédé selon la revendication 7, dans lequel on choisit ledit courant d'hydrocarbure léger dans le groupe constitué par le naphta et le kérosène.
  9. Procédé selon l'une quelconque des revendications précédentes dans lequel ledit passage dudit courant d'hydrocarbure léger de l'étape (b) est suivi par un dégazolinage par entraînement à la vapeur d'eau.
  10. Procédé selon l'une quelconque des revendications précédentes, dans lequel ledit courant d'hydrocarbure léger de l'étape (b) est un mélange d'hydrocarbure léger et de vapeur d'eau.
  11. Procédé selon la revendication 2, dans lequel ledit hydrocarbure léger est recyclé à travers ladite colonne à plateaux et renvoyés au réacteur de coke.
  12. Procédé selon l'une quelconque des revendications précédentes, dans lequel ledit courant d'hydrocarbure léger de l'étape (b) est un mélange d'hydrocarbure léger, de vapeur d'eau et de tout additif inerte.
EP91303657A 1990-04-27 1991-04-23 Procédé pour la fabrication de coke à faible teneur en matières carbonées volatiles Expired - Lifetime EP0454425B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT91303657T ATE100486T1 (de) 1990-04-27 1991-04-23 Verfahren zur herstellung von koks mit einem niedrigen gehalt an fluechtigen kohlenstoffhaltigen stoffen.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US51537790A 1990-04-27 1990-04-27
US515377 1990-04-27

Publications (2)

Publication Number Publication Date
EP0454425A1 EP0454425A1 (fr) 1991-10-30
EP0454425B1 true EP0454425B1 (fr) 1994-01-19

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EP91303657A Expired - Lifetime EP0454425B1 (fr) 1990-04-27 1991-04-23 Procédé pour la fabrication de coke à faible teneur en matières carbonées volatiles

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EP (1) EP0454425B1 (fr)
AT (1) ATE100486T1 (fr)
CA (1) CA2041339A1 (fr)
DE (1) DE69101023T2 (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BR112013029341B1 (pt) 2011-05-13 2019-08-27 Catalytic Distillation Tech método para a produção de coque com alta concentração de vcm

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4547284A (en) * 1982-02-16 1985-10-15 Lummus Crest, Inc. Coke production

Also Published As

Publication number Publication date
EP0454425A1 (fr) 1991-10-30
CA2041339A1 (fr) 1991-10-28
DE69101023T2 (de) 1994-05-05
DE69101023D1 (de) 1994-03-03
ATE100486T1 (de) 1994-02-15

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