US1767283A - Continuous low-temperature process and apparatus for treating hydrocarbons - Google Patents

Continuous low-temperature process and apparatus for treating hydrocarbons Download PDF

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US1767283A
US1767283A US676760A US67676023A US1767283A US 1767283 A US1767283 A US 1767283A US 676760 A US676760 A US 676760A US 67676023 A US67676023 A US 67676023A US 1767283 A US1767283 A US 1767283A
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William L Gomory
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Standard Oil Development Co
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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
    • C10G9/00Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G9/14Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils in pipes or coils with or without auxiliary means, e.g. digesters, soaking drums, expansion means

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  • the first step, the heating is accomplished in sucha. manner that the crude materia'l is rapidly heated underepressure in liquid formto a predetermined temperature, but without any substantial de composition. There -is no carbon deposition in the heating zone, thereby the continuity of the process is not impaired.
  • the cru e material, leaving the heating zone with a predetermined temperature, passes'into the cracking zone where it remains under the same temperature andQpressure for a length of time necessary to obtain a thorough decomposition and the deposition of carbon.
  • the properly decomposed material passes into a vaporizlng chamber and can be treated in any convenient manner according to,
  • the heating can be accomplished, for instance, in a coil set in a furnace.
  • the decomposition occurs in the cracking 'zone,
  • the subject-matter of this present application is a specific improvement in connection with the cracking zbne (converters) and its operation.
  • the present process and apparatus enables periodic removal of carbon from any one of the converters without disturbing the continuity of the operation and furthermore makes it possible to obtain commercial results at very much lower temperatures than usedby other methods.
  • Fig. 1 is a diagrammatic illustration of the system.
  • Fig. 2 is a diagrammatic illustration of the'heating zone
  • FIG.3 is a diagrammatic illustration of a l means for heating a converting chamber.
  • Theheating of the cracking chambers for maintaining the cracking temperature can be accomplished either by heating the tanks 'onthe outside, or inside, with 'fire tubes, for; instance,but preferably in such a manner that the temperature ofthe heating agent is kept close to the temperature of the oil,
  • inFig. 2, 5 is a furnace heated by burner 40, and within which is a coil 6 into which oil is forced, preferably through a heat interchanger 9, by pressure pump 7.
  • the heated oil passes out of the coil into pipe line I of Fig. 1'.
  • the cracking or decomposition chambers are heated in any suitable manner, e. g. as
  • a burner 41 by a burner 41, or by hot waste gases, a series of baflies 27 forming an encircling flue terminating in stack 28.
  • Oil is introduced through pipe a (see Fig. 1) and flows out through pipe I).
  • H is a valved exit pipe (see Fig. 1), for releasingvapors during the filling of the chamber, the
  • valve being closed at other times.
  • the setting of the chambers is so arranged that their bottoms or sides up to a certain height are bricked in to prevent direct impingement of heat on that portion of the shell within which carbon deposits.
  • the series of cracking chambers ' (converters through a reducin verters) is connected with a heating zone at one end and with the vaporizer at the other end. Further, the cracking chambers are inter-connected in such a manner that it is possible to connect in or cut-out any one of the converters from the system without disturbing the same, Another pipe line serves to charge the cracking chambers withpreheated oil.
  • the vapors which might develop while the cracking chambers are being charged canescape through the properly set relief valves and their connections, commurliicating through a cooler with a receiving tan
  • the high pressure pump forces the crude material through the heating zone into the main line No. I, from which through properly valved connection the hot crude mate rial can be directed through any of the converters.
  • any one of the converters can be periodically charged with pre-heated crude material.
  • Line No. II with its valved branches, establishes connection among the converters and renders it possible to cut out any one of the converters and connect in any other converter without disturbing the continuity ofthe operation.
  • No. III line continuously'carriesr the decomposed material from anyone of the con.- valve to vaporizer J and through line 0.
  • V the decom' posed material can pass from any one ofthe converters which has been cut out for cleaning, through a reducing valve into the va-.
  • Branch-lines b b carry away the material from the top of the converters thereby keeping them substantially full with oil.
  • the crude material which has been heated to the predetermined decomposing temperature during its rapid passage through the heating coil, continuously passes throu h main-line I and valves 11 and '21 (va ms 11' and 71 are closed) through a branch-line and 31 check valve (valve 91 is closed) into F converter and therefrom through b branch-line and valves 41 and 51 (valves 81 and 61 being closed) into return-line II from which it 'passes through valves 72 and 22, (valves 62 and 1 12 are closed) through a branch-line and 32 check valve (valve 92 being closed) into F converter; from F converter through I) branch-line and valves 42 and 52 (valves 82 through F converter the material travelsthrough I) branch-line and valves 43 and 53 (valves 83 and ,63 being closed) into -return-line II, and therefrom through valves I 74 and: 24 (valves 64 and 14 are closed) through a branch-line and 34 check'valve (valve 94 being closed
  • the next step in the operation is to cut outF converter from the system for cleanmg, respectively to prepare F converter tobe connected into the system.
  • F con- .verter will be charged through chargingline IV and .valve 105' (valves 101, 102, 103
  • valve 64 is opened,
  • valves 74, 24, 84 and 44 are closed, then valve 94 is opened and thereby the decomposed material will pass through discharge-line V and reducing valve 100 into vaporizer J.
  • F converter Simultaneously with the discharging of the decomposed material from F converter, F converter, which has been previously filled with preheated material, is connected into the system by opening valves 75, 25, 45, and and closin valve 85, so that the material leaving a converter through 6? branch-line and valves 43 and 53 will pass through return-line II (valves 63, 65, 83, 74 and-54 being closed) through valves 75 and 25 (valve 15 is closed) through a branch-line "and 35 check valve (valve being closed) into F converter and through it and b branch-line, passing valves 45 and With this arrangement the apparatus iscontinuously operating with full capacity without any interruption. The continuity of operation of the heating zone is assured by avoiding any carbon deposition in same,
  • the cleaned converter already filled with preheated material should be connected into the system as the first or the last member of the series of converters in regard to the direction of the oil travel through the system. If the converter, which contained in the incoming rial by reabsorbing them and thereby stahas just been charged with preheated mate-.
  • the decomposed material arising from the previous converters with the decomposing temperature will have to pass through the preheated material contained in that last converter and necessarily of a' lower temperature than the incoming decomposed oil.
  • the forced passage of the incoming high temperature decomposed oil through the large body of lower temperature material is very advantageous as it delays the vaporization of the li ht hydrocarbons decomposed matebilizing them.
  • the present process and apparatus has the following advanta es.
  • the quality of the produced gasoline is far superior (less unsaturated hydrocarbons) than with rapid decomposition carried out at exceedingly high temperatures.
  • the low temperature decomposition is more economic as less permanent gas is produced and the carbon (coke) is of a softer and looser consistency. and does not adhereto the walls of the converters.
  • the same crude material can be used which arrives from the heating coil.
  • the number of converters to be used naturally can be larger or smaller than five and the method of connecting in and cutting out, as well as the nature of the ipe-lincs and connections can vary in wi e limits, without departing from the spirit of my I invention.
  • A. continuous low temperature process for cracking heavy hydrocarbons into lighter hydrocarbons which comprises heating the raw material to a predetermined decomposing temperature while rapidly forced under pressure through a heating coil at such rate that no substantial decomposition occurs and then continuously passing the heated oil through a series of decomposing chambers, without distillation, while the temperature and pressure are maintained, cutting out from the system any intermediate one of the series of decomposing chambers for cleaning and reconnecting it into the system after ithas been cleaned, each while continuing the chambers on each side of said intermediate chamber in normal series operation.
  • a continuous low temperature recess for cracking heavy hydrocarbons into ighter hydrocarbons which comprises heating the raw material to a predetermined decomposing temperature while rapidly forced under pressure through a heating coil at such rate that no substantial decomposition occurs and then continuously assing the heated oil through a series of decomposing chambers, without distillation, while the temperature and pressure are maintained, cutting out from the system any one of the seriesot decomposing chambers for cleaning, and charging the cleaned chamber with raw material, and reconnecting it into the system after it has been cleaned, without disturbing the continuity of the process.
  • a continuous process as claimed in claim 2 in which simultaneously with the disconnection of a decomposing chamber for cleaning, another clean decomposing chamber charged with raw material is connected into the system without disturbing the continuity of the process.
  • An apparatus for cracking hydrocar- Vfbons comprising a plurality of cracking chambers connected in series and means for dellvering heated 011 under pressure to and in succession through said chambers,'a va- I 'porizing chamber to which the series of cracking chambers is connected, means for maintainin the temperature and pressure, and means including the necessary pipe connections and valves for charging and conmotion or disconnection of anyone of the chambers forming a part of said series into and from the system while maintaining f series flow through all of the remaining chambers in said series.
  • An apparatus for cracking hydrocarbons a plurali of cracking chambers, a series connecting manifold, connections between each of said chambers andsaid series connecting manifold whereby oil ma caused to flow in series through said c "ambers, means for charging heated oil into the first of said chambers to flow therethrou h bons, a plurality of crackin chambers, a-
  • loop conduit forming a series connecting manifold, means for controllably connecting the individual oracln'ng chambers with said manifold whereb oil may be flowed 1,7emes said chambers whereby heated oil may be charged to any one of said chambers forming the initial one of the series, a discharge bons, a plurality of cracking chambers, a
  • loop conduit forming a series connecting manifold, means for controllably connecting the individual cracking chambers with said manifold whereby oil may be flowed in. se-
  • a charging manifold ries through said chambers with any one of said chambers as the starting point there-' of, a charging manifold, controllable connections between .the charging manifold and said chambers whereby heated oil may be charged to any one of said chambers forming the initial one of the series, a dispharge manifold, and controllable means connecting said discharge manifold with each of said chambers whereby oil may be discharged from the last one of said series.

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

Description

June 24, 1930. w. GOMORY 1,767,283
CONTINUOUS LOWTEMPER ATURE PROCESS AND APPARATUS FOR TREATING HYDROCARBONS Filed NOV. 24, 1923 WITNESSES 1| NYENTOR www Patented June 24, 1930 UNITED. STAT ES PATENT" OFFICE YWILLIAM L. GOMORY, OF CHICAGO, ILLINOIS, ASSIGNOR TO STANDARD OIL IDZEV'ELOP- MENT COMPANY, A CORPORATION OF DELAWARE CoNTINUOUS LOW-TEIIPEBATURE PROCESS-AND APPARATUS non IREAfIING I-IYDRO- cannons Application filed November 2' 1, 1923, Serial Nd. 676,760, and in Hungary August 1, 1928.
The subject-matter ofmy previous appli-. cations, Serial Nos. 498,670, 557,040, and 616,156 of which this application is a continuation in partfis a process and apparatus for decom osing heavy hydrocarbons into lighter hy roca'rbons characterized by the fact that the heating, decomposing. and. vaporizingoccur in three distinctly sepas rate steps. The first step, the heating, is accomplished in sucha. manner that the crude materia'l is rapidly heated underepressure in liquid formto a predetermined temperature, but without any substantial de composition. There -is no carbon deposition in the heating zone, thereby the continuity of the process is not impaired. The cru e material, leaving the heating zone with a predetermined temperature, passes'into the cracking zone where it remains under the same temperature andQpressure for a length of time necessary to obtain a thorough decomposition and the deposition of carbon.
. The properly decomposed material passes into a vaporizlng chamber and can be treated in any convenient manner according to,
the description of my" previous ap lications, Serial Nos.- 498,670, 557,040, and 616,156. The heating can be accomplished, for instance, in a coil set in a furnace. The decomposition occurs in the cracking 'zone,
conslsting of one or more' cracking chambers (converters) which are provided with the necessary appliances for the maintenance of the proper temperatures and pressures. The distillation of the decomposed oil can be carried out with or without the use of a cooler which is interposed between the vaporizer and cracking chambers.
The subject-matter of this present application is a specific improvement in connection with the cracking zbne (converters) and its operation. The present process and apparatus enables periodic removal of carbon from any one of the converters without disturbing the continuity of the operation and furthermore makes it possible to obtain commercial results at very much lower temperatures than usedby other methods.
In the accompanying drawings Fig. 1 'is a diagrammatic illustration of the system.
Fig. 2 is a diagrammatic illustration of the'heating zone; and
'Fig."3 is a diagrammatic illustration of a l means for heating a converting chamber.
the industry and'are not shown in Fig. 1.
Theheating of the cracking chambers for maintaining the cracking temperature can be accomplished either by heating the tanks 'onthe outside, or inside, with 'fire tubes, for; instance,but preferably in such a manner that the temperature ofthe heating agent is kept close to the temperature of the oil,
so that an overheating of thecracking cham ber or'fire tubes is avoided. This can be achieved for instance by rapidly circulating flue gases of proper temperaturearound the tank or through the fire tubes in any known manner.
As shown, for example, inFig. 2, 5 is a furnace heated by burner 40, and within which is a coil 6 into which oil is forced, preferably through a heat interchanger 9, by pressure pump 7. The heated oil passes out of the coil into pipe line I of Fig. 1'. The cracking or decomposition chambers are heated in any suitable manner, e. g. as
shown in Fig. 3, by a burner 41, or by hot waste gases, a series of baflies 27 forming an encircling flue terminating in stack 28. Oil is introduced through pipe a (see Fig. 1) and flows out through pipe I). H is a valved exit pipe (see Fig. 1), for releasingvapors during the filling of the chamber, the
valve being closed at other times. The setting of the chambers is so arranged that their bottoms or sides up to a certain height are bricked in to prevent direct impingement of heat on that portion of the shell within which carbon deposits.
The series of cracking chambers '(converters through a reducin verters) is connected with a heating zone at one end and with the vaporizer at the other end. Further, the cracking chambers are inter-connected in such a manner that it is possible to connect in or cut-out any one of the converters from the system without disturbing the same, Another pipe line serves to charge the cracking chambers withpreheated oil. The vapors which might develop while the cracking chambers are being charged canescape through the properly set relief valves and their connections, commurliicating through a cooler with a receiving tan The high pressure pump forces the crude material through the heating zone into the main line No. I, from which through properly valved connection the hot crude mate rial can be directed through any of the converters. Through line No. IV any one of the converters can be periodically charged with pre-heated crude material. Line No. II, with its valved branches, establishes connection among the converters and renders it possible to cut out any one of the converters and connect in any other converter without disturbing the continuity ofthe operation. No. III line continuously'carriesr the decomposed material from anyone of the con.- valve to vaporizer J and through line 0. V the decom' posed material can pass from any one ofthe converters which has been cut out for cleaning, through a reducing valve into the va-.
porizer J. I
The heated crude material coming from the heating zone into the main line No. I ;can
ass throu h branches a a into I F geonverters preferably on or close to their bottoms. Branch-lines b b carry away the material from the top of the converters thereby keeping them substantially full with oil.
As an example of the operation of the' process,let itbe assumed that F, F F and F converters are in operation and F will have to be cut out for cleaning, while F whlch has been previously cleaned is ready to be connected into the system.
The crude material, which has been heated to the predetermined decomposing temperature during its rapid passage through the heating coil, continuously passes throu h main-line I and valves 11 and '21 (va ms 11' and 71 are closed) through a branch-line and 31 check valve (valve 91 is closed) into F converter and therefrom through b branch-line and valves 41 and 51 (valves 81 and 61 being closed) into return-line II from which it 'passes through valves 72 and 22, (valves 62 and 1 12 are closed) through a branch-line and 32 check valve (valve 92 being closed) into F converter; from F converter through I) branch-line and valves 42 and 52 (valves 82 through F converter the material travelsthrough I) branch-line and valves 43 and 53 (valves 83 and ,63 being closed) into -return-line II, and therefrom through valves I 74 and: 24 (valves 64 and 14 are closed) through a branch-line and 34 check'valve (valve 94 being closed) into F converter. The cracked material, after passing through F converter goes through 5 branch-line and valves44and 84 (valves 54 and 84 being closed) arriving into transfer-line III, through which, passing valve '85 (valve 85 being closed) then (either through cooler J or byassing cooler J) throug'h reducing valve into vaporizer J. In this way the heated material arising from the heating coil passed throngh'converters' F F, F and F in series and was decomposed to the desired degree during this passage and the properly decomposed oilby-passing F converterreaches the vaporizer.
The next step in the operation is to cut outF converter from the system for cleanmg, respectively to prepare F converter tobe connected into the system. For this purpose,without disturbing the operation of the plantwith Ii 'F converters, F con- .verter will be charged through chargingline IV and .valve 105' ( valves 101, 102, 103
and 104 are closed) with crude material, preheatedvby passing it through any convenient reheater under pressure. Of course, the air from F converter must have been ceed to cut out F converter from the-sysing of F contem. To maintain the continuity of the process, first of all, valve 64 is opened,
valves 74, 24, 84 and 44 are closed, then valve 94 is opened and thereby the decomposed material will pass through discharge-line V and reducing valve 100 into vaporizer J.
Simultaneously with the discharging of the decomposed material from F converter, F converter, which has been previously filled with preheated material, is connected into the system by opening valves 75, 25, 45, and and closin valve 85, so that the material leaving a converter through 6? branch-line and valves 43 and 53 will pass through return-line II (valves 63, 65, 83, 74 and-54 being closed) through valves 75 and 25 (valve 15 is closed) through a branch-line "and 35 check valve (valve being closed) into F converter and through it and b branch-line, passing valves 45 and With this arrangement the apparatus iscontinuously operating with full capacity without any interruption. The continuity of operation of the heating zone is assured by avoiding any carbon deposition in same,
The continuity of the distillation from the vaporizer, while the cleaned converter is being connected into the system and properly operating, is assured by the decomposed material discharged from the converter which has been cut out from the system for cleaning.
The cutting out of any other converter of the system for cleaning purposes occurs identically with the above proceeding;.
naturally the cleaned converter is always to be filled with preheated material before the converter which is to be cleaned is cut out from the system.
Preferably the cleaned converter already filled with preheated material should be connected into the system as the first or the last member of the series of converters in regard to the direction of the oil travel through the system. If the converter, which contained in the incoming rial by reabsorbing them and thereby stahas just been charged with preheated mate-.
rial and connected into the system, is so connected that it is the last member of the series, then the decomposed material arising from the previous converters with the decomposing temperature will have to pass through the preheated material contained in that last converter and necessarily of a' lower temperature than the incoming decomposed oil. The forced passage of the incoming high temperature decomposed oil through the large body of lower temperature material is very advantageous as it delays the vaporization of the li ht hydrocarbons decomposed matebilizing them.
Beside the advantages already cited above,
' the present process and apparatus has the following advanta es.
The exceedingly long time which the crude material has'to spend in this process under .suficiently prolonged to enable to obtain the same or better results from the same crude material with materially lower temperatures, for instance, with 395? to 400 C.
The importance of the lower temperature is obvious for both process and apparatus. The exceedingly high temperatures used by other processes Wear out the equipment very rapidly, consequently by decreasing the reaction temperature the life of the equipment .is being prolonged. The decomposing temas there is no decomposition in the coil.
erature which is bein used in any process has a very decided influence on the quality.
of the gasoline produced, that is, with a slow decomposition carried out at lower temperatures the quality of the produced gasoline is far superior (less unsaturated hydrocarbons) than with rapid decomposition carried out at exceedingly high temperatures. The low temperature decomposition is more economic as less permanent gas is produced and the carbon (coke) is of a softer and looser consistency. and does not adhereto the walls of the converters.
For the charging of the cleaned converters to be connected into the system the same crude material can be used which arrives from the heating coil. In other instances it is preferable to use a difl'erent material for this purpose.
The number of converters to be used naturally can be larger or smaller than five and the method of connecting in and cutting out, as well as the nature of the ipe-lincs and connections can vary in wi e limits, without departing from the spirit of my I invention.
What I claim is:- V
l. A. continuous low temperature process for cracking heavy hydrocarbons into lighter hydrocarbons which comprises heating the raw material to a predetermined decomposing temperature while rapidly forced under pressure through a heating coil at such rate that no substantial decomposition occurs and then continuously passing the heated oil through a series of decomposing chambers, without distillation, while the temperature and pressure are maintained, cutting out from the system any intermediate one of the series of decomposing chambers for cleaning and reconnecting it into the system after ithas been cleaned, each while continuing the chambers on each side of said intermediate chamber in normal series operation.
2. A continuous low temperature recess for cracking heavy hydrocarbons into ighter hydrocarbons which comprises heating the raw material to a predetermined decomposing temperature while rapidly forced under pressure through a heating coil at such rate that no substantial decomposition occurs and then continuously assing the heated oil through a series of decomposing chambers, without distillation, while the temperature and pressure are maintained, cutting out from the system any one of the seriesot decomposing chambers for cleaning, and charging the cleaned chamber with raw material, and reconnecting it into the system after it has been cleaned, without disturbing the continuity of the process.
3. A continuous process as claimed in claim 2, in which the chamber charged with raw material is connected into the system as the last member of the series of decomposing chambers so that the decomposed material continuously passing through the system at the decomposing temperatures passes through the lower temperature char e of the newly connected converter and t on discharging the decomposed material at reduced pressure into a vaporizing chamber.
4. A continuous process as claimed in claim 2 in which simultaneously with the disconnection of a decomposing chamber for cleaning, another clean decomposing chamber charged with raw material is connected into the system without disturbing the continuity of the process.
5. A process as claimed in claim 2 in which the clean converter is charged with raw material different from that continuously passing through the system.
6. An apparatus for cracking hydrocar- Vfbons comprising a plurality of cracking chambers connected in series and means for dellvering heated 011 under pressure to and in succession through said chambers,'a va- I 'porizing chamber to which the series of cracking chambers is connected, means for maintainin the temperature and pressure, and means including the necessary pipe connections and valves for charging and conmotion or disconnection of anyone of the chambers forming a part of said series into and from the system while maintaining f series flow through all of the remaining chambers in said series.
7. An apparatus for cracking hydrocarbons, a plurali of cracking chambers, a series connecting manifold, connections between each of said chambers andsaid series connecting manifold whereby oil ma caused to flow in series through said c "ambers, means for charging heated oil into the first of said chambers to flow therethrou h bons, a plurality of crackin chambers, a-
loop conduit forming a series connecting manifold, means for controllably connecting the individual oracln'ng chambers with said manifold whereb oil may be flowed 1,7emes said chambers whereby heated oil may be charged to any one of said chambers forming the initial one of the series, a discharge bons, a plurality of cracking chambers, a
loop conduit forming a series connecting manifold, means for controllably connecting the individual cracking chambers with said manifold whereby oil may be flowed in. se-
ries through said chambers with any one of said chambers as the starting point there-' of, a charging manifold, controllable connections between .the charging manifold and said chambers whereby heated oil may be charged to any one of said chambers forming the initial one of the series, a dispharge manifold, and controllable means connecting said discharge manifold with each of said chambers whereby oil may be discharged from the last one of said series.
, WILLIAM L. GOMORY.
in series through said 0 ambers with any one of said chambers as the starting point thereof, a charging manifold, controllable connections between the charging manifold g
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