US3691056A - Process for retorting oil shale in the absence of shale ash - Google Patents

Process for retorting oil shale in the absence of shale ash Download PDF

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Publication number
US3691056A
US3691056A US133507A US3691056DA US3691056A US 3691056 A US3691056 A US 3691056A US 133507 A US133507 A US 133507A US 3691056D A US3691056D A US 3691056DA US 3691056 A US3691056 A US 3691056A
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shale
oil
heat
ash
zone
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US133507A
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John H Barney
Franklin B Carlson
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Oil Shale Corp
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Oil Shale Corp
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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
    • C10B53/00—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form
    • C10B53/06—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form of oil shale and/or or bituminous rocks

Definitions

  • the present invention relates to a process for the recovery of shale oil from oil shale which contains substantial amounts of carbonate-containing minerals.
  • the spent shale is a waste product comprising coke-like residue which contains large quantities of calcite (CaCO and dolomite (MgCO -CaCO having a particle size as small as /1- inch and smaller.
  • This shale matrix is to be distinguished from other oil-bearing matrixes such as coal which contains minor amounts of ash and tar sands which consist mainly of dense particles of silica.
  • Green River shale typically contains carbonate minerals in the range of about 35 weight percent dolomite and 15 weight percent calcite.
  • the spent shale also averages about 3 to 6 weight percent fixed organic carbon, depending, of course, on the specific pyrolysis process employed.
  • This amount of fixed carbon in terms of energy constitutes enough heat to sustain a very large retorting facility without resorting to the use of a portion of the oil or gaseous pyrolysis products for supplying the heat requirement.
  • many processes have been envisioned which contemplate the use of this available energy source for conducting the pyrolysis reaction, but none of these processes have fully anticipated the gamut of problems inherent in actually recovering and utilizing this energy source. At least one process (see U.S. Pat. No.
  • the principal object of the present invention to provide a process for the recovery of shale oil from oil shale whereby the loss of shale oil by sorption on porous shale ash in the pyrolysis zone is prevented entirely or at least substantially.
  • the process of the present invention provides for the recovery of shale oil from oil shale via solid-to-solid heat transfer techniques while preventing the loss of shale oil by sorption on porous shale ash in the pyrolysis zone. This is achieved to the process herein described by insuring that the heat-carrying bodies recycled to the pyrolysis zone are free entirely or substantially of shale ash.
  • the heat-carriers used herein may be any small attrition resistant material such as silica, minute alumina beads, or the like.
  • the shale ash is removed from the heat carrier body circuit by attrition and elutriation steps. These steps are preferably carried out in conjunction, however, each step may be performed independently of the other.
  • the spent shale is converted to friable particles of shale ash which are attrited to fines by frictional contact in the turbulent dense phase fluid bed combustion zone and the fines elutriated therefrom by the hot flue gas by-product of combustion.
  • the remainder of the friable shale ash particles are separated from the reheated heat-carrying bodies by attriting them to fines at a location downstream of the fluid bed combustion zone.
  • the process further provides for the economical recovery of the heat content of the hot flue gas.
  • This heat may be used to preheat raw oil shale fed to the pyrolysis zone if the sorbent shale ash is first removed from the gas stream.
  • the heat may be more conveniently recovered via indirect heat exchange with the combustion air to the dense phase fluidized bed.
  • Oil shale previously crushed to a particle size of nominal minus /2-inch, is fed from source 1 to the pyrolysis zone (retort) 2.
  • the shale may be preheated prior to being fed to the retort by passing the cold shale at about 60 F. through preheater 3.
  • Shale preheating may be accomplished by recovering the sensible heat from the discharge flue gas product of spent shale combustion described below.
  • the sensible heat may be recovered either directly by entraining the cold shale in a stream of hot flue gas from which the solid combustion zone products have been removed, or indirectly by passing the flue gas through a heat exchanger of the type resembling a bundle of fin tubes. Regardless of the preheat procedure, it is desirable to preheat the shale to at least 220 F. to remove as much of the free moisture as possible and reduce the size of the downstream shale oil recovery equipment.
  • the crushed oil shale was preheated to about 230 F. in a dilute phase fluid bed and fed at an average rate of about 1180 pounds per hour into the retort 2 operating at a pressure of 0.75 p.s.i.g.
  • Hot heat-carrying bodies substantially free of shale ash and having an average temperature of about 1215 R which are preferably highly attrition resistant silica sand particles having the granular particle size distribution set forth in Table 1 below, are fed from the heat-carrier accumulator 4 to the retort 2 via line 5 at an average rate of about 4000 pounds per hour.
  • the present process contemplates the use of all attrition resistant heat-carrying fluidizable solids having a particle size range in the order of 100 mesh to about 4.0 mesh.
  • the hot heat-carrying sand particles are mixed with preheated oil shale and conveyed therethrough.
  • the retention time required in the retort is in the order of 2 to 5 minutes.
  • the hot sand particles exchange heat with the preheated oil shale to convert the kerogen content thereof into shale oil vapors at a temperature of about 950 F. and a spent shale residue.
  • the shale oil vapors comprise noncondensable or gaseous hydrocarbons as well as vaporized condensable hydrocarbons.
  • the spent shale or shale coke contains fixed residual carbon in amounts ranging from about 3% to about 6%.
  • the typical carbon content of the Green River oil shale found in western Colorado and processed via solidto-solid heat exchange techniques is in this range.
  • the fixed carbon content of oil shale usually varies with its origin or location and can be as high as 10% or more by weight. Since the fixed carbon represents an available energy source, all efforts should be exerted to recover or utilize it efiiciently.
  • the solids blend of cooled heat-carrying bodies, i.e., sand, and spent shale particles plus the shale oil vapors pass from the retort 2 into a solids-vapor separator vessel 6.
  • the shale oil vapors collect in the upper portion of the separator 6 and are removed therefrom via conduit 7 and passed to a vapor recovery zone or fractionator 8 for further downstream processing.
  • the solids blend of cooled heat-carrying bodies and spent shale particles is withdrawn from the bottom of the separator 6 through the solids flow control valve 9 via line 10 and passed therethrough to a dense phase fluidized bed combustion zone 11 by conventional dense phase transport procedures. If the solids blend contains a substantial quantity of large spent shale particles, for example, minus one-inch to plus Az-inch size, the particles may be comminuted via crusher 12 prior to entry into the combustion zone 11. Because spent shale is somewhat friable and easily crushed, the crusher rolls are disposed to impose only moderate pressure on the larger spent shale particles without fracturing the heat-carriers.
  • the carbon content of the solids blend is combusted to provide the heat for reheating the heat-carrying bodies therein.
  • the heat-carrying bodies are generally covered with deposited coke, while the spent shale contains coke throughout its fine-grained matrix. If the fuel requirement provided by the carbon content of the solids blend fed to the combustion zone 11 is insufficient to accomplish the desired retorting, additional extraneous fuel may be added to the fluid bed in the form of heavy oil, tar or the like.
  • the fluidized bed is operated to provide turbulent frictional contact within the bed section 13 and freeboard section 14 to thereby cause severe attrition of the friable spent shale ash into shale ash fines having a particle size preferable less than 200 mesh.
  • the fluidized bed is operated at temperatures ranging from about 1100 F. to about 1650 F. and at fluidizing superficial air velocities of from about 2.5 to 6.0 feet per second.
  • the higher combustion temperatures of 1400 to 1650 F. are desired because carbonate decomposition of the spent shale more readily occurs, thereby enhancing the breakdown and degree of attrition of shale ash in the combustion zone.
  • a further product of the combustion reaction is hot flue gas.
  • the attrited shale ash fines are elutriated from the reheated heatcarrying bodies by the hot flue gas and withdrawn from the freeboard section 14 via cyclone separator 15 and line 16.
  • the cyclone separator 15 returns any of the larger heat-carrying bodies which may be jetted out of the fluidized bed back to the bed.
  • the hot flue gas which contains shale ash fines is conveyed via line 25 through a cooler 17 and into a solids removal zone 18, i.e., bag filter, prior to being discharged to the atmosphere via line 19.
  • the reheated heat-carrying bodies and any larger remaining particles of the friable shale ash not removed with the hot flue gas are withdrawn from the dense phase fluid bed combustion zone 11 via standpipe 20.
  • the reheated heat-carrying bodies and the small remainder of the friable shale ash particles are fed through line 22 by hot air transport gas from source 21 into the heat carrier accumulator 4 having therein an elutriator 23 equipped with a plurality of attriter bars or baflles 24.
  • the friable shale ash particles are attrited and comminued by impacting against the attriter bars 24 and thereby converted into shale ash fines having an average particle size of about 200 mesh (U.S.
  • the elutriator also serves to disperse the shale ash fines so as to significantly improve the elutriation thereof from the heat-carrying bodies.
  • the suspension of shale ash fines in the hot air transport gas is withdrawn from the elutriator 23 via line 25 which joins line 16 and passes through cooler 17 for cooling prior to subsequent fines-gas separation and disposal.
  • the hot heat-carrying bodies now entirely or substantially free from shale ash, accumulate in a bed 26 within the base of the heat carrier accumulator 4.
  • the heat carriers are fed from the accumulator 4 via line at a temperature of from 1100" F. to 1650 F. into the retort 2 to eifect pyrolysis of fresh oil shale introduced therein. Excess solids are withdrawn from accumulator 4 via line 27.
  • a process for the recovery of shale oil from oil shale which comprises:
  • a process for the recovery of shale oil from oil shale which comprises:

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
US133507A 1971-04-13 1971-04-13 Process for retorting oil shale in the absence of shale ash Expired - Lifetime US3691056A (en)

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Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3976558A (en) * 1974-06-26 1976-08-24 Hall Robert N Method and apparatus for pyrolyzing oil shale
US4038100A (en) * 1975-05-16 1977-07-26 The Oil Shale Corporation (Tosco) Char composition and a method for making a char composition
DE2704032A1 (de) 1976-03-26 1977-09-29 Chevron Res Verfahren zum vergasen und destillieren fester, kohlenstoffhaltiger materialien sowie zum in-beruehrung-bringen zweier feststoffe in einem fuellkoerper enthaltenden reaktor
US4054492A (en) * 1975-02-28 1977-10-18 Metallgesellschaft Aktiengesellschaft Process for treating bituminous or oil-containing material using dry distillation
US4105536A (en) * 1976-04-23 1978-08-08 Morrell Jacque C Processes including the production of non-congealing shale oil from oil shales
DE2709671A1 (de) * 1977-03-05 1978-09-14 Oconnor Chadwell Fliessbett-drehrohrofen zur pyrolythischen verbrennung von abfaellen
US4161442A (en) * 1978-01-05 1979-07-17 Mobil Oil Corporation Processing of tar sands
US4191630A (en) * 1976-04-23 1980-03-04 Morrell Jacque C Process for the production of shale oil from oil shales
DE2937065A1 (de) * 1979-09-13 1981-04-02 Metallgesellschaft Ag, 6000 Frankfurt Verfahren zum kuehlen heisser, koerniger feststoffe
US4312740A (en) * 1978-04-08 1982-01-26 Tosco Corporation Process for maximizing oil yield in the retorting of oil shale
DE3100117A1 (de) * 1981-01-05 1982-07-29 Tosco Corp., 90067 Los Angeles, Calif. "verfahren und vorrichtung zum gewinnen von schieferoel"
CN102504850A (zh) * 2011-11-21 2012-06-20 江苏鹏飞集团股份有限公司 一种油砂固体热载体低温干馏工艺
CN103205269A (zh) * 2013-05-06 2013-07-17 陕西冶金设计研究院有限公司 小颗粒油页岩干馏装置及其干馏工艺

Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3976558A (en) * 1974-06-26 1976-08-24 Hall Robert N Method and apparatus for pyrolyzing oil shale
US4054492A (en) * 1975-02-28 1977-10-18 Metallgesellschaft Aktiengesellschaft Process for treating bituminous or oil-containing material using dry distillation
US4038100A (en) * 1975-05-16 1977-07-26 The Oil Shale Corporation (Tosco) Char composition and a method for making a char composition
DE2759823C2 (de) * 1976-03-26 1984-02-23 Chevron Research Co., 94105 San Francisco, Calif. Verfahren zur Destillation eines festen kohlenstoffhaltigen Materials
DE2704032A1 (de) 1976-03-26 1977-09-29 Chevron Res Verfahren zum vergasen und destillieren fester, kohlenstoffhaltiger materialien sowie zum in-beruehrung-bringen zweier feststoffe in einem fuellkoerper enthaltenden reaktor
US4105536A (en) * 1976-04-23 1978-08-08 Morrell Jacque C Processes including the production of non-congealing shale oil from oil shales
US4161441A (en) * 1976-04-23 1979-07-17 Morrell Jacque C Process for the production of distillate fuels from oil shales and by-product therefrom
US4191630A (en) * 1976-04-23 1980-03-04 Morrell Jacque C Process for the production of shale oil from oil shales
DE2709671A1 (de) * 1977-03-05 1978-09-14 Oconnor Chadwell Fliessbett-drehrohrofen zur pyrolythischen verbrennung von abfaellen
US4161442A (en) * 1978-01-05 1979-07-17 Mobil Oil Corporation Processing of tar sands
US4312740A (en) * 1978-04-08 1982-01-26 Tosco Corporation Process for maximizing oil yield in the retorting of oil shale
DE2937065A1 (de) * 1979-09-13 1981-04-02 Metallgesellschaft Ag, 6000 Frankfurt Verfahren zum kuehlen heisser, koerniger feststoffe
DE3100117A1 (de) * 1981-01-05 1982-07-29 Tosco Corp., 90067 Los Angeles, Calif. "verfahren und vorrichtung zum gewinnen von schieferoel"
CN102504850A (zh) * 2011-11-21 2012-06-20 江苏鹏飞集团股份有限公司 一种油砂固体热载体低温干馏工艺
CN102504850B (zh) * 2011-11-21 2013-08-07 江苏鹏飞集团股份有限公司 一种油砂固体热载体低温干馏工艺
CN103205269A (zh) * 2013-05-06 2013-07-17 陕西冶金设计研究院有限公司 小颗粒油页岩干馏装置及其干馏工艺
CN103205269B (zh) * 2013-05-06 2014-12-17 陕西冶金设计研究院有限公司 小颗粒油页岩干馏装置及其干馏工艺

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CA965721A (en) 1975-04-08
AU4104972A (en) 1973-08-30
BR7202175D0 (pt) 1973-05-31

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