US2235329A - Method and apparatus for treating a plurality of heavy hydrocarbon oils for subsequent cracking - Google Patents

Method and apparatus for treating a plurality of heavy hydrocarbon oils for subsequent cracking Download PDF

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US2235329A
US2235329A US189136A US18913638A US2235329A US 2235329 A US2235329 A US 2235329A US 189136 A US189136 A US 189136A US 18913638 A US18913638 A US 18913638A US 2235329 A US2235329 A US 2235329A
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Ernest A Ocon
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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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  • This preliminary treatment is carried out to form from the vaporized and unvaporized blended fractions at least two preconditioned or purified streams of material having different characteristics and boiling ranges, each stream being adapted for separate treatment under conditions selectively controlled for subsequent conversion.
  • two streams may be led to different heating zones and subjected to different thermal treatments for a maximum conversion of the materials into high anti-knock motor fuels with a minimum formation of gas and coke.
  • this invention In promoting this main object of preconditioning a plurality of .materials to obtain an optimum yield of desired products, this invention also provides for economies realized through novel features of using hot conversion products as distillation aids and in the ecient removal of deleterious substances from the conversion products.
  • a regulated stream of uncracked initial oil e. g. crude oil, which is preferably preheated to below a cracking temperature
  • a regulated stream of oil containing products from a previously cracked oil Vapors from these materials are blended and increased in temperature by an added blast of vapors', preferably a blast of hot hydrocarbon products from a moderate splitting of heavy hydrocarbons at low cracking temperatures in the presence of a hydrogenous gas, e.
  • blast serves a threefold purpose: (l) to increase the fluidity of materials injectedA into the tower; (2) to increase the vaporization of volatiles in the injected materials so as to releasev therefrom more lower boiling fractions without cracking; (3) to obtain a conservation of heat energy.
  • This contact mass may contain desulfurizing agent suoliv as metals or metal compounds of lthe desulfurizing type over which vapors passing to the upper part of .said tower for fractionating may pass.
  • the metals or compounds may advantageously be mixed or bound with adsorbents such as Florida earth, attapalgus clay, fullers earth, bentonite, bauxite, and the like.
  • the desulfurizing agentV may also be in granular form or on the surface of an inorganic carrier, e. g., granules of Portland cement, fibrous asbestos or similar materials.
  • the preliminary tower or preconditioning and fractionating zone at least two bodies of oil ⁇ preconditioned for further processing are formed, one of gas oil type with substantially virgin gas oil quality for high temperature cracking to produce high anti-knock motor fuel with a minimum of coke formation and another for obtaining lubricating oil or for further conditioning to obtain more virgin quality cracking stock by moderate heat treatment at low cracking temperature.
  • conversion products from both zones can be blended and further purified, if desired, and the blended vapors are subjected to common fractionation and condensation.
  • the pressure employed in the preliminary tow-v er is preferably low compared with other parts ofthe system, e. g. subatmospheric, especially iny rsf.
  • the vapor blend of cracked and uncracked hydrocarbons, comprising constituents of straight run and cracked character formed in the preliminary tower is purified and fractionated to obtain at least a highly desirable gas oil type cracking stock of lower sulphur content.
  • a reforming stock can be condensed from the overhead following the condensation of the gas oil type fraction.
  • the purified gas oil type cracking stock formed in the preliminary tower may be led to a cracking zone to be cracked. at about 900 to 1100 F., at a superatmosphericpressure, or be blended with more recycle stock for cracking at about the same pressure and temperature conditions.
  • Heavier fractions and unvaporized oil formed in the preliminary tower make upA matev rials which can be used to refine into lubricants or be led to the separately controlled moderate heating zone to obtain more conditioned, productsfor, blending with the gas oil type fraction beforeY or after the high temperature cracking of saidgas oil type fraction.
  • This moderate heating treatment of oils higher boiling than. gas oil is carried outk at about 700 to 850 F., under pressure, with lowered temperatures if a catalyz'ing contact mass is used, and preferablywith the aid of a hydrogenous gaseousagent, e. g. steam, to obtain mainly a moderate splittingof its constituents.
  • this invention contains improvements inrenhancing the virginl qualities of distillates to be condensed from vapors containing partially converted recycle stock and straightrun cracking stock constituents and for enhancing the yields of such vapors for obtaining increased yields of purified fractions for high temperature cracking with a minimum coke formation.
  • attachments to the fractionating towers give this improved purification and a novel use, of high temperature cracking products in forcing vaporization olf more moderately cracked oils with increased stripping of volatiles to enhance the yields.
  • Fig. 1 is a diagrammatic representation of apparatus for effecting one embodiment of the process
  • Fig. 2 is an isometric drawing of the blending cham-ber.
  • theV charging stock for example, a crude oil
  • pipe I flows through pipe I through heat exchanger 2, and similar heat exchanger 2x, to be thereby heated to a temperature of about 400 to 700 F.
  • the chargingstock thus preheated is flashed into the bottompart of the lower section of the preliminary tower 3 forpreconditioning and fractionating.
  • valved lines 6 and/or 4 and 6 hot reflux condensates from tower 5 are passed into said tower 3, by valved lines 6 and/or 4 and 6 hot reflux condensates from tower 5, these condensates having a temperaturein the vrange of about 400 to 700 F., and containing insufliciently converted products higher boiling than gasoline.
  • a lighter and purer fraction led from above a partition a: in tower byline 4 ⁇ is preferably led into, tower 3 above partition 311:.l
  • These condensates in passingsfromzthe tower, generallyrhavinga. higher ⁇ pressure, into the lower pressure zone in tower 3 will flash into tower 3 with a substantial liberation of vapors.
  • vapors from the crudeoil vaporizing section of tower 3, below partition 3x may be passed to the fractionation section above partititon 3x, through apurifying agent I2,via valvedpipe; I0, for sulphurous and tar'forming material removal, I5 beinga by-pass for the vapor if purification is not necessary, and apreiluxing andcoolinglagent may be injectedin the fractionating section. by line I4, from anyl suitable. source,r for example, tank I3 such as shownand. ammoniaby. valved line
  • Preconditionedresidual fractions higher boiling 3, and .for a timeto obtainonly a small amount.
  • the steam may be superheated in coil 49, with reducing gases such as natural gas, xed gas from the cracking process etc.
  • the heating coils 9, 9.1:, and 49 are disposed in furnace K, having a burner B.
  • This furnace is represented as being of a type which has a bridge wall 50, forming a radiant heat section in which coil 9m, is mainly located.
  • the products of the moderate thermal treatment are preferably divided into two controlled streams under regulated pressure, one of these streams may pass through pipe 36, into a Iblending zone 31, wherein such products are blended with cracked products from coil 91:, passed into this blending zone through pipe 34, the discharge of materials into this zone being under eXpansio-n.
  • the other stream passes through pipe 8, and discharges with expansion into the lower part of tower 3, through spray 1.
  • Fig. 2 illustrates by isometric drawing the method in which the low temperature split products of coil 9 of the furnace are forced into circulation under great turbulence by the high velocity of the products from coil 9x that have been cracked under pressure and temperature cracking conditions higher than the said products of coil 9, and which are passed into the blending chamber tangentially through pipe 34 to provide perfect mixing, circulating and turbulent movement with improved conditioning of both products.
  • the pressure employed in the blending zone 31, and the following separating tower 39 will be less than the pressure in the heating coils 9, and 9m, but preferably greater than the pressure in tower 3.
  • the cracked products are passed entirely by line 35 into the lower part of separator 39, or partly thereto and partly by pipe 34, into the blending zone 31.
  • Chamber 31 discharges into the vapor separating tower 35, which is specially equipped at its midsection with a means 33, and 32, designed for retaining a pool of liquids in heated condition and in a state of high circulatory motion and turbulence induced largely by vapors and gases arising by upcomers 21, from the lower part of tower 39, the circulation being guided by the walls of the vessel 30, and cylindrical projection 32.
  • Residual liquids retained by means 33 tend to drop down outlets such as downcomer pipes 29, indicated, and to pass countercurrent to rising hot vapors in the lower part of tower 30, where they are subjected to a further stripping action, and nally the stripped residues collect in a lower pool of liquids, which is cooled by the injected cool fuel oil, through line 52 which may be a portion of the residual withdrawn by line 53, through cooler 54.
  • This novel arrangement serves to increase greatly the yield of vapors to be passed fro-m separator 30, to fractionator 5, by pipe 3l.
  • Hot gas oil from line l8r, passed by line 42, into the upper part of tower 30, aids in knocking down tar and developing a blend of vapors of cracked and uncracked hydrocarbons.
  • a gasoline condensate passed by pipe 43, from receiver 38, to condense out a heavy gas oil fraction.
  • Light hydrocarbons remaining in the vapor phase including gasoline, in the lower part of tower 5, may be passed to the upper part of said tower 5, for further fractionation, by
  • valved line 10x through an adsorptve contact mass 121:, which may be similar in composition and function to purifying contact mass l2, previously described, especially if contact mass l2, is not used, Ix being a by-pass for the vapors if purification is not necessary.
  • the vapors led thereto from below partition 5x are further fractionated to form a reux condensate of higher boiling range than gasoline, permitting uncondensed vapors containing gasoline hydrocarbons to p ass overhead through line 39, to condenser 40, whence uncondensed gaseous material and condensate pass to receiver tank 38, in which the gasoline is subsequently separated from the fixed gases and any water condensate, line 38x being gas outlet, line 54, to withdraw gasoline from the system, and line 4l, for withdrawing Water condensate.
  • Some of the gasoline condensate may be run back by pipe 43, into the upper and lower parts of tower 5, to act as a refluxing agent.
  • Ammonia from any suitable source may be passed also to the upper part of tower 5 by valved line 1411i.
  • Hydrogenous gas composed of compounds containing or yielding hydrogen under cracking conditions e. g., steam
  • lubricating oil stock may be withdrawn from a lower pan such as I9, through line 20 or lfrom a lower part of tower 5, to be further refined.
  • a lubricating oil stock it is desirable not to introduce high temperature cracking products from tower 5 into tower 3, below partition 3x, or to reduce the quantity of such products thus introduced.
  • Any solid materials, heavy tar, or sludge that may drop to the base of towers 3, 5, or 30, is preferably drained from the system by valved lines 45, 46, and 53, respectively.
  • a sediment trap 24, may be provided in line 23, for further removal of such materials.
  • the preconditioning and fractionating tower 3 was conceived with the idea of forming from Ia plurality of stocks including initial uncracked charging stock, increased quanti-ties of cracking stock which can contain recycle stock in such a purified condition as to be ,close lto virgin oil quality for high temperature cracking without an appreciable amount of coke formation.
  • Tower 5, and its appurtenances provides a means for obtaining a high quality composite reflux fraction or a high quality and puried composite reux fraction containing recycle stock which form the stream containing insuiciently converted products higher boiling than gasoline passed into the preconditioning and selective fraction-ating tower 3.
  • Tower 30, is equipped to obtain and increase stripping of converted products.
  • Coil 9 provides for the moderate splitting of heavy fraction of the charge oil and of reflux containing heavy recycle stock to condition or recondition such oils into oils which are bettersuited for high tem- Iperature cracking.
  • the contact mass also may be'Inaint-ained in-an active condition for a prolonged periodl by thepresence of controlled small amounts of regenerative agents; e. g., steam, air, carbon dioxide, oxygen, or oxygen compounds, etc., mixed With the hydrocarbon- Vapor passed through the cont-act mass.
  • the size of the furnace, sizes of coils, vessels; and conditions, depend upon the capacity of .the unit plant to be operated and upon the desired yieldsi It is to beA understoody that additional heating ⁇ equipment, ⁇ cooling equipment, con-trols, pumps, meters for :measuring temperature,Y pressure, flow :and other physical or chemical changes,
  • a process-for producingxhighyield'sfof antiknock gasoline motor fuel-With negligible"- coke' formation which comprisesl distilling an initial uncracked hydrocarbonoil. charging stock in a preconditioning and primary fraction-ating zone into which ⁇ a blast of hothydrocarbons conversion products is injected' it'o' increase greatly the degree of. vaporizatiom of ⁇ saidcharging stock without. causing.' substantial cracking andl in which mixed vapors? o1"l the conversion' products' and vaporized .crude uncrackedl charging stock arefilt'ered?
  • fractienating zone to' relatively lower' crackingxtemperatures to y obtainr a moderate splitting conversion of its constituents to more-volatile products with negligible coke formation; mixing conversion products from thea'bove mentioned two heat treatments'in' a blending and' separation zone distinct fromthe preconditioning and fractionating zone, the: morehighly -heated productsV acting toincrease vaporization; passing blended vapors from said "separation zoneA to ⁇ said secondary fractionating 'zone wherein above mentioned tar free puriedcondensates'are condensed from the blended vapors after they are filtered' throughl la solid adsorbent contact mass'for revaporization in the nrst mentionedpreconditioning and fractionatingzone leavingl an overhead vapor'fraction from which4 anti-knock gasoline yis recovered, and using part ofthe products from the moderatefspli-tting conversion as said hot conversion products injected into the preconditioning andprimary frac- -tionating zone.
  • A' process for' producing yan increased yield of high' anti-knock gasoline motor fuel with negligible coke formation which comprises heating a substantiallyA tar free puriiied ⁇ composite distillatel higher boiling than gasoline and composed bothof converted and uncracked hydrocarbonsA to high cracking temperatures to con"- vert aY substantial part of its lconstituents into low boiling lvapor products including anti-knock gasoline hydrocarbons,v separately heating a less volatile oil mainly composed of uncracked hydrocarbons'to ⁇ lower cracking temperatures to obtain a moderate splitting of its constituents into'more volatile products with negligible coke formation; passing conversionl products from the above mentioned two heat treatments'through a blending zone into-a vaponseparating zone into which vapor products of the highv temperature cracking treatment are 'injected' to act as a strippingdblast" and -totimposeia circulation on residual liquids from themoderate splitting conversion which areV collected in ⁇ a highly turbulent pool in ⁇ a m-idsection of the separation
  • a ⁇ process for converting. hydrocarbon oils into relatively low boiling. hydrocarbons suitable as-motor fuel with negligible coke formation which comprises distillinghydrocarbon oils including an initial uncracked chargingstock in a preconditioning and'l primary fractionating Zone to produce residual oils and-purified intermediate condensates higher boiling than gasoline containings. cracked andv uncracked' hydrocarbons substantially free. from.
  • a process for converting purified hydrocarbon oils into relatively low boiling hydrocarbons suitable as motor fuels which comprises vaporizing in a preconditioning zone hydrocarbon oils including an initial uncracked charging stock to produce vapors and residual oils, flashing substantially tar free hot condensate higher boiling than gasoline collected in fractionating cracked vapor products into said preconditioning zone to increase the amount of vapors, passing mixed vapors of the vaporized initial charging stock and of the iiashed condensate through an adsorptive contact mass to remove any entrained tar bodies, tar and coke forming bodies, and sulfur compound impurities, fractionally condensing a puried composite cracking stock higher boiling than gasoline from thus purified mixed vapors, subjecting said puried composite cracking stock to cracking to convert a substantial part of its constituents into gasoline hydrocarbons with negligible coke formation, fractionating vapor products of the cracking to collect additional quantities of the aforementioned substantially tar free hot condensate higher boiling than gasoline for flashing into the preconditioning zone
  • a process for producing increased yields of high anti-knock gasoline motor fuel with negligible coke formation which comprises substantial- 1y vaporizing an initial uncracked hydrocarbon oil charging stock to form a volatilized fraction higher boiling than gasoline, treating said volatilized fraction with a solid adsorbent capable of removing tar forming impurities from the volatiles in said volatilized fraction, heating an unvaporized portion of the charging stock to a low cracking temperature to obtain a moderate splitting of its constituents into more volatile products conditioned for higher temperature cracking, passing products of said moderate splitting into a blending and vapor separating zone whence separated vapors are passed through an adsorptive contact mass for purification and then through a fractionating zone, fractionally condensing in said fractionating zone a puried condensate higher boiling than gasoline, forming a blend of said purified condensate with part of said solid adsorbent treated volatiles from the charging stock of similar boiling range to said puried condensate, heating said blend to a
  • Apparatus for treating hydrocarbon oils which comprises a plurality of means for heating vaporizable liquids of different characteristics at least one of which is a hydrocarbon liquid, means for applying higher heat to one of said heating means, a blending device having an outlet for the removal of the products blended therein comprising intermixed vapors and liquids and having inlet communications from each of said heating means, said blending device having a horizontally elongated cylindrical shape, means for delivering the heated products from both of said heating means tangentially into one end ofy said blending device, said delivery means and the blending chamber being so formed and correlated as to cause a whirling turbulence of the heated prod-r ucts in the blending device, and an enlarged vapor-liquid separating means into which the thus blended products are totally discharged from the outlet of said blending device.
  • Apparatus for treating hydrocarbon oils conducted in accordance with claim 8 in combination with means for passing a purifying material into said blending chamber during the turbulent movement of the heated hydrocarbon products therethrough.
  • a process for treating hydrocarbon oils which comprises heating a high boiling liquid hydrocarbon oil to an elevated temperature insufficient to completely vaporize said oil and heating a vaporizable liquid to a relatively higher temperature to convert said liquid substantially into vapor products, passing the heated oil products to a blending zone simultaneously with the injection therein of the ⁇ heated vaporizable-liquid products, at least one of said products passing tangentially within said zone and thereby effecting a whirling turbulence of the zone contents, main-

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Description

E. AQocoN FO March 18, 1941.
2,235,329 LITY oF HEAVY RACKING METHOD AND APPARATUS R TREATING A PLURA HYDROCARBON OILS FOR SUBSEQUENT C Filed Feb. 7, 1958 INVENTOR.
Patented Mar. 18, 1941 UNITED STATES PATENT OFFICE METHOD ANI APPARATUS FOR TREATING A PLURALITY OF HEAVY HYDROCARBON OILS FOR SUBSEQUENT CRACKING Ernest A. (lcon, Yonkers, N. Y.
Application February'?, 1938, Serial No. 189,136
1o Claims.
This application is a continuationy in part of my application Serial No. 67,199, filed March 5, 1936, now Patent No. 2,130,596, granted Sep-` liminary common vaporization treatment, with` the aid of hot gases, vapors, or both, in a preconditioning and selective fractionating tower, of materials having different characteristics, .as (a) an initial uncracked hydrocarbonoil charg` ing stock, such as crude petroleum oil, and/or a topped crude oil, liquefied coal products, ground coal or coke mixed with liquid hydrocarbons as a carrier, shale oil, and the like, (b) insufficiently converted hydrocarbons, such as an intermediate reflux condensate, substantially free from tarry material formed from vapors of cracking, and (c) products from a Inild heat or splitting treatment for conditioning or reconditioning heavy oils containing refractory materials, such as heavy ends of reduced crude oil and heavy reflux condensate of converted products, `for higher temperature cracking. `This preliminary treatment is carried out to form from the vaporized and unvaporized blended fractions at least two preconditioned or purified streams of material having different characteristics and boiling ranges, each stream being adapted for separate treatment under conditions selectively controlled for subsequent conversion. Thus, two streams may be led to different heating zones and subjected to different thermal treatments for a maximum conversion of the materials into high anti-knock motor fuels with a minimum formation of gas and coke.
In promoting this main object of preconditioning a plurality of .materials to obtain an optimum yield of desired products, this invention also provides for economies realized through novel features of using hot conversion products as distillation aids and in the ecient removal of deleterious substances from the conversion products. These objects and the manner and means for accomplishing them will become apparent from the description which follows.
For example, in the preliminary vaporization treatment for the formation of two or more preconditioned streams of hydrocarbon oils having different characteristics and boiling ranges there are passed at least two streams of hydrocarbons, to wit: a regulated stream of uncracked initial oil, e. g. crude oil, which is preferably preheated to below a cracking temperature, and a regulated stream of oil containing products from a previously cracked oil. Vapors from these materials are blended and increased in temperature by an added blast of vapors', preferably a blast of hot hydrocarbon products from a moderate splitting of heavy hydrocarbons at low cracking temperatures in the presence of a hydrogenous gas, e. g., steam, and 'having a temperature of about 800 F.; which blast serves a threefold purpose: (l) to increase the fluidity of materials injectedA into the tower; (2) to increase the vaporization of volatiles in the injected materials so as to releasev therefrom more lower boiling fractions without cracking; (3) to obtain a conservation of heat energy.
Connected with the said prelimnary,1pre conditioning tower may be provided purifying contact mass which is capable of removing sulfurous impurities, tar and coke forming impurities, etc. This contact mass may contain desulfurizing agent suoliv as metals or metal compounds of lthe desulfurizing type over which vapors passing to the upper part of .said tower for fractionating may pass. The metals or compounds may advantageously be mixed or bound with adsorbents such as Florida earth, attapalgus clay, fullers earth, bentonite, bauxite, and the like. The desulfurizing agentV may also be in granular form or on the surface of an inorganic carrier, e. g., granules of Portland cement, fibrous asbestos or similar materials.
VIn the preliminary tower or preconditioning and fractionating zone at least two bodies of oil `preconditioned for further processing are formed, one of gas oil type with substantially virgin gas oil quality for high temperature cracking to produce high anti-knock motor fuel with a minimum of coke formation and another for obtaining lubricating oil or for further conditioning to obtain more virgin quality cracking stock by moderate heat treatment at low cracking temperature. In leading a stream from each of these bodies to separately controlled heating zones for conversion under different thermal conditions, conversion products from both zones can be blended and further purified, if desired, and the blended vapors are subjected to common fractionation and condensation.
The pressure employed in the preliminary tow-v er is preferably low compared with other parts ofthe system, e. g. subatmospheric, especially iny rsf.
forming lubricating oil stocks, atmospheric, or less than about 10 atmospheres.
In brief, the vapor blend of cracked and uncracked hydrocarbons, comprising constituents of straight run and cracked character formed in the preliminary tower is purified and fractionated to obtain at least a highly desirable gas oil type cracking stock of lower sulphur content. A reforming stock can be condensed from the overhead following the condensation of the gas oil type fraction. The purified gas oil type cracking stock formed in the preliminary tower may be led to a cracking zone to be cracked. at about 900 to 1100 F., at a superatmosphericpressure, or be blended with more recycle stock for cracking at about the same pressure and temperature conditions. Heavier fractions and unvaporized oil formed in the preliminary tower make upA matev rials which can be used to refine into lubricants or be led to the separately controlled moderate heating zone to obtain more conditioned, productsfor, blending with the gas oil type fraction beforeY or after the high temperature cracking of saidgas oil type fraction. This moderate heating treatment of oils higher boiling than. gas oil is carried outk at about 700 to 850 F., under pressure, with lowered temperatures if a catalyz'ing contact mass is used, and preferablywith the aid of a hydrogenous gaseousagent, e. g. steam, to obtain mainly a moderate splittingof its constituents.
In addition, this invention contains improvements inrenhancing the virginl qualities of distillates to be condensed from vapors containing partially converted recycle stock and straightrun cracking stock constituents and for enhancing the yields of such vapors for obtaining increased yields of purified fractions for high temperature cracking with a minimum coke formation. In particular, attachments to the fractionating towersgive this improved purification and a novel use, of high temperature cracking products in forcing vaporization olf more moderately cracked oils with increased stripping of volatiles to enhance the yields.
The process will be described in conjunction with the accompanying, drawing in which Fig. 1 is a diagrammatic representation of apparatus for effecting one embodiment of the process, and Fig. 2, is an isometric drawing of the blending cham-ber.
Referring to the drawing, Fig. 1, theV charging stock, for example, a crude oil, flows through pipe I through heat exchanger 2, and similar heat exchanger 2x, to be thereby heated to a temperature of about 400 to 700 F. The chargingstock thus preheated is flashed into the bottompart of the lower section of the preliminary tower 3 forpreconditioning and fractionating. Simultaneously, there is passed into said tower 3, by valved lines 6 and/or 4 and 6 hot reflux condensates from tower 5, these condensates having a temperaturein the vrange of about 400 to 700 F., and containing insufliciently converted products higher boiling than gasoline. A lighter and purer fraction led from above a partition a: in tower byline 4` is preferably led into, tower 3 above partition 311:.l These condensates in passingsfromzthe tower, generallyrhavinga. higher` pressure, into the lower pressure zone in tower 3 will flash into tower 3 with a substantial liberation of vapors. The unvaporized portions of the hotzcondensates from tower 5 and fromthe crude oilztpassby; gravity countercurrent inV direction tolvapors inttowerV 3; these vapors including, be-
sides the volatiles from the ashed condensates and crude oil, gaseous products from the blast of materials injected through jets 'I, connected by pipe 8, with a heating coil 9, in the convection section of furnace K, which coil is termed the conditioning and reconditioning coil and in which the heaviest fractions formed in tower 3, are heated to low cracking, temperatures. By this means, hot' products fromy coil 9, hot reflux condensate products from tower 5, and preheated crude oil components are mixed and jointly vaporized in the crude vaporizing section of tower 3, thedegree ofivapori'zation being increased with a; conservation of heat energy, the fluidity of the bodies` lbeing increased, and a vapor blend being produced under conditions conducive to read;r purification and formation of a high quality cracking stock distillate. If desired, vapors from the crudeoil vaporizing section of tower 3, below partition 3x, may be passed to the fractionation section above partititon 3x, through apurifying agent I2,via valvedpipe; I0, for sulphurous and tar'forming material removal, I5 beinga by-pass for the vapor if purification is not necessary, and apreiluxing andcoolinglagent may be injectedin the fractionating section. by line I4, from anyl suitable. source,r for example, tank I3 such as shownand. ammoniaby. valved line |4111. Light gasoline-constituent. vapors pass .upwardly in tow- I er; 3,` to be led overhead by pipe I6, to condenser II, thenceto receiver I3; Part of the. condensate in receivenIS, canbe led byline, I8, to storage or be passed; byline, I8:L',1to. join materialsundergoinghighltemperature cracking inthe section of the. multi-coilsystem in. furnace K, receiving the mostV heat, e. g. coil 9x. Water from receiver I3' 'is withdrawn,=by line 4l. A stream of heavy nap'hthafraction lfrom pan.2I, may be added by line 2l;c, to the gasoline. stream passed by line l8r4 to, coil 19m; or may entirely replacesaid gasoline streamin |81', or may basent to storagebyl line4 51| Apreconditionedand purified distillate of about gasoil yboiling range, with substantially virgin gas oil'N quality formed: above parition 31, disposedk withintower 3, isdrawn off to be passed by valved linef44; and; pi.z.rnp.22:1:;toV the hightemperature cracking coil 9x, wherein such oil is; heated preferably` under: a. superatmospheric pressure of about from 5` to 50. atmospheres and to `an antiknock gasoline formingv cracking-,temperature of.
aboutz900to 1100-F., for a periodto obtain substantialconversion of the oiltreated into gasoline hydrocarbons.
Preconditionedresidual fractions higher boiling 3, and .for a timeto obtainonly a small amount.
of splitting yofthe hydrocarbons... Heavy distillate collected in pan I9 below'partition 3a: of the tower 3.may. be i withdrawn separately as lubricantY stock: isdesired. Water or steam from any suitable. source is passed through pipe 48, into superheating steam coil 49, then, as superheated steam passes-Sinto themoderately heatedv coil 9,
in which said residuals oil fractions are treated. The steam may be superheated in coil 49, with reducing gases such as natural gas, xed gas from the cracking process etc.
The heating coils 9, 9.1:, and 49, are disposed in furnace K, having a burner B. This furnace is represented as being of a type which has a bridge wall 50, forming a radiant heat section in which coil 9m, is mainly located. Leaving coil 9, the products of the moderate thermal treatment are preferably divided into two controlled streams under regulated pressure, one of these streams may pass through pipe 36, into a Iblending zone 31, wherein such products are blended with cracked products from coil 91:, passed into this blending zone through pipe 34, the discharge of materials into this zone being under eXpansio-n. The other stream passes through pipe 8, and discharges with expansion into the lower part of tower 3, through spray 1.
Fig. 2 illustrates by isometric drawing the method in which the low temperature split products of coil 9 of the furnace are forced into circulation under great turbulence by the high velocity of the products from coil 9x that have been cracked under pressure and temperature cracking conditions higher than the said products of coil 9, and which are passed into the blending chamber tangentially through pipe 34 to provide perfect mixing, circulating and turbulent movement with improved conditioning of both products. Provision can be made for the addition of sulfur absorbent agents in a iiuid form to blending zone 31, as by pipe 28 and the turbulent action within said zone results in more effective desulfurizing interface contact. The pressure employed in the blending zone 31, and the following separating tower 39, will be less than the pressure in the heating coils 9, and 9m, but preferably greater than the pressure in tower 3.
Leaving the convection heated section of coil 9x, the cracked products are passed entirely by line 35 into the lower part of separator 39, or partly thereto and partly by pipe 34, into the blending zone 31. Chamber 31, discharges into the vapor separating tower 35, which is specially equipped at its midsection with a means 33, and 32, designed for retaining a pool of liquids in heated condition and in a state of high circulatory motion and turbulence induced largely by vapors and gases arising by upcomers 21, from the lower part of tower 39, the circulation being guided by the walls of the vessel 30, and cylindrical projection 32. Residual liquids retained by means 33, tend to drop down outlets such as downcomer pipes 29, indicated, and to pass countercurrent to rising hot vapors in the lower part of tower 30, where they are subjected to a further stripping action, and nally the stripped residues collect in a lower pool of liquids, which is cooled by the injected cool fuel oil, through line 52 which may be a portion of the residual withdrawn by line 53, through cooler 54. This novel arrangement serves to increase greatly the yield of vapors to be passed fro-m separator 30, to fractionator 5, by pipe 3l. Hot gas oil from line l8r, passed by line 42, into the upper part of tower 30, aids in knocking down tar and developing a blend of vapors of cracked and uncracked hydrocarbons.
Vapors from the separation zone of tower 30, pass overhead by line 3|, to enter the lower part of lower section of tower 5, in which the vapors may be made to pass through conventional trays, or the like, and relatively cool reuxing oil, for
example, a gasoline condensate passed by pipe 43, from receiver 38, to condense out a heavy gas oil fraction. Light hydrocarbons remaining in the vapor phase including gasoline, in the lower part of tower 5, may be passed to the upper part of said tower 5, for further fractionation, by
valved line 10x, through an adsorptve contact mass 121:, which may be similar in composition and function to purifying contact mass l2, previously described, especially if contact mass l2, is not used, Ix being a by-pass for the vapors if purification is not necessary. In the upper part of tower 5, above partition 51:, the vapors led thereto from below partition 5x, are further fractionated to form a reux condensate of higher boiling range than gasoline, permitting uncondensed vapors containing gasoline hydrocarbons to p ass overhead through line 39, to condenser 40, whence uncondensed gaseous material and condensate pass to receiver tank 38, in which the gasoline is subsequently separated from the fixed gases and any water condensate, line 38x being gas outlet, line 54, to withdraw gasoline from the system, and line 4l, for withdrawing Water condensate. Some of the gasoline condensate may be run back by pipe 43, into the upper and lower parts of tower 5, to act as a refluxing agent. Ammonia from any suitable source may be passed also to the upper part of tower 5 by valved line 1411i.
Hydrogenous gas composed of compounds containing or yielding hydrogen under cracking conditions, e. g., steam, may be passed through superheating coil49, into either or both of the heating coils 9, and 9m, for their benecial eiect of lowering coke formation and moderating the cracking, this being specially useful in coil 9x.
When lubricating oil is desired, lubricating oil stock may be withdrawn from a lower pan such as I9, through line 20 or lfrom a lower part of tower 5, to be further refined. To obtain a lubricating oil stock it is desirable not to introduce high temperature cracking products from tower 5 into tower 3, below partition 3x, or to reduce the quantity of such products thus introduced.
Any solid materials, heavy tar, or sludge that may drop to the base of towers 3, 5, or 30, is preferably drained from the system by valved lines 45, 46, and 53, respectively. A sediment trap 24, may be provided in line 23, for further removal of such materials.
The preconditioning and fractionating tower 3, was conceived with the idea of forming from Ia plurality of stocks including initial uncracked charging stock, increased quanti-ties of cracking stock which can contain recycle stock in such a purified condition as to be ,close lto virgin oil quality for high temperature cracking without an appreciable amount of coke formation. Tower 5, and its appurtenances provides a means for obtaining a high quality composite reflux fraction or a high quality and puried composite reux fraction containing recycle stock which form the stream containing insuiciently converted products higher boiling than gasoline passed into the preconditioning and selective fraction-ating tower 3. Tower 30, is equipped to obtain and increase stripping of converted products. Coil 9, provides for the moderate splitting of heavy fraction of the charge oil and of reflux containing heavy recycle stock to condition or recondition such oils into oils which are bettersuited for high tem- Iperature cracking.
The purifying vessels I2, and 12x, attached to towers 3 and 5, respectively, contain purifying Contactl masses of adsorptive an'dor absorptive activity' in removing'imp'urities such as entraine'd tarry bodies; tarV and gum'v forming bodies, and sulfurous impurities; Such V masses mayv contain sulfur combining met-als or metal oxides, e. g. meta'lsvof the iron group, and metals of the-second groupy of the Periodic system' and such ma- .terialsV combinedwithclaysl` orl adsorbent earths as previouslyexplained.- Several of such'v vessels can `beconnected in parallel withl eachk fractionating'tower lto provide for alternate', use' of the vessels while oneor others lare d isconectedr from the hydrocarbons'vaporl stream for regeneration y by regenerative agents, such as oxidizing gas,
etc. By-passesY I\and l5 `are-provided so'th'at any essential :amount of vapors can be purified in* either of these puriiicationzones. The contact mass also may be'Inaint-ained in-an active condition for a prolonged periodl by thepresence of controlled small amounts of regenerative agents; e. g., steam, air, carbon dioxide, oxygen, or oxygen compounds, etc., mixed With the hydrocarbon- Vapor passed through the cont-act mass.
The size of the furnace, sizes of coils, vessels; and conditions, depend upon the capacity of .the unit plant to be operated and upon the desired yieldsi It is to beA understoody that additional heating` equipment,` cooling equipment, con-trols, pumps, meters for :measuring temperature,Y pressure, flow :and other physical or chemical changes,
and'other conventional equipment of similar types well-known inV the -art may be used where desirable. y
Although the heretofore described method covers in detail a preferred mode of operation, the
system may .be varied in accordance with my invention and I do not Wishto limit the apparatus and operation-described.
Having. described my' invention, the method and apparatus of carrying it intopractice, it is to be understood thait-modincation and changes may be made provided! they do not depart from the scope of :the invention and the following claimscovering thelinvent'ion.
I claim:
1`. A process-for producingxhighyield'sfof antiknock gasoline motor fuel-With negligible"- coke' formation which comprisesl distilling an initial uncracked hydrocarbonoil. charging stock in a preconditioning and primary fraction-ating zone into which `a blast of hothydrocarbons conversion products is injected' it'o' increase greatly the degree of. vaporizatiom of` saidcharging stock without. causing.' substantial cracking andl in which mixed vapors? o1"l the conversion' products' and vaporized .crude uncrackedl charging stock arefilt'ered? through av solid' adsorbent `contacty mass which removes tar and coltevr forming impurities, .thenfractionatedto form1 composite tar freel oondensates higher boiling. than gasoline cornstituents,` collecting in.` a `seco'ndary fractionatingfzone other tar free; puriiedfc'omposite condensates-including conversion products and-havheatingafportionofheaviervresidualoils produced inl` theV preconditioning and? fractienating zone" to' relatively lower' crackingxtemperatures to y obtainr a moderate splitting conversion of its constituents to more-volatile products with negligible coke formation; mixing conversion products from thea'bove mentioned two heat treatments'in' a blending and' separation zone distinct fromthe preconditioning and fractionating zone, the: morehighly -heated productsV acting toincrease vaporization; passing blended vapors from said "separation zoneA to`said secondary fractionating 'zone wherein above mentioned tar free puriedcondensates'are condensed from the blended vapors after they are filtered' throughl la solid adsorbent contact mass'for revaporization in the nrst mentionedpreconditioning and fractionatingzone leavingl an overhead vapor'fraction from which4 anti-knock gasoline yis recovered, and using part ofthe products from the moderatefspli-tting conversion as said hot conversion products injected into the preconditioning andprimary frac- -tionating zone.
2.' A' process for' producing yan increased yield of high' anti-knock gasoline motor fuel with negligible coke formation, which comprises heating a substantiallyA tar free puriiied` composite distillatel higher boiling than gasoline and composed bothof converted and uncracked hydrocarbonsA to high cracking temperatures to con"- vert aY substantial part of its lconstituents into low boiling lvapor products including anti-knock gasoline hydrocarbons,v separately heating a less volatile oil mainly composed of uncracked hydrocarbons'to` lower cracking temperatures to obtain a moderate splitting of its constituents into'more volatile products with negligible coke formation; passing conversionl products from the above mentioned two heat treatments'through a blending zone into-a vaponseparating zone into which vapor products of the highv temperature cracking treatment are 'injected' to act as a strippingdblast" and -totimposeia circulation on residual liquids from themoderate splitting conversion which areV collected in `a highly turbulent pool in` a m-idsection of the separation zone for forced'vaporization, passingvapors from the separation zone to a fractionating.zonewhere a substantially tar free purified distillate higher boiling vthan gasoline'is condensed', and using a portion of said distillate from said fractionating zone. to makeup the tar free -composite distillate heated to high cracking temperatures.
3; Alproce'ss in accordance with claim 2, in which saidsubstantially tar free distillate formed in said fractionation zone is condensedl from vapors which h'av'e been purie'd by passage through an alosor'ptive solidr absorbent contact l'naSS.
4. A` process for converting. hydrocarbon oils into relatively low boiling. hydrocarbons suitable as-motor fuel with negligible coke formation, which comprises distillinghydrocarbon oils including an initial uncracked chargingstock in a preconditioning and'l primary fractionating Zone to produce residual oils and-purified intermediate condensates higher boiling than gasoline containings. cracked andv uncracked' hydrocarbons substantially free. from. tar forming .and sulphurous impurities; heating a portion of'said residual oils at low cracking temperatures to moderatelyl split its constituents into more volatile products With negligiblev coke formation, commingling such products in` heated condition from' the-thus treatedA residual oilsowith the oils undergoing distillation in the"pr'econditionin'gi and primary fractionating zone to increasethevaporization, passing vapors of the cracked and uncracked hydrocarbons formed in said primary fractionating zone through a solid adsorbent contact mass capable of eliminating tar forming bodies prior to condensation of said intermediate condensates from these vapors, subjecting said intermediate condensates to cracking at temperatures and pressures higher than those imparted to the residuals subjected to moderate splitting to convert a substantial part of the condensates into gasoline hydrocarbons, separating vapor conversion products of the thus treated condensates from less volatile tarry liquid products, fractionally condensing from the thus separated vapor conversion products a substantially tar free condensate in a secondary fractionating zone, passing the tar free condensate thus formed in said secondary fractionating zone into the preconditioning and fractionating zone where said condensate is revaporized by purified vapors passed through said solid adsorbent contact mass to increase the amount of intermediate condensates composed of cracked and uncracked hydrocarbons formed therein.
5. A process in accordance with claim 4, in which the moderate splitting of residual oil at low cracking temperatures is carried out in the presence of a gaseous hydrogenous compound for moderating the splitting and inhibiting coke formation.
6. A process for converting purified hydrocarbon oils into relatively low boiling hydrocarbons suitable as motor fuels which comprises vaporizing in a preconditioning zone hydrocarbon oils including an initial uncracked charging stock to produce vapors and residual oils, flashing substantially tar free hot condensate higher boiling than gasoline collected in fractionating cracked vapor products into said preconditioning zone to increase the amount of vapors, passing mixed vapors of the vaporized initial charging stock and of the iiashed condensate through an adsorptive contact mass to remove any entrained tar bodies, tar and coke forming bodies, and sulfur compound impurities, fractionally condensing a puried composite cracking stock higher boiling than gasoline from thus purified mixed vapors, subjecting said puried composite cracking stock to cracking to convert a substantial part of its constituents into gasoline hydrocarbons with negligible coke formation, fractionating vapor products of the cracking to collect additional quantities of the aforementioned substantially tar free hot condensate higher boiling than gasoline for flashing into the preconditioning zone wherein said condensate is distilled in contact with the purified mixed vapors which have passed through the adsorbent contact mass.
7. A process for producing increased yields of high anti-knock gasoline motor fuel with negligible coke formation, which comprises substantial- 1y vaporizing an initial uncracked hydrocarbon oil charging stock to form a volatilized fraction higher boiling than gasoline, treating said volatilized fraction with a solid adsorbent capable of removing tar forming impurities from the volatiles in said volatilized fraction, heating an unvaporized portion of the charging stock to a low cracking temperature to obtain a moderate splitting of its constituents into more volatile products conditioned for higher temperature cracking, passing products of said moderate splitting into a blending and vapor separating zone whence separated vapors are passed through an adsorptive contact mass for purification and then through a fractionating zone, fractionally condensing in said fractionating zone a puried condensate higher boiling than gasoline, forming a blend of said purified condensate with part of said solid adsorbent treated volatiles from the charging stock of similar boiling range to said puried condensate, heating said blend to a high cracking temperature to convert a substantial part of its constituents into gasoline hydrocarbons, and injecting highly heated products from said converted blend into said separating zone wherein they contact with and increase the vaporization of products of said moderate splitting.
8. Apparatus for treating hydrocarbon oils, which comprises a plurality of means for heating vaporizable liquids of different characteristics at least one of which is a hydrocarbon liquid, means for applying higher heat to one of said heating means, a blending device having an outlet for the removal of the products blended therein comprising intermixed vapors and liquids and having inlet communications from each of said heating means, said blending device having a horizontally elongated cylindrical shape, means for delivering the heated products from both of said heating means tangentially into one end ofy said blending device, said delivery means and the blending chamber being so formed and correlated as to cause a whirling turbulence of the heated prod-r ucts in the blending device, and an enlarged vapor-liquid separating means into which the thus blended products are totally discharged from the outlet of said blending device.
9. Apparatus for treating hydrocarbon oils conducted in accordance with claim 8 in combination with means for passing a purifying material into said blending chamber during the turbulent movement of the heated hydrocarbon products therethrough.
10. A process for treating hydrocarbon oils which comprises heating a high boiling liquid hydrocarbon oil to an elevated temperature insufficient to completely vaporize said oil and heating a vaporizable liquid to a relatively higher temperature to convert said liquid substantially into vapor products, passing the heated oil products to a blending zone simultaneously with the injection therein of the` heated vaporizable-liquid products, at least one of said products passing tangentially within said zone and thereby effecting a whirling turbulence of the zone contents, main-
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2615831A (en) * 1949-12-08 1952-10-28 Socony Vacuum Oil Co Inc Desulfurization of hydrocarbon mixtures with nickel carbonyl
US2924568A (en) * 1955-02-28 1960-02-09 Exxon Research Engineering Co Process for hydrodesulfurizing and subsequently catalytically cracking gas oil
US4714542A (en) * 1986-01-06 1987-12-22 Encon Associates Inc. Distillation vapor and feed mixing process
US20110036751A1 (en) * 2006-12-11 2011-02-17 Louis Edward Stein Apparatus and method for superheated vapor contacting and vaporization of feedstocks containing high boiling point and unvaporizable foulants in an olefins furnace

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2615831A (en) * 1949-12-08 1952-10-28 Socony Vacuum Oil Co Inc Desulfurization of hydrocarbon mixtures with nickel carbonyl
US2924568A (en) * 1955-02-28 1960-02-09 Exxon Research Engineering Co Process for hydrodesulfurizing and subsequently catalytically cracking gas oil
US4714542A (en) * 1986-01-06 1987-12-22 Encon Associates Inc. Distillation vapor and feed mixing process
US20110036751A1 (en) * 2006-12-11 2011-02-17 Louis Edward Stein Apparatus and method for superheated vapor contacting and vaporization of feedstocks containing high boiling point and unvaporizable foulants in an olefins furnace
US8070938B2 (en) * 2006-12-11 2011-12-06 Shell Oil Company Apparatus and method for superheated vapor contacting and vaporization of feedstocks containing high boiling point and unvaporizable foulants in an olefins furnace

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