EP1015529A1 - Procede ameliore d'obtention de rendements importants d'olefine a partir de charges d'alimentation residuelles - Google Patents

Procede ameliore d'obtention de rendements importants d'olefine a partir de charges d'alimentation residuelles

Info

Publication number
EP1015529A1
EP1015529A1 EP97931426A EP97931426A EP1015529A1 EP 1015529 A1 EP1015529 A1 EP 1015529A1 EP 97931426 A EP97931426 A EP 97931426A EP 97931426 A EP97931426 A EP 97931426A EP 1015529 A1 EP1015529 A1 EP 1015529A1
Authority
EP
European Patent Office
Prior art keywords
solids
reaction zone
zone
feedstock
contact time
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.)
Withdrawn
Application number
EP97931426A
Other languages
German (de)
English (en)
Other versions
EP1015529A4 (fr
Inventor
Willibald Serrand
Mitchell Jacobson
Paul K. Ladwig
John F. Pagel
Michael R. Parrish
Noel Seimandi
Hans A. Weisenberger
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.)
ExxonMobil Technology and Engineering Co
Original Assignee
Exxon Research and Engineering Co
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 Exxon Research and Engineering Co filed Critical Exxon Research and Engineering Co
Publication of EP1015529A1 publication Critical patent/EP1015529A1/fr
Publication of EP1015529A4 publication Critical patent/EP1015529A4/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • 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
    • C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
    • C10G1/02—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal by distillation
    • 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
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/20—C2-C4 olefins

Definitions

  • the present invention relates to a process for obtaining a substantial amount of olefinic product from a residua feedstock by use of a short vapor contact time thermal process unit comprised of a horizontal moving bed of fluidized hot particles.
  • crude oils are subjected to atmospheric distillation to produce lighter fractions such as gas oils, kerosenes, gasolines, straight run naphtha, etc.
  • Petroleum fractions in the gasoline boiling range, such as naphthas, and those fractions which can readily be thermally or catalytically converted to gasoline boiling range products, such as gas oils, are the most valuable product streams in the refinery.
  • the residue from atmospheric distillation is distilled at pressures below atmospheric pressure to produce a vacuum gas oil distillate and a vacuum reduced residual oil which often contains relatively high levels of asphaltene molecules.
  • asphaltene molecules typically contain most of the Conradson Carbon residue and metal components of the residua. It also contains relatively high levels of heteroatoms, such as sulfur and nitrogen.
  • feeds have little commercial value, primarily because they cannot be used as a fuel oil owing to ever stricter environmental regulations. They also have little value as feedstocks for refinery processes, such as fluid catalytic cracking, because they produce excessive amounts of gas and coke. Their high metals content also leads to catalyst deactivation. Thus, there is a great need in petroleum refining for better ways to utilize residual feedstocks or to upgrade them to more valuable cleaner and lighter feeds. Unlike residual feedstocks, more valuable feedstocks such as gas oils are used in fluid catalytic cracking to produce transportation fuels as well as being used as feedstock to make olefinic chemical products in a steam cracker.
  • a steam cracker is a thermal process unit comprised of fired coils where the feedstock is cracked at temperatures of about 540° to 800°C in the presence of steam. While gas oils are adequate feedstocks for such purposes, they are also relatively expensive feedstocks because they are a preferred feedstock to a fluid catalytic cracker. It would be desirable from an economic point of view to use lower valued feeds, such as residual feeds in steam cracking. Residual feedstocks are generally not suitable for use in steam crackers because of excessive cracking, coke formation, and coke deposition in the cracking coils which leads to overheating and equipment plugging. In addition, it has been found that steam can react with coke at process temperatures to form substantial amounts of CO which dilutes product vapors and seriously complicates product recovery.
  • a process for producing olefins from a residual feedstock comprises converting the feedstock in a process unit comprised of: (i) a heating zone wherein solids containing carbonaceous deposits are received from a stripping zone and heated in the presence of an oxidizing gas;
  • a short vapor contact time reaction zone containing a horizontal moving bed of fluidized hot solids recycled from the heating zone, which reaction zone is operated at a temperature from about 670°C to about 870°C and under conditions such that the solids residence time and the vapor residence time are independently controlled, which vapor residence time is less than about 2 seconds, and which solids residence is from about 5 to about 60 seconds;
  • Residual feedstocks which are suitable for use in the present invention are those petroleum fractions boiling above about 480°C, preferably above about 540°C, more preferably above about 560°C.
  • Non-limiting examples of such fractions include vacuum resids, atmospheric resids, heavy and reduced petroleum crude oil; pitch; asphalt; bitumen; tar sand oil; shale oil; coal; coal slurries; and coal liquefaction bottoms. It is understood that such residual feedstocks may also contain minor amounts of lower boiling material.
  • feedstocks typically cannot be used as feeds to steam crackers to produce olefinic products because they excessively coke.
  • Such feeds will typically have a Conradson carbon content of at least 5 wt.%, generally from about 5 to 50 wt.%. As to Conradson carbon residue, see ASTM Test D 189- 165.
  • Olefinic products are produced from the residual feedstocks in accordance with the present invention in a short vapor contact time process unit which is comprised of a heating zone, a short vapor contact time horizontal fluidized bed reaction zone and a stripping zone.
  • a short vapor contact time process unit which is comprised of a heating zone, a short vapor contact time horizontal fluidized bed reaction zone and a stripping zone.
  • a residual feedstock is fed via line 10 to one or more short vapor contact time reaction zones 1 which contains a horizontal moving bed of fluidized hot solids.
  • the solids in the short vapor contact time reactor be fluidized with assistance by a mechanical means.
  • the particles are fluidized by use of a fluidizing gas, such as steam, a mechanical means, and by the vapors which result in the vaporization of a fraction of the feedstock.
  • the mechanical means be a mechanical mixing system characterized as having a relatively high mixing efficiency with only minor amounts of axial backmixing. Such a mixing system acts like a plug flow system with a flow pattern which ensures that the residence time is nearly equal for all particles.
  • the most preferred mechanical mixer is the mixer referred to by Lurgi AG of Germany as the LR-Mixer or LR-Flash Coker which was originally designed for processing oil shale, coal, and tar sands.
  • the LR-Mixer consists of two horizontally oriented rotating screws which aid in fluidizing the particles.
  • the solid particles be coke particles, they may also be any other suitable refractory particulate material.
  • Non-limiting examples of such other suitable refractory materials include those selected from the group consisting of silica, alumina, zirconia, magnesia, mullite, synthetically prepared or naturally occurring material such as pumice, clay, kieselguhr, diatomaceous earth, bauxite, and the like. It is within the scope of the present invention that the solids can be inert or have catalytic properties. The solids will have an average particle size of about 40 microns to 2,000 microns, preferably from about 50 microns to about 800 microns.
  • the fluidized hot solids which will preferably be at a temperature from about 670°C to about 870°C, more preferably from about 700°C to 800°C
  • a substantial portion of the high Conradson Carbon and metal-containing components will deposit on the hot solid particles in the form of high molecular weight carbon and metal moieties.
  • the remaining portion will be vaporized on contact with the hot solids.
  • This vaporized portion will contain a substantial amount of olefinic products, typically in the range of about 20 to 50 wt.%, preferably from about 25 to 50 wt.%, and more preferably from about 30 to 50 wt.%, based on the total weight of the product stream.
  • the olefin portion of the product stream obtained by the practice of the present invention will typically be comprised of about 5 to 15 wt.%, preferably about 7 to 10 wt.% methane; about 10 to 20 wt.%, preferably about 12 to 18 wt.% ethylene; and about 5 to 15 wt.%, preferably 7 to 12 wt.% propylene, based on the feed.
  • the residence time of vapor products in reaction zones 1 will be an effective amount of time so that substantial secondary cracking does not occur. This amount of time will typically be less than about 2 seconds, preferably less than about 1 second, and more preferably less than about 0.5 seconds.
  • the residence time of solids in the reaction zone will be from about 5 to 60 seconds, preferably from about 10 to 30 seconds.
  • One novel aspect of the present invention is that the residence time of the solids and the residence time of the vapor products, in the reaction zone, are independently controlled. Most fluidized bed processes are designed so that the solids residence time, and the vapor residence time cannot be independently controlled, especially at relatively short vapor residence times.
  • the short vapor contact time process unit be operated so that the ratio of solids to feed be from about 30 to 1, preferably 20 to 1, more preferably about 10 to 1, and most preferably from about 5 to 1. It is to be understood that the precise ratio of solids to feed will primarily depend on the heat balance requirement of the short vapor contact time reaction zone. Associating the oil to solids ratio with heat balance requirements is within the skill of those having ordinary skill in the art, and thus will not be elaborated herein any further. A minor amount of the feedstock will deposit on the solids in the form of combustible carbonaceous material. Metal components will also deposit on the solids. Consequently, the vaporized portion will be substantially lower in both Conradson Carbon and metals when compared to the original feed.
  • the vaporized fraction is passed via line 11 to cyclone 20 where most of the entrained solids, or dust, is removed.
  • the dedusted vapors are then passed to quench zone 13 via line 24 where the vapors are reduced to temperatures below which substantial thermal cracking occurs. This temperature will preferably be below about 450°C, more preferably below about 340°C.
  • Solids, having carbonaceous material deposited thereon are passed from reaction zones 1 via lines 15 to the bed of solids 17 in stripper 3. The solids pass downwardly through the stripper and past a stripping zone at the bottom section where any remaining volatiles, or vaporizable material, are stripped from the solids with use of a stripping gas, preferably steam, introduced into the stripping zone via line 16.
  • a stripping gas preferably steam
  • Stripped vapor products pass upwardly in stripper vessel 3, through line 22 to cyclone 20 to quench zone 13 via line 24 where a light product, containing a substantial amount of olefins, is removed overhead via line 28.
  • the light product will typically be a 510°C minus product stream.
  • This 510° C minus product stream will typically contain about 7 to 10 wt.% methane, 12 to 18 wt.% ethylene, and 7 to 12 wt.% propylene, and 6 to 9 wt.% unsaturated C 4 's, such as butanes and butadienes, based on the total weight of the feed.
  • a 510°C plus stream will be collected from the quench zone via line 26.
  • the stripped solids are passed via line 18 to heater 2 which contains a heating zone.
  • the heating zone is operated in an oxidizing gas environment, preferably air, at an effective temperature. That is, at a temperature that will meet the heat requirements of the reaction zone.
  • the heating zone will typically be operated at a temperature of about 40°C to 200°C, preferably from about 65°C to 175°C, more preferably from about 65°C to 120°C in excess of the operating temperature of reaction zones 1. It is understood that preheated air can be introduced into the heater.
  • the heater will typically be operated at a pressure ranging from about 0 to 150 psig, preferably at a pressure ranging from about 15 to about 45 psig.
  • Excess solids can be removed from the process unit via line 50. Flue gas is removed overhead from heater 2 via line 40. The flue gas is passed through a cyclone system 36 and 39 to remove most solid fines. Dedusted flue gas will be further cooled in a waste heat recovery system (not shown), scrubbed to remove contaminants and particulates, and passed to a CO boiler (not shown). The hot inert solids are then recycled via lines 12 to thermal zone 1.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

L'invention concerne un procédé d'obtention de quantités importantes de produits oléfiniques à partir de charges d'alimentation résiduelles. Ledit procédé consiste à mettre en contact les charges avec des matières solides fluidisées très chaudes dans une unité de traitement thermique à courte durée de contact avec la vapeur. L'unité comprend un lit mobile horizontal de particules fluidisées très chaudes.
EP97931426A 1997-06-25 1997-06-25 Procede ameliore d'obtention de rendements importants d'olefine a partir de charges d'alimentation residuelles Withdrawn EP1015529A4 (fr)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/US1997/011108 WO1998059018A1 (fr) 1997-06-25 1997-06-25 Procede ameliore d'obtention de rendements importants d'olefine a partir de charges d'alimentation residuelles

Publications (2)

Publication Number Publication Date
EP1015529A1 true EP1015529A1 (fr) 2000-07-05
EP1015529A4 EP1015529A4 (fr) 2002-08-14

Family

ID=22261158

Family Applications (1)

Application Number Title Priority Date Filing Date
EP97931426A Withdrawn EP1015529A4 (fr) 1997-06-25 1997-06-25 Procede ameliore d'obtention de rendements importants d'olefine a partir de charges d'alimentation residuelles

Country Status (5)

Country Link
EP (1) EP1015529A4 (fr)
JP (1) JP2002505704A (fr)
AU (1) AU3505797A (fr)
CA (1) CA2291189A1 (fr)
WO (1) WO1998059018A1 (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20020038778A1 (en) * 2000-05-01 2002-04-04 Maa Peter S. Process for upgrading residua

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2768127A (en) * 1951-05-17 1956-10-23 Exxon Research Engineering Co Improved residual oil conversion process for the production of chemicals
US4172857A (en) * 1978-04-03 1979-10-30 Arthur G. Mckee & Company Process and apparatus for ethylene production
US4411769A (en) * 1982-03-23 1983-10-25 Exxon Research & Engineering Co. Integrated two stage coking and steam cracking process and apparatus therefor
US4975181A (en) * 1984-12-10 1990-12-04 Utah Tsao Process and apparatus for ethylene production
WO1997004043A1 (fr) * 1995-07-17 1997-02-06 Exxon Research And Engineering Company Enrichissement integre de residuum et craquage catalytique fluide
US6179993B1 (en) * 1996-02-23 2001-01-30 Exxon Chemical Patents Inc. Process for obtaining olefins from residual feedstocks

Also Published As

Publication number Publication date
AU3505797A (en) 1999-01-04
JP2002505704A (ja) 2002-02-19
WO1998059018A1 (fr) 1998-12-30
CA2291189A1 (fr) 1998-12-30
EP1015529A4 (fr) 2002-08-14

Similar Documents

Publication Publication Date Title
US5714663A (en) Process for obtaining significant olefin yields from residua feedstocks
AU717437B2 (en) Process for obtaining olefins from residual and other heavy feedstocks
US5714056A (en) Process for deasphalting residua (HEN9511)
CA2370591C (fr) Procede ameliore de desasphaltage de residus faisant appel a un recyclage reactif d'une matiere a point d'ebullition eleve
AU726958B2 (en) Two-stage process for obtaining significant olefin yields from residua feedstocks
EP0993499A1 (fr) Procede ameliore de cokefaction en lit fluidise
US6352638B2 (en) Two-stage process for converting residua to gasoline blendstocks and light olefins
AU745188B2 (en) Two-stage process for obtaining significant olefin yields from residua feedstocks
WO1998059018A1 (fr) Procede ameliore d'obtention de rendements importants d'olefine a partir de charges d'alimentation residuelles
US6652739B2 (en) Process for deasphalting residua by reactive recycle of high boiling material
RU2173695C2 (ru) Усовершенствованный способ достижения значительного выхода олефинов из остаточного исходного сырья
CN1259982A (zh) 从残油进料中获得高烯烃收率的改进方法

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 19991221

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): BE DE FR GB IT NL

RIN1 Information on inventor provided before grant (corrected)

Inventor name: WEISENBERGER, HANS, A.

Inventor name: SEIMANDI, NOEL

Inventor name: PARRISH, MICHAEL, R.

Inventor name: PAGEL, JOHN, F.

Inventor name: LADWIG, PAUL, K.

Inventor name: JACOBSON, MITCHELL

Inventor name: SERRAND, WILLIBALD

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: EXXONMOBIL RESEARCH AND ENGINEERING COMPANY

A4 Supplementary search report drawn up and despatched

Effective date: 20020627

AK Designated contracting states

Kind code of ref document: A4

Designated state(s): BE DE FR GB IT NL

17Q First examination report despatched

Effective date: 20020930

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 20030211