US1825294A - Treating hydrocarbons - Google Patents

Treating hydrocarbons Download PDF

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Publication number
US1825294A
US1825294A US719958A US71995824A US1825294A US 1825294 A US1825294 A US 1825294A US 719958 A US719958 A US 719958A US 71995824 A US71995824 A US 71995824A US 1825294 A US1825294 A US 1825294A
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chlorid
still
hydrocarbons
hydrogen
oil
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US719958A
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Edson R Wolcott
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Texaco Inc
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Texaco Inc
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    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING 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
    • C10G11/00Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G11/02Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used
    • C10G11/08Halides

Definitions

  • umrso is'ra'rss PATENT; oFFica IDSOH nawowo'ra', 01 PORT THUR, TRA S, ASSIGNOB, BY IESNE ASSIGNMENTS, 1'0
  • This invention relates to the treatment of hydrocarbons with certain materials to effeet a conversion of higher boiling hydrocarbons into lower boiling hydrocarbons, and relates particularly to improvements in methods of treatment in which metallic halids,
  • a vapor line 14 which may extend to one or more air condensers 15, or other suitable refluxing or fractionating means, from which a vapor line 16 extends to a outlet 18.
  • a pipe 19 is provided which preferably depends into the still to a point near the bottom thereof.
  • the pipe 19 may terminate in one or more spray pipes, as the perforated pipe 20, in order to thoroughly 'difiuse the hydrogen chlorid through the mass in the still.
  • a layer of porous or permeable mate: rial may be placed in the still and the hydrogen chlorid caused to be introduced by dif-' fusion through the porous substance thereby apparatus which has hitherto been considere condenser 17 provided with an.
  • the hydrocarbon material to be treated which may be a petroleum product such as gas oil, or kerosene, or other hydrocarbon oil which it'is desired to convert into a lower boiling oil, is in-.
  • a suitable metallic halid, preferably anhydrous aluminum, chlorid, is charged through the pi 12, either in the form of the lum or ulveru ent chlorid or in the form of a l1qui obtained by ing the chlorid with a suitable solvent or car-- rier, such as hydrocarbon oil or other suitable protective medium in which. the. chlorid is dissolved or contained.
  • a suitable solvent or car-- rier such as hydrocarbon oil or other suitable protective medium in which. the. chlorid is dissolved or contained.
  • the hydrochloric acid gas- is introduced through the pipe 19 and thence through the spray pipe 20, or 4 through porous material or other sultable diffusing means, into the mass in the still.
  • the lower boiling point product obtained maybe removed as a condensate through the condensate outlet 18.
  • reaction is not a hydrogenating one; in fact, I do not undertake to explain the chemical reactions which 100 occur in the practice of my invention. It is sufiicient to state that in conductingthe treatment of hydrocarbons with a treatm mate'- rial, such as aluminum chlorid, the e ectiveness of the operation is increased by the addition of extraneous hydro n chlorid.
  • the hydrogen chlorid em loyed in the practice of the invention may e in the form of dry as or moist hydro en chlorid or hydroch oric acid may be einp oyed, since the presence of moisture or the a ueous solution causes the production of hydrogen chlorid due to the decomposition of the aluminum chlorid by water. if desired, water itself may be added to the treating vessel or moist oil may be admitted thereto, the presence of the moisture insuring the production of the necessary hydrogen chlorid.
  • What 1 claim is: 1. The process of treatinr hydrocarbon oils to sheet conversion'of higher boiling hydrocarbons into lower boiling hydrocarbons which comprises chewing a high boiling petroleum oil, and a catai anhydrous aluminum chloride to a still, maintaining said still at a temperature sufficient to sheet material conversion of the oil therein, introducing hydrogen chloride into.
  • said still to thoroughly commin is with the oil and aluminum chloride, where y a smooth evolution of vapors is obtained and the aluminum chloride is maintained in an active condition, condensing the evolved vapors to form a distillate of low boilig hydrocarbons, and withdrawing, before substantial accumulation of coke ocurs, the residual liquid from the still-for disposal without further treatment.

Description

Sept. 29, 1931. E. R. WOLCOTT 1,825,294
TREATING HYDROCARBONS Filed June 14, 1924 351 Gwen 1401;;
umrso is'ra'rss PATENT; oFFica IDSOH nawowo'ra', 01 PORT THUR, TRA S, ASSIGNOB, BY IESNE ASSIGNMENTS, 1'0
TH] arms COIPAHY, 0! NEW YORK, I. Y. A CORPORATION 01' DEL AWL rmrmc mnocmons Application m June 14. 1924. Serial 1 .71am.
This invention relates to the treatment of hydrocarbons with certain materials to effeet a conversion of higher boiling hydrocarbons into lower boiling hydrocarbons, and relates particularly to improvements in methods of treatment in which metallic halids,
' such as aluminum chlorid, are employed.
I have found that if the hydrocarbons be .heated or distilled in the presence of a me- 10 tallic halid, such as aluminum chlorid, and if the heating or distillation be carried on in the presence of hydrogen chlorid, or while introducing the hydrogen chlorid into the still that an efiectual conversion of higher s boiling point products into lower boiling products may be obtained. The addition of the h drogen chlorid-- insures an even and smoot operation of the still and materially increases the yield of lower boiling products.
so The invention is such that it can be most conveniently described by reference to certain apparatus adapted for carrying out the process. The accompanying drawing is '8. diagrammatic elevation of an apparatus suitable or this purpose.
In the a paratus thus illustrated a stil1 10.
is arrange to be heated by any suitable heatingmeans (not shown) and provided with a charging line 11 for introducing the hydrocarbon material to be treated, a charging conduit 12 for admitting the treating material, and a draw-ofi pipe 13 for drawing oil .residue. The still is equipped with a vapor line 14 which may extend to one or more air condensers 15, or other suitable refluxing or fractionating means, from which a vapor line 16 extends to a outlet 18.
For introducing the hydrogen chlorid a pipe 19 is provided which preferably depends into the still to a point near the bottom thereof. The pipe 19 may terminate in one or more spray pipes, as the perforated pipe 20, in order to thoroughly 'difiuse the hydrogen chlorid through the mass in the still. If desired, a layer of porous or permeable mate: rial may be placed in the still and the hydrogen chlorid caused to be introduced by dif-' fusion through the porous substance thereby apparatus which has hitherto been considere condenser 17 provided with an.
admitting the gas in a finely divided state and thoroughly commingling it with the materials in the still. a Y r In the operation of the process the hydrocarbon material to be treated, which may be a petroleum product such as gas oil, or kerosene, or other hydrocarbon oil which it'is desired to convert into a lower boiling oil, is in-.
- troduced through the pipe 11. A suitable metallic halid, preferably anhydrous aluminum, chlorid, is charged through the pi 12, either in the form of the lum or ulveru ent chlorid or in the form of a l1qui obtained by ing the chlorid with a suitable solvent or car-- rier, such as hydrocarbon oil or other suitable protective medium in which. the. chlorid is dissolved or contained. The hydrochloric acid gas-is introduced through the pipe 19 and thence through the spray pipe 20, or 4 through porous material or other sultable diffusing means, into the mass in the still. The lower boiling point product obtained maybe removed as a condensate through the condensate outlet 18.
' The use of mixing, stirring, or scrapin 75 necessary in carrying on the treatment of oils with aluminum chlorid is practically. dispensed with in the practice of my invention, since the passage of the hydrogen chlorid gas through the mass in the still produces an effective agitation tending to prevent the sludge and tarry matters from collecting and coking in the bottom of the still and bringing about good contact between the catalyst and the hydrocarbon material. Stirring, agitating or scraping mechanism may, however, be employed, if desired.
An idea whlch induced the present invention was that by passing the hydrogen chlorid through the hydrocarbon material in the presence of aluminum chlorid (AhCh) it might be possible to cause a hydrogenating efiect'by combining the hydrogen with the heavier hydrocarbons to increase the yield of lighter and more saturated hydrocarbons, while at the same'time the chlorin would operate to regenerate the aluminum chlorid.
It may be, however, that the reaction is not a hydrogenating one; in fact, I do not undertake to explain the chemical reactions which 100 occur in the practice of my invention. It is sufiicient to state that in conductingthe treatment of hydrocarbons with a treatm mate'- rial, such as aluminum chlorid, the e ectiveness of the operation is increased by the addition of extraneous hydro n chlorid.
meme
when the reaction has proceeded to the desiredextent.
In witnem whereof I have hereunto set my handthis22n in one method of con ucting my process the hydrocarbon material is first saturated with hydrogen chlorid, after which the aluminum chlorid is added and the distillation carried on. In the preferred method of opera-- tion, however, the hydrogen chlorid gas is introduced into the still during the distillation.
The hydrogen chlorid em loyed in the practice of the invention may e in the form of dry as or moist hydro en chlorid or hydroch oric acid may be einp oyed, since the presence of moisture or the a ueous solution causes the production of hydrogen chlorid due to the decomposition of the aluminum chlorid by water. if desired, water itself may be added to the treating vessel or moist oil may be admitted thereto, the presence of the moisture insuring the production of the necessary hydrogen chlorid.
()bviousiy, various modifications oi the invention may effected without departing from the spirit ens scope ofthe invention.
\ u u d I The true scope of the invention is defined 1n the appended claims.
What 1 claim is: 1. The process of treatinr hydrocarbon oils to sheet conversion'of higher boiling hydrocarbons into lower boiling hydrocarbons which comprises chewing a high boiling petroleum oil, and a catai anhydrous aluminum chloride to a still, maintaining said still at a temperature suficient to sheet material conversion of the oil therein, introducing hydrogen chloride into.
said still to thoroughly commin is with the oil and aluminum chloride, where y a smooth evolution of vapors is obtained and the aluminum chloride is maintained in an active condition, condensing the evolved vapors to form a distillate of low boilig hydrocarbons, and withdrawing, before substantial accumulation of coke ocurs, the residual liquid from the still-for disposal without further treatment.
2. The process of treating hydrocarbon oils to sheet conversion of higher boiling hydrocarbons into lower boiling hydrocarbons which comprises subjecting a higher boiling petroleum oil to distillation tem ratures in the presence of a catalyst consist1n solely of anhydrous aluminum chloride, intimately commingling hydrogen chloride with the hot mixture of oil and aluminum chloride to produce an even evolution of vapors of low boilin hydrocarbons and to prevent the oil and a uminum chloride from coking, subjecting the evolved vapors to dephlegmation to produce a vapor fraction of the desired quality and wit drawing the unvaporized residue, which is not returned to the still,
yet consisting solely of d da of Ma 1924.
i E SON WQLCOTT.
US719958A 1924-06-14 1924-06-14 Treating hydrocarbons Expired - Lifetime US1825294A (en)

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2443606A (en) * 1939-12-09 1948-06-22 Standard Oil Co Production of branched chain paraffin hydrocarbons
US2529590A (en) * 1950-11-14 Preparation of a hydrocarbon
US4504378A (en) * 1983-02-18 1985-03-12 Marathon Oil Company Sodium tetrachloroaluminate catalyzed process for the molecular weight reduction of liquid hydrocarbons
US4505810A (en) * 1983-12-30 1985-03-19 Marathon Oil Company Hydrogen tetrachloroaluminate as a co-catalyst with sodium tetrachloroaluminate for the conversion of heavy hydrocarbons
US4513163A (en) * 1983-12-30 1985-04-23 Marathon Oil Company Conversion of aromatics to iso-paraffins using a NaAlCl4 /HAlCl4 molten salt catalyst system
US4555327A (en) * 1984-07-02 1985-11-26 Marathon Oil Company Cracking with tetrachloroaluminate catalysts and water
US4557803A (en) * 1984-07-02 1985-12-10 Marathon Oil Company Cracking process catalyst selection based on cation electronegativity

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2529590A (en) * 1950-11-14 Preparation of a hydrocarbon
US2443606A (en) * 1939-12-09 1948-06-22 Standard Oil Co Production of branched chain paraffin hydrocarbons
US4504378A (en) * 1983-02-18 1985-03-12 Marathon Oil Company Sodium tetrachloroaluminate catalyzed process for the molecular weight reduction of liquid hydrocarbons
US4505810A (en) * 1983-12-30 1985-03-19 Marathon Oil Company Hydrogen tetrachloroaluminate as a co-catalyst with sodium tetrachloroaluminate for the conversion of heavy hydrocarbons
US4513163A (en) * 1983-12-30 1985-04-23 Marathon Oil Company Conversion of aromatics to iso-paraffins using a NaAlCl4 /HAlCl4 molten salt catalyst system
US4555327A (en) * 1984-07-02 1985-11-26 Marathon Oil Company Cracking with tetrachloroaluminate catalysts and water
US4557803A (en) * 1984-07-02 1985-12-10 Marathon Oil Company Cracking process catalyst selection based on cation electronegativity

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