US2039981A - Process for treating hydrocarbon oils - Google Patents

Description

May '5, 12935 E. w. REMBERT 2,039,981

PROCESS FOR TREATING HYDROCARBON OILS Filed July 22, 1952 9 Sheets-S1186?l 2 Q M INV TOR May 5, 1936- E. w. REMBERT j 2,039,981

I PROCESS FOR TREATNG HYDROCARBON OILS Filed July 22, 1952 9 sheets-sheet 's May 5, 1936. E. w. REMBERT PROCESS FR TREATING HYDROCARBON OILS Filed July 22, 1932 Hasgarn. @f W PP QP mh@ mr Hbuanom J NwfUlllllllll. mb H wruaoo .WQ/WV om I am JL f ,2 mMW/ L" N @R E O l L n l .A m,\ Ercanoz X 9 w m om Q w@ me Wd@ N Om E25 QON A No* no? Y #ON K mw .o9 +9 mo. xorzzknun WN mu-lok( @Ov Afmwrzzcnun NN r2 3 l l mm\ @Y o@ LME May 5, 1936 E. w. REMBERT A 2,039,981

v PROCESS FOR TREATING HYDROCARBON OILS Filed July 22, 19152 9 Sheets-Sheet '7 ,rf i ,Y ww: 1W. am m mm .\Nm

INVEN WW E. W. REMBERT PROCESS FOR TREATING HYDROCARBON OILS May 5, 1936. l

Filed July 22, 1932 9 Sheets-Sheet m i l M N A ow mm mN mM- NN 1L o@ HTD V m.n\

May 5, 1936.

E. w. REMBERT PROCESS FOR TREATING HYDROCARBON OILS Filed July 22, 1932 9 Sheets-Sheet 8 HHFUDBOKA INVENT [Tm E N m TIVAINI- v om mf y. .vm 4 A bu A Om ,1 m@ WAN@ FQ n V V A MNHN... 3. m Nl .|||l||||. of :MHUMIMW ||l||||\| Il: N mm i E lllllll ll IC QH www@ o\ b'il Patented Mey s,v 1,936

rnocsss Fon, raslvc maocAnBoN Ernest Wayne Rembert,

manuela, N. J., assigner of three-fourths to Tide Water Oil Company.. Bayonne, N. J., a' corporation of New Jersey Application July 22,1932, semi No. 623,911

11 Claims.

This invention relates to an improved method of treating mineral oils and similar material in continuous process, including operations in which thermal decomposition and recomposition of hydrocarbons are effected in vapor phase to produce oils or liquids containing compounds of the same or different chemical series from those treated, and more especially to producelower boilingoils and liquidssuch as motor fuel products, gasoline, and the like. A particular application of the invention is in the production of motor fuel material having .excellent anti-knock properties. The invention also relates to operations for the purpose of separating mineral oils and similar.

l5 materials into classes of constituents having dennite and predetermined boiling ranges, for the production of finished and semi-finished oils, in connection with the thermal decomposition and recomposition step.

The invention may be regarded, without limitation, however, as constituting improvements in process over an invention described in my Patent No. 1,892,534, dated December 27, 1932. The materials for which this improved process is specifically suitable are mineral oils from any source..

Such oils include crude oils land other residualcontaining material, including topped crudes such. -as crudes from which the gasolinehas been removed, and. redu 1d crudes, which include vcrudes from whichall or some of the normally*distillable` constituents have been removed, and which range from heavy fuel oils to light residues. By residual-containing material is meant oils containing or composed of high-boiling hydrocarbonsl 3 which can not readily be vaporized withoutcracking, or 'in ordinary distillation, the remainder that does not go overhead as a distillate. Distillates of any nature, such as naphthas, kerosenes, gas oils` and the like, are alsov suitable for treatment by 40 this improved process, as well mixtures of these with residual-containing materials.

The object of this invention is to provide im proveniente in process for the conversion of relatively heavy hydrocarbons, including. distillates ..45 and materials containing residuals, for the production of lower-boiling materials in` an economic and eiiicient manner. n 3 y IOne of theob'i of this invention, in common l with that of my Patentx No. 1.892,53, is to pro- 50 vide for the productionof low-boiling hydrocar bons, suitable for use as a motor fuel, from higher boiling hydrocarbons, in such amanner that vno solid coke need be formed in the-apparatus.; only a minimum amount of free carbon orlarpf black, auch 'an amount .of,free carbon \Another obiect thediighest yields of .material suitable for motor pendent on the nature of the material to be con. verted.

A further object is the production of a motor fuel containing relatively large amounts of aromatic hydrocarbons orother hydrocarbons hav- 5 ing good anti-knock qualities', for example, such as naphthenes or hydrocarbons of an unsaturated nature having similar qualities. Such a motor fuel, after suitable treatment, may be blended with .other motor 'fuels for theproduction of a 10 very satisfactory anti-knock gasoline, or may be used without -blending as an improved gasoline.

Objects of this invention are to bring the material to be converted to a temperature high enough for conversion in a relatively infinitesimal 15 time, to maintain this temperature for an optimum reaction time, and thereupon to stop the conversion reaction practically instantaneously by an intimate mixing with a cooling material such as charging stock, together with, preferably, 20 a cool oil recovered from a later step in the process, to remove in a subsequent operation any lampblack and/or heavy voil fog, and to separate out the liquid material and to deliver a clean vapor for subsequent fractionation. 25

Another object, as in my prior invention, is to control the reaction time andthe reaction temperatu'rein a very denite and precise manner, so that the extent of conversion or cracking will be thatdesired andso that tliere will b e definite 30 control of the nature of the compounds that are `formed.

of this inventionis to obtain fuelsand to limit the formation of tar and the gas loss to the least possible.`

Another object of this invention is to obtain substantially complete lconversion of distillate charging stocksinto motor fuel and gas; the amount of gas being held ata minimum.

A further object, as in my patent, is to crack hydrocarbons in such a manner thatsubstanw tially no overcracking shall take place.

vAnother object is to convert residual-'contain- 4s l ing' materials into low-boiling hydrocarbons with remarkably little production'of .tars or fuel oils.` Another object is to provide va process of improved fle'gibility of operation, to the end that Without .any change .in the construction of the equipment it will be possible to obtain motor vfuels of' various types by controlling the reaction time and reaction temperat while also can be obtainedva plurality of products, .the products not to motor fuels'.v tbe eco- 55 nomical production of'ga's oil and/or fuel'oil being contemplated. 1

J A further object is to provide improvements in rprocess with which it is possible to remove the natural gasoline from crude oil, and at the same time crack the heavier distillates contained in the crude oil. In such` an operation, the, excess heat required for the cracking step is used to supply the heat necessary for the vaporization of such gasoline,.a'nd also, if desired, heavierdistillable constituents or fractions.

to coking, plugging or any other causes.

Another object `of. this invention is to provide improvements in process suitable for the treatment of hydrogen-poor stocks, which lgive rise to the formation of lampblack when such materials Another object is to eliminate shut-downs, dus

. are converted to low-boiling hydrocarbons.

. :operation and returned to the unit, the heat.

- selected from the materials contained in a crude` 45 heated by some external means.

introduced in the form of vapor, to thedeter-l divided state, or in of a fog .ing lchamber-itself. `'I'he A specific object or objects of this invention are to insure the delivery of a clean vapor to the fractionating equipment by the wetting out and -removal of lampblack and the separation of any .entrained heavy mate Another speciiicobiect of the invention is to make theamo'unt of charging stock used for the quick cooling of the reaction product independent of the amount of cooling to be accomplished, this being made oi' liquid material obtained from a subsequent stage of the operation, material. A further object of this invention is to provide a more economical.' operation, in which gasoline contained in the tau gas formed is .ln the feed stock orl a stock withdrawn from'the n for Vthe removal of the gasoline recoveredto be supplied by the sensible heat in the reaction products. Another object of this inventionis to provide any predetermined desired boiling range tobe mineraloil, when'such a crude oil serves as raw material for the process. y

' Another object of this invention is to provide a method advantageous for thelreforming of a light distillate for the production of anti-knock gasolines and motor fuels, also to use the sensible heat ofthereaction products asa method of distilling and fractionating .an independent material such as crude or reduced crude.

A further object of the invention is to improve the process in respect to the mannerof introducing the material to be cracked and of mixing this material and the heating gas.

In general, the preferred mode of executing the invention may be summarized as follows:

The oil to be cracked is introduced in a yiinely vapor form, or in the form Y or mist, into a stream of hot and preferably non-oxidizing gas, which but is preferably hotcombustion Agases produced by the burning -of fuel and air in a closed chamberadjoining the cracking chamber, or in a portion of the crackoil and the hot gas are quickly and intimately mixed so that the oil is suddenly vaporiaed' if in the'form of a mist' or ne articles, and thereupon quickly superheatmined, cracking temperature. As a result of rapidand thorough mixing. and the large or possible by the re-circulation after cooling such liquid y v be added a col heavy y has and vapors, with mayhave beenA .theliquid .and the Iphase after. leaving the quencherand the innite surface of contact, extremely rapid transfer of heat takes place between the heating medium of gas and the oil to be treated. The mixture of hot gas and superheated vapor is maintained, or continues to be, for a definite period of time, at the predetermined cracking temperature, by virtue of continuous kpassage at the proper speed` through the cracking chamber. 'I'he length of this reaction time has as a natural factor the volume of the cracking chamber, that is to say its length and Width, and may be variedA with precision within relatively wide limits by varying the rapidity, otherwise not of absolute significance, vwith which the mixture of'l heating gas and oil vapor ,streams through the cracking chamber.

The reaction time for virtuallyall portions of the vapors to be converted is controllable withV an exactitude on the order of one one-hundredth of a second.L The reaction temperature is readily and' exactly controlled by regulating the amount and temperatureof the hot inert gas. and/or by regulating the proportion and/or the degree lof preheat of the hydrocarbon material fed-'in to be vaporized and/or superheated byV the heating mixing with a. relatively cool oil. This quenching is practically instantaneous and precludes any overcrack'ing. In general, the quenching materialconstitutes the charging stock, to which may oil obtainedfrom a later stepin the process.

Following this' quenching step, lthe resulting mixture of cooled reaction products, and any vaporized quenching oil, and quenching oil which not been vaporized, kpasses to an operation, which involves a thorough mixing of the gases a hot liquid oil, which may or may not be identical withthe oil left unvaporized fin the quenching step, A thorough and complete mixing is obtained between this hotoil and the products from the quencher by the use of spray nozzles.' Any-lampblack which may have been formed in the cracking operationl andl which in itself is.very diilicult to wet is taken out of the ABases at this point-or islargely taken out. Leaving thehot spray, the materials enter a separator which,'by changing the direction of flow of these materials a pluralityof times, and by exposing to 4them liquid 1lms,.insures the removal of any mist or particles, ofA heavy liquid or lampblackV l from the vapor and finally allows passage to a fractionatingtower of clean ',vaporand gas..

In somecases. the hot spray step may be omitted and the liquid,l gaseous and vaporous materials lfrom the quencher may be delivered directly to a louveredl separator or its equivalent. With such a separatonsumcient contact between gas andva'por can be obtained, to remove heavy liquid vparticles and carbon particles,ii."any.;l

. The material which 1ste-be' racked a'prefrably the'liqu'id material collected in anaccumulatorat' thev base oi the fractionatingtower or elsewhere, that is, material which Vis in the liquid rator, orV it may be reflux condensate material Sepa" material as will be described later. This material may be introduced in the reaction chamber in any one of three ways. It may be introduced directly through atomizing nozzles in the form of liquid, such atomizing nozzles being preferably of a mechanical type although nozzles of the steam atomizing type may also be used. Again, the material to be cracked may be introduced in the formv of vapor, and in such a case the ma-y terial Withdrawn from the fractionating tower is passed through a pipe still, after which it enters a vaporizer under reduced pressure, the vapors released passing through a separator to the nozzles of the reaction unit and the liquid material be` ing recirculated or being withdrawn as will be described in detail later. The third method of introducing material .to the cracking chamber involves the step of preheating the material to a relatively high temperature, vaporizing a portion of the material and usingthis vapor as a vehicle for the -unvaporized material, the unvaporized material being carried in the form of a nedmist or fog, from which any large liquid particles are removed by a separating step. A modification of this form of feed is one in which preheated liquid is atomized in other vapor, or in a gas, to form, after separation, a stable fog.

The gas or heating material which is used for raising the material to be cracked to the reaction temperature is preferably an inert gas, that is, one that is non-oxidizing. More especially the process employs gases produced by complete combustion of air and practically as generated, and preferably generated in the same unitvor immediately adjacent themixing and reaction unit, these gases containing substantially no uncombined oxygen and beingof a temperature upwards of at least 2500u F. In connection with some of the aspects of the invention, other suitable gases heated to a suilicient temperature might be utilized, for example, such as externally heated flue gases or externally heated fixed gases derived from the system, or similar gases obtained from other rening operations.l For a definite volume of material to be converted, the temperature of the gas determines the amountnecessary, since this gas must contain sufficient sensible heat at a high enough temperature so that when mixed with the material to be cracked the temperature of the entire mixture of heating gasvand the hydrocarbon material is that which has been determined for carrying out of the reaction. The

process permits of mixingvery hot gases with the hydrocarbons to be converted, yet without danger of detrimental local overheating, and this is an important advantage since the amount of the gases to be mixed, to be quenched along with the vapors, and to be passed through the reflux fractionating, condensing and gas separating and absorption equipment is kept as small as possible. Besides heating inert gas externally, it is possible to form hot products of combustion of fuel and air outside of the reaction chamber and introduce these in the reaction chamber.

An important step for the successful operation of the process involves complete and instantaneous mixture of the hot gas andthe material to be cracked. If the material to be cracked is fed to the reaction chamber in the form of a vapor or a mist or ne fog, as has been described, it has been found that the most 'satisfactory mix- .ing which may be obtained results from the feed4 ing of this material in the form of a thin sheet or stream, preferably a hollow cylindrical stream. The products of combustion are formed in an annular space around the path o'f this stream and,impinge radially on the material to be cracked. Such a mixing apparatus insures an intimate mixing of the heating gas and the ,ma-l terial and substantially instantaneous temperature equilibrium without local overheating. In

general, the temperature of vapor or mist or fog 'so fed should be in the neighborhood of 'Z50/850 F., the temperature b eing detennined by the refractoriness of the material; that is, if the materialcan be cracked easily the temperature at which it is permissible to feed the vapor is relativelylow.

When liquid materials are fed to the reaction apparatus, it is desirable to feed the material in the form of a thin conical sheet which flares across the stream of the hot heating gases. Y The resulting turbulence insures instantaneous mixing of the materials and immediate attaining of the reaction temperature. The mixing may be accomplished either by the use of mechanically atomizing nozzles or by steam atomizing nozzlesl or by any other suitable methodofatomization which will bring about the desired result. y

The mixture of gases and material to be cracked travelat high Velocity through the reaction chamber, the rate being dependent on the time of reaction desired.

For ordinary cracking, that is to say where conversion to lower-'boiling products is wanted but formation of aromatic or like bodies is not particularly sought, the cracking temperature may range from about 700 to about 1000 F., depending upon the material treated and the degree of conversion desired, and likewise upon the reaction time, and the reaction time may range,u 'consistently with other conditions, from a small fraction of a second up to several seconds or longer, but I wish to emphasize that the best results are obtainable with conditions adjusted to Very brief reaction times, preferably less than cause there is a reciprocal relation between thefactors of time and temperature, as I have demonstrated by passing a mixture of heating 'medium and hydrocarbon vapors from the point of commingling to the point of quenchingl so rapidly that, notwithstanding the hydrocarbons were exposed to a temperature far above the accepted cracking range, no alteration in the structure of the hydrocarbons was discoverable.

- In cracking crudes, fuel oil or the like. the cracking temperature should be adjusted to avoid the deposition. of coke or the formation of any material amount of lampblack. For the production of liquids having a low hydrogen-carbon ratio 'from such materials the cracking temperature should be above about 1050. When products of a different composition are sought, the temperature may be considerably lower.

Dependent upon the other conditions, the reaction time for the production of aromatics or other anti-knock bodies should be brief. Such reaction times are' accompanied by the best results. Reaction times that are most favorable are on the order of a fraction of a second to av yields and decreases the size of equipment reldenite reaction time, it enters the quencher,

. in the crude.

quired for a given throughput. Operating pressures in the order of about 50 pounds per square inch are economical for this process. In general, the pressure selected is a matter of economic balance vbetween yields to be obtained, the size and strength of the equipment and the cost of compressing the air and the fuel.

After the material to be cracked has been maintained at the reaction temperature for a Where it is immediately mixed with a very tine spray of relatively cold material. The mixing to be obtained must be substantially instantaneous and this is insured by the very ilne sub-division of the cooling material and the high velocity of the reaction products which impinge on and mix with the cooling material. 'I'he temperature is decreased to approximately '750 F. or as much lower as may be necessary to insure that substantially no further cracking will take place, orV

to a temperature whereasufiiclent quantity of the quenching liquid remains in the liquid phase to balance the operation., A

The quenching or cooling oil is in most cases the material to be charged to the unit. In case the amount of raw material and the cooling effect obtainable therewith are insuillcient to reduce the temperature of the products of the reaction "below the reaction range, it is my purpose, as in the preferred form of the invention, to increase this cooling eifectby the addition of cooled material from the fractionating tower, such as gas oil reflux or accumulator stock.

When crude oils are charged to the quencher, the excess heat contained in vthe products of reaction is used to distill thenatural gasoline content of the crude oil as well as the kerosene and an appreciable amount of the gas oil contained The amount of the lower boiling material distilled is controlled by the temperature maintained in the quenching step. This step also serves to preheat the material to be converted.

In the cases in which distillates serve as the material to be converted, it is advantageous to use this material to absorb gasoline contained in the gas leaving the fractionating equipment. After the absorption operation, the enriched oil is charged to the quencher and the heat contained in the reaction products serves to distill lout such gasolines. In this manner Vit is possible to recover the maximum amount of gasoline from the gaseous products of reaction and to eliminate any special distilling-step for the removal of absorbed gasoline. Gas oil redux may be taken from the fractionating tower and cooled, and before being reintroduced in the quencher, it may be used for this absorbing operation. This is particularly beneficial when crude oils serve as charging materials to the quencher, since such material is not adapted f or the absorption of gasoline from gasoline rich gas.

However, any other suitable liquid, such as i water, either alone 'or in admixture with the mn.-A

terial to vbe converted, may be used for quenching. A portion, all or none of the quenching liquid may be vaporized. Usually, at least a considerable portion of the quenching liquid emerges from the quench unvaporized, and it is usually from this unvaporized andvheated quenching material that the feed to the reaction zone is ultimately derived.

In the cracking of materials poor in hydrogen for the production of aromatic and desirable unsaturated hydrocarbons, it is important to produce light motor fuels containing relatively low percentages of hydrogen and to avoid as far as possible the production of ilxed hydrogen r hydrogen-rich gases or liquids, since the formation of these from low-hydrogen materials necessitates the concomitant formation of large amounts of lampblack. By maintaining a temperature which favors the recomposition of the cracked constituents to form benzol and similar aromatic compounds, the amount of lampblack can be much reduced.

A speciiic novelty of this invention is the step of insuring the removal of lampblack from the material which has been cracked. In the cracking of heavy hydrocarbons poor in hydrogen for the production of low-boiling hydrocarbons, it is generally true that carbon will be formed since all low-boiling hydrocarbons, whether produced by decomposition or decomposition and recomposition, must contain a certain amount of hydrogen. When such materials poor in hydrogen are cracked, the formation of low-boiling hydrocarbons may necessitate the formation of some free carbon which appears in the reaction products in the form of lampblack. This material is always found in a very nely divided form and, as'I have discovered, is very diiiicult to Wet with oil and remove from the vaporous and gaseous mixture lobtained from the reaction chamber. Unless a step in which these reaction products are treated for they removal of lampblack is introduced in the process, it is virtually impossible to deliver vapor to the fractionating step which is clean and which can be fractionated for long periods of time without causing plugging of the column due to deposited carbon. I have found' that carbon or lampblack suspended in the products of the cracking reaction can be removed by carbon is wetted and any ne droplets of heavy hydrocarbons are aggiomerated, so thatv it is relatively easy to separate these from the vapor and deliver the` vapor to the fractionating step free from any materials which would tend to interrupt the continuity of the operation. The liq` uid oil which is used for this scrubbing operation is the oil which accumulates at the base' of the fractionating tower or elsewhere. This oil is practizally identical with the oil which remains unvaporzed in the quenching operation, sincev no heat is added to or withdrawn from the oil in passage from the 'quencher. The temperature of the oil so introduced is substantially the same as the temperature obtained in the quencher. Even in the operation to be described later, in

which the gas oil reflux from the fractionating droplets of. heavy unvaporized material, wet particles of lampblack and similar materials, which, if allowed to enter the fractionating column withoutfa previous separating step, would cause diiliculty in the operation. An additional novelty in this improved processinvolves the step of separating such materials from the vapor. The separator is preferably one containing louvers, which will insure a very tortuous passage for the mixture of gases, vapors and liquids as it passes through the separator so that the material to be removed as liquid will impinge on these louvers and agglomerate. 'I'hese louvers are preferably arranged in banks so that they can be easily. r'emoved from the side of the separator for cleaning when such is necessary. From the separator a clean vapor is delivered to the base of the fractionating tower so that subsequent fractionation of the vapors may take place without any interruptions in the process. The removal of any liquid particles also insures a clean gas oil on the lower plates ofthe fractionating column. In some forms of this invention, this gas oil is withdrawn through reflux coolers to be recirculated to the quencher and by preventing, any residual material from being carried up into the tower by the vapors, the operation of the cooling equipment used on the gas oil will be improved and higher heattransfer rates will be obtained since the transfer surface will not become fouled.

The various matters which constitute this invention will be apparent in the detailed description which follows.

In the accompanying drawings, forming a part hereof:

Fig. 1 is a vertical longitudinal section of one form of cracking unit with appurtenant apparatus;

Fg..2 is a similar view of another form of cracking unit, parts being in elevation and the piping for supplying the feed nozzles being .illustrated schematically;

Fig. 3 is a cross-section on the line 3-3 of Fig. 2;

Fig. 4 is a cross-section, on a the line 4-4 of Fig. 2;

larger scale, on

Fig. 5 is a fragmentary longitudinal section on l a still larger scale through one of the feed nozzles shown in Figs, n 2 and 4; and

Figs. 6-11 are schematic views illustrating different forms of systems for carrying out the invention. l

The cracking unit, two forms of which are illustrated, -is designated generally by the reference character A.

The form shown in Fig. 1 is adapted for liquid feed, vapor feed or fog feed, by substitution of appropriate nozzles. The unit is encased 'in a metal shell 2, which is lined with thick walls 3 of refractory and heat-insulatingmaterials, enfA closing a combustion chamber 4, a mixing chamber 5, and a reaction chamber or tubl` 6. The mixing chamber may be considered as part of the reaction chamber. It is preferably enlarged in order to keep the hydrocarbon material, more particularly when it is introduced in liquid phase, from striking and coking on the Walls, and when -thus enlarged its forward portion 'l is contracted on a slope to join the reaction" tube.

The combustion chamber is located in the entrance end of the unit, and is'separated from the mixing chamber by a refractory bridge wall 8 containing a central. narrow-'edge orifice 9.

A wide entrance I at the back of the Wall converges to this orice to contract thestream of the hot combustion gases and increase their Velocity as they pass from the combustion chamber to the orifice. Refractory filling II at the back of the mixing chamber is formed to provide reversely ilaring surfaces extending outward and forward to the walls which surround the largest diameter of the chamber. The flaring ends of the mixing chamber eliminate eddy or back-flow regions, which would tend to cause deposition of carbon. Since irregularities in the operation of the system can not always be avoided and since some materials are particularly rich in carbon, the reactionor mixing chamber may be provided with removable plugs I2.

One or more burners I3 are carried by a rear head I3a and deliver the mixture of air and fuel, the latter being preferably gas, into the combustion chamber. Pipes I4 and I5, provided with regulating valves I6 and Il, conductthe air and fuel gas under suitable pressure, the air and fuel are mixed in accordance with known practice and the mixture is supplied to the burners as indicated.

One or more nozzles I8 introduce the oil as liquid, vapor or fog into the rear .portion of the reaction or mixing chamber. This nozzle may be disposed in various positions, but in the particular construction being described it is located in or near the orifice 9 and is designed to project a conical sheet or spray of the vapor or liquid across the stream of hot gas, the abrupt intersection of the streamzresulting in a quick and uniform mixing, with quick vaporization and/or superheatlng of the hydrocarbons to the converting temperature. In the case of liquid feed, known mechanical atomizer nozzles of the whirling or centrifugal type are suitable. The supply line I9 leading to thev feed nozzle mail7 have a regulating valve 200, or the amount of materialI that is fed may be controlled by other means.

A thermo-couple 45 held in a plug I2 projects into the reaction chamber, to afford a reading of the temperature therein.

Connected directly to the shell at the outlet .end of the reaction chamber is a small quenching chamber20. This chamber contains one or more spray nozzles 2I of such character and disposition as to disperse quenching liquid in finely divided form, in intimate and thorough contact with the entirety of the issuing mixture of gas a'nd vapors, or as they may be termed for convenience, the reaction products. Mechanical atomizing nozzles of the centrifugal type are preferably employed in the quencher.

' From the quenching spray, the reaction products and the unvaporized quenching liquid pass to scrubbing and separating 'apparatus forming part of the present invention. The precise form, constitution and arrangement of this apparatus are susceptible of modification, but in the preferred embodiment a vertical cylindrical section `2 is connected directly to the bottom of the 23, which are supplied with the hot oil by piping 24. This treatment Wets any particles of lampblack that-may still be suspended in the gaseous,.-

and vaporous reaction products after they pass the quench, and causes some droplets of liquid hydrocarbons to coalesce.

The materials next pass to a separator` 25, which is preferably connected directly beneath the spray scrubber section. This separator comprises a much enlarged chamber in which the velocity of travel of the mixture is materially reduced so that droplets of heavy hydrocarbons' resulting from either the quenching or the vscrubpromoted in various ways, but the most effective apparatus for this purpose is one which compels the materials to change their direction of flow repeatedly inconilned spaces, while presenting an extensive amount of surface on which the liquid portions can gather together and entrap carbon Particles. l

To this end the separator chamber is preferably equipped with banks of reversely inclined louvers 28, which divide the interior into .zigzag channels or narrow communicating interspaces. For the purpose of cleaning, the banks oi' louvers are preferably made removable.

I'he final separation of the body of liquid on the one' hand and the clean vapors and 'gases on the other hand may be effected adjacent this separator, and the liquids and gaseous uids may be conducted oif separately to an accumulator and to fractionating equipment, respectively. Economy in construction, however, is to be realized by constructing a liquid accumulator tank 21 at the base of the reflux fractionating colunm 28, as shown in the schematic views, in which event all the liquid, gases and vapors, already separatedl as far as removal of fog and lampblack from the lgases and vapors isconcerned, are conducted through a large pipe Il to said tank.

Before describing the system -as a whole, in its several embodiments, .the form of mixing and reaction unit shown in Fiss. 2 and 3 will be taken up. This construction is particularly well adapted to heating and converting material which is fed in the form .of either vapor or fog. As in the other example, the unit is built of refractory. and insulating material l inside a metal shell The combustion chamber I2 built in the entrance end of the unit surrounds a mixing tube I3 built of material such as carborundum brick inthe form of a checker-work. This tubular checkerwork may be supported at the middle in a bridge wall Il, so that two rings of checker brick are provided at opposite sides of the wall. One or more vapor or fog feed nozzles 3l, supplied through pipes 5i, for introducing the material to be converted, are disposed inline withv the mixing tube, being supported in a removable rear head 31. The hydrocarbon vapor, or the j exceedingly nely dispersed hydrocarbon liquid carried in vapor or gas, is consequently delivered at high velocity, and as it passes through the mixing' tube this stream is abruptly inter- .sected' by streams of the hot combustion gases pouring inward through the Openin' in the checkerwork. Maximum turbulence and very rapid mixing and superheating and/or Vaporizing of the material is the result. In both types of mixing, heating and reaction unit, the com.

bustion chamber is carefully designed to insure complete combustion before the hot combustio products encounter the hydrocarbons.

'Ihe burners (Fig. 3), supplied byvalved air and fuel pipes Il, Il, open transversely into the combustion chamber I2, preferably from opposite sides, and preferably so' disposed that their products impinge against surfaces of the bridge wall Il. vThe highest possible velocity is maintained on the combustion gases consistent with the permisslble pressure-drop in these gases as they enter the mixing tube or chamber, and the internal diameterof themixing tube is kept as small as 'I'he perfect mixture of the hydrocarbons in the vapor phase and of the heating gas issues from Ythe mixing tube at the reaction temperature 5 determined by the proportions, states and heat contents of the constituents that entered into the mixture, and at this temperature passes vrapidly through the heat insulated reaction chamber I2,

the volume of which, together with the rate at which the mixture is passed, determines the time during which the mixture is fkept at the predetermined temperature. From the delivery end of the mixing tube, the reaction chamber expands to a much enlarged diameter and is thereafter contracted again to a tubular portion 43, to which .thequencher is connected. The expanding and contracting zones of the enlargement of the reaction chamber are flared and tapered, respectively, on gradual slopes' or curves designed to suppress backflow or persistent eddy currents. The gradual expansion from the mixing tube prevents eddyk currents being established at this region, and by so doing minimizes the formation of lampblack. 'I'he contraction of the downstream section of the reaction chamber is advantageous, since it is in this section that thel production of a certain amount of lampblack may result from the reactions, for which reason it is f desirable tov maintain a high velocity through 3,0 this section in order to sweep the necarbon out of the reaction chamber into the quencher 20 andf thence to the scrubber and/or separator that have already been described. The enlarged section of the reaction chamber has the advantage/o! reducing the over-all length of the reaction unit. without altering the condition of rapid, continuous flow of all portions of the mixture throughout the length of the reaction zone.' If through any faulty control or functioning of some part of the system, or because of operating on material particularly disposed to carbon formation, an appreciable amount 8f carbon should be deposited in the reaction chamber, it will fall) out in expanded section, where it will not interfere with the operation. Under favorable conditions, the unit will operate indenitely without thenecessity for cleaning. If the necessity" arises, the re- .action chamber can be cleaned expeditiously and easily, on removing the plugs Il. The upper of these plugs is utilized as a holder for a thermocouple 45* for measuring the temperature', in this part of 4the reaction chamber, a-nd` another thermo-couple I5 is supported in a plug 41 in the contracted section.

'I'he vapor or fog feed nozzles ll embodiednin either form of the mixing and reaction unit are of a construction to deliver a thin sheet stream of large surface. Compactness and eifectivenes's of mixing are best served by the use of nozzles that deliver hollow tubular streams of the vapor or fog. As illustrated'in Figs. 4 and 5, a vcylindrical nozzle body." is applied/to the end of a nozzle pipe Il, and in this body there is a spider l2 which holds a forwardly projecting stem ll, to which is secured a disc M centered in theoutlet end of the nozzle body, leaving an annular oriilce 5lbetween the disc and the inner' wall of the body. v A single nozzle oi' this character will sufce, but for the plan of mixing utilized in Figs. 70 2 and 3 a considerable volume of feed with large stream surface can besecured by grouping a number of the'hollow stream nozzles in the head I1, these nozzles being preferably arranged in circular series. and the nozzle bodies being supported 75 in a refractory plug 56. 'Ihe several nozzles are supplied through a manifold pipe 51, and the individual nozzle pipes are provided with valves 58 (Fig. 2). The jets of hot combustion gases strike the group of vapor streams at right angles and from all sides, and the intermingling is exceptionally rapid.

Fig. 6 illustrates a preferred form of the complete equipment and process. In this operation the charging material is raised to a suitable pressure which may be in the neighborhood of 100 to 200 pounds per square inch by pump 60 and meets the enriched scrubbing oil passing by way of pipe 6I from absorption tower 62, which scrubbing oil has been raised to a suitable pressure equal to that mentioned above by pump 63. These two materials are mixed in pipe-58 or elsewhere, and enter quencher 20 through spray nozzles 2l, at which point they are mixed intimately with the cracked products leaving the reaction chamber of cracking unit A. Naturally, instead of mixing these two quenching materials outside the quencher, they could be supplied to separate spray nozzles in the quencher.Y The vaporized and unvaporized feed material, the products of the reaction and the heating gas pass to scrubber 22, wherein they are intimately mixed with the accumulator stock which has collected in accumulator 21 and which has been raised to a suitable pressure by pump 64 and finally atomized by spray nozzles 23 after passing through pipe 65. At this point any lampblack is wetted-out and the mixture of finely divided liquid, lampblack and vapors pass through separator 25 where louvers, vanes or baiiles of suitable construction insure the separation and agglomeration of the small liquid particles held in the vapors.

accumulator 21, at which point the liquids separate out while the vapors and gases pass upward through fractionating trays 66 in the column 28 in counter-current to the reuxing oil pumped over the top tray by pump 61. The vapors and 4gases from which the gasoil has been fractionated pass from the top plate of the tower through pipe 68 to condenser and cooler 69 and pass from lmentioned refluxing oil. 'The gas separated from the gasoline in separator 1| passes through pipe 14 to the base of tower 62 in counter-current to scrubbing oil, which may be the gas oil redux obtained on thelower fractionating trays and transferred through pipe 15 by pump 16 to the top of tower 62. Ths reflux condensate coming from the fractionating column 28 passes through a reflux cooler 11, where its temperature is great ly lowered so that 'it is cold enough to serve as the absorbing liquid in the absorption tower 62 and as part of the quenching liquid in the quencher 20. An accumulator tank 18 may be connected in the reflux offtake piping.

If low cold test gas oil is charged, it may be substituted for the reflux gas oil in the absorption tower 62.

As the cooled gas oil passes down tower 62, it'

'Ihe vapors and liquids pass through pipe 28 and enter;v

withdrawn from the base of tower 62 by pump 63 and is circulated to the quencher, as has been described.

y The material withdrawn from the accumulator 21, at the base of the tower 28 by pump 64 is split and part of it is circulated through pipe '65 and scrubbing nozzles 23, the remainder passing through pipe 88 to enter pipe still 8l where the oil is raised to a temperature onthe order of '750850 F. The pressure is reduced by valve 82 and the material enters vaporizer 83, in which enlarged zone the greater portion of material is flashed into vapor. The unvaporized material is recirculated to accumulator 21 through pip'e 84. In the case when this material is particularly heavy or tarry, or in the case when it is desired to make substantial amounts of fuel oil, it may be withdrawn through cooler 86 -as product DI.

The vaporized material leaves vaporizer 83 through pipe 81 and enters separator 88, which serves to remove any entrained liquid material or liquid formed by condensation in line 81. These materials are withdrawn from the separator through pipe 98, and may be recirculated either to accumulator 21 or to separator 25. Separator 88 is placed very close to the reaction unit A, so that the vapors pass directly to nozzles I8 or 35. After passing through this nozzle or nozzles the vapors are intimately mixed with products of combustion from the burners, after which they pass through reaction chamber 6 for the desired length of time, after which they pass through quencher 28, as has been described.

In the case when it is desired to produce large quantities of fuel oil, it is possible to withdraw such material from accumulator 21 through pipe 92 and. cooler 83 to Iform product IV. ,It will be seen that fuel oil may be produced at this point or as product III after passing through cooler 86, and in most cases it will not be desirable to produce such material at these two points but at either one or the other.

-Gas oil may be drawn off from the system at the point marked product V.

This particular flow is of great value in that it linsures continuous operation of the equipment without any difilculties due to coke formation at operation. When little or no fuel oil is withdrawn, practically all. of the charge will be converted' into low-boiling hydrocarbons. This is particularly true when distillates are charged, for in such cases, only material which can not be ultimately vaporized in the pipe still is withdrawn as tar. This `is a very small percentage of the material charged since, owing to the precision with which the reaction time and temperature can be controlled, the amount of polymeriza` tion leading to the formation of tar which occurs during the operation is very small and the production of tar may be practically eliminated. When charging residual containing materials, the fuel oil produced may also be held to a minimum since in the case where a fuel oil product is withdrawn from vaporizer 83, a definite amount of liquid phase cracking may take place in pipe still 8l, where the conditions may be held such that the heavy materials arev preferentially cracked, thus reducing the amount of tar andheavy material which can not be vaporized in vaporizer 88 and must be eventually withdrawn either through cooler 86 or cooler 83.

y In case it is desired vto feed liquid material through nozzlesl to cracking chamber 6, the plan just described may be simplified. In such a flow the material withdrawn from accumulator 21 is raised to a sumcient pressure by pump 84 and passes through line 94 directly to the nozzle |8. In this flow the pipe still 8|, vaporizer 83 and separator 88 are eliminated,` or ,bypassed, as well as the necessity for re-circulatlng liquid material to accumulator 21. As heavy material builds up in the equipment, it is withdrawn through pipe 92 and cooler 93 as a product. The remainder of .the operation is the same as that already described. 1 o

Fig. 7 illustrates a method of feeding highly atomized, unvaporized material suspended in its own vapor. In this flow the material withdrawn from. accumulator 21 is raised to a high pressure by pump 84 and passes through pipe 80 to enter pipe still 8|, where it is raised to a suitable temperature. 'I'he pressure is then reduced by valve 82, and the oil enters vaporizer 83, where the low-boiling constituents are flashed off as vapors.4 These leave the vessel by pipe |00. The liquid material which is unvaporized leaves by f pipe |0|, and the vapors and liquid, both under relatively high pressure, enter a mixing and atomizing device |02, where the liquid material is broken up more or less into a very ne mist.

'I'he atomizer discharges into a pipe |03, which admits the vapor, and vapor-home liquid particles, together with any unatomized liquid, into separator |04, which is preferably of a tangential type. Any liquid material which is not brolteny up into sufliciently fine particles is separated out and in this method the low-boiling constituents and withdrawn as liquid through pipe |05 connected to a second atomizer |08. The vapor and the suspended particles leave by pipe |01 to enter into the second mixing and atomizing device |08, where theliquid material is further broken down` and the materials are then ,delivered through pipe |08 into a separator |09, which is similar to separator |04. Any large particles of liquid which remain after atomizer |08 are separated out here and are withdrawn through pipe 201 for recirculation either to separator 28 or accumulator 21. The vapor and finely atomized liquid which has thus been classified by repeated .atomizing and separating steps passes from separator |09 directly to the feed nozzle I8 of the cracking unit. In this manner finely divided liquid of definite particle size may be carried in its own vapor and charged to the cracking reaction. This treatment prevents the possibility of large droplets entering the cracking chamber and insures a greater amount of feed in a suitable form at a definite temperature for the reaction. 'I'he description has shown a two-stage atomizing and separating treatment of the liquid material but this invention is not necessarily limited to this number .of,steps, since it is possible to use either one or more than two steps for the preparation of the liquid and vapor fog. `In other respects the operation and equipment are the same as described under Fig. 6, with the exception that no fuel oil is withdrawn from vaporizer 83. In some cases it may be desirable to withdraw heavy material from line 201 through line 208 and cooler 209 as product III. Fig. 8 illustrates` a modification which is primarily adapted for the cracking of clean materials in any one of the three methods of feed whichhas been described. Itis well ,adapted to the treatment of residual containing materials are fed to the cracking reaction and the heavy residual-containing material which might cause diillculty in the cracking step, due to polymerization and concomitant coke formation, is removed as fuel oil. In this operation hotliquid gas oil reflux from one of the lower fractlonating trays' 88 is withdrawn from the tower through a pipe ||0 and reservoir 18 and raised to a suitable y pressure byv pump 84. It passes through pipe and enters pipe still 8|, where it is raised to a suitable temperature which will be on the order of 750/850" F. 'Ihe pressure on the material is reduced after it leaves the pipe still by valve 82, and the material enters vaporizer 88, from which the vapors pass through pipe 81 to separator 88 for introduction to the cracking step. Unvaporized material is recirculated to accumulator 21 through pipes and 84. The material in the accumulator is withdrawn by pump I2 and part 'sent through pipev 85 to the nozzles of scrubber 22. Part of the gas oil reflux withdrawn from the lower plates oi' the fractlonating column is withdrawn through a cooler 11 and circulated by pump through pipe 18 over absorption tower 82, to recover gasoiene-like hydrocarbons from the fixed gases, and after being` thus enriched,

is circulated, as described in connection with Fig. 6, to join the charging stock supplied through pipe 59 to the nozzles of the quencher 20.

If, instead of crude -oil or other residual con` taining material. a distillate, such as gas oil, for example, is charged to the process, the material collecting in the accumulator 21 may be entirely suitable for use in the absorption tower 82. In that event part of this material may be pumped by pump |I2, or by another pump, through-a pipe ||4 and a cooler ||8 to the pipe 18 leading to the top oi' the absorption column 82, or the fresh feed may be pumped directly to the gas absorption tower, and thence to the quencher 28. If residual-containing material is charged to the process, it is advisable to take reflux distillate from the lower plates of the fractlonating column i 28, to serve asl the absorption medium for scrub-l bing th fixed gases and as supplemental quenching medium in the quencher 28, since in such a case the heavy material in the accumulator 21 would makem'for a diilicult absorption operation,

4on vaccount of its high viscosity at the absorption temperature. v

Assuming residual-containing material to be the charging stock, tar or fuel oil is taken out of the system at one or both of the places marked Product III and Product IV, respectively. Depending upon whether the charging stockf is a residual-containing material or is a distillate, gas

oil may be taken out of the system at` one or other of the places marked Product IV and Product V.

As was described in connection with Fig. 6, the flow may be vmodified when it is desired to feed liquid material to the mixing, heating and J reaction unit A. In such a case. pipe still 8|, vaporizer 83 and separator, will be by-passed or omitted, vand the oil will be supplied directly by pump 84 through line 94 to the atomizing nozzle of the cracking unit. Likewise, the fog feed flow which was described in connection with Fig. 7

may be substituted in this or in any other the embodiments of the process.

Fig. 9 shows a form of operation suitable for any type of charging stock. In thislcase the gas oil reflux formed in trays 88 `is allowed to fall dlrectly into accumulator 21, from which it is withdrawn by pump 84 and charged to the nozzles in l the cracking unit through anyone of the three methods of eed described;V thatds, either as a vapor. as a og or as a liquid. Part of the ma- Fig. 10 shows a modification of the improved process, which is especially adapted for the cracking of selected raw materials, such as light gas oil or naphthas. It is particularly adapted for improving the anti-knock qualities of the latter materials in' that it is possible to take a naphtha of high detonating qualities and high boiling range and reform this material so that gasolines of high anti-knock properties and suitable boiling ranges are obtained. The sensible heat contained in the reaction products of such a cracking operation are used to distill the lighter fractions from a crude oil or similar material charged by pump 60 through line 59 to the quencher 20. The material to be cracked, supplied through line H9, is raised to a suitable pressure by pump |20, passes through pipe |2| and heat exchanger |22, where it is preheated by gas oil withdrawnfrom one of the lower trays in the fractionating column. This material then passes through pipe 89 to pipe still 8 where it is raised to a temperature high enough to vaporize substantially all of the material after the pressure has been reduced by valve 82 and the material flashed in vaporizer 83. Any unvaporized material is withdrawn by pipe 84 and recirculated to accumulator 21. The

vapor leaves through pipe 8l, enters separator 83, in which any entrained liquid and/or liquid con-j,.-

densed in the line are separated from the vapors to be recycled either to separator 25 or accumulator 2l. The vapor passes to the cracking reaction, where the operation proceeds as has been described above. The reaction products enter quencher 20, and are cooled by raw material introduced by pump 6i) and pipe 53 through spray nozzles in the quencher. 'Ihis raw material is distinct from that' charged by pump |20 and is preferably a crude although other materials may be used at this point. The rest of the operation is substantially similar to that described in the other cases. Fuel oil is withdrawn by pump |25 from accumulator 21'. Part of this is used to scrub the quencher products in scrubber 22, the remainder being withdrawn through cooler |21v and recovered as a product. In case additional preheat is desired in the material charged by pump |29, it is possible to recover some of the heat contained in the fuel oil withdrawn from the accumulator, by vheat exchange in a heat exchanger |28. The gas oil withdrawn from the tower through heat exchanger |22 passes through a cooler |29 and may be withdrawn as a product. It is also possible towithdraw through a pipe |39, from one of the upper trays of the fractionating tower, material which may be a naphtha or a light gas oil, and after suitable cooling, if necessary, in a cooler |32, this may be used vwith the material charged by pump |20. Such material is only mixed with the selected stock to be cracked when its refractoriness is similar to that of the selected charging stock so that the same condi.

tions of time and temperature will give economical yields for both this material and the selected charging stock. This operation may be modiiied for liquid feed to the cracking unit, as heretofore described.

Fig. 11 shows a further modiilcation of the process which is particularlydesigned for the cracking of heavyvresidual material contained in the charging stock. Such a flow is particularly advantageous when it is desired to reduce the' yield of fuel oil to a minimum. In this ow the material in the accumulator 21 is withdrawn and raised t'o a suitable pressure by pump BI, part of it being circulated through pipe and the nozzles of scrubber 22, the remainder passing through pipe still 8l, where it is raised to a temperature which will insure the vaporization of a substantial amount of the material. After the pressure is reduced by valve 82, the material ashes in vaporizer 83, vapors are withdrawn through pipe |35 and enter the basepf the-fractionating column 28, either below the trays or above a lower tray, for fractionation in fractionating trays 66. The liquid material is withdrawn from the vaporizer by line |36 and raised to a pressure in the order of 200 pounds per square inch by pump |31. It is then introduced into the atomizing nozzles of the reaction unit through line |38. The untreatedresidual-containing material is used as aquenching agent in quencher 28. Otherwise the operation tis similar to those described above. Gas oil may be withdrawn through a cooler 11 as product V, and fuel oil or heavy tar which accumulates in accumulator 2l may be withdrawn through line 92 and cooler 93 as product IV.

In some operations suiiicient separation may be obtained in the separator 25 to insure the delivery oi clean vapors to the fractionating tower, in which event the scrubbing step (22) may be omitted.

I claim:

1. A continuous vapor-phase process for eiecting thermal conversion of hydrocarbon oils', which comprises intimately mixing the material to be converted with hot gas and thereby heating the hydrocarbons to a predetermined converting temperature, conducting the mixture of gas and hydrocarbon vapor through a reaction chamber where conversion is eilected, then immediately quenching the mixture sufliciently so that the reactions are deiinitely arrested, this being accomplished by spraying the mixture with cool oil, then spraying the mixture with hot oil the temperature o! which approximates the temperature resulting from the quench, agglomerating fog particles and separating the same, together with any lampblack, from the gases and vapors, and only after this has been accomplished passing the vapors and gases to a reiiux fractionating treatment.

2. A continuous vapor-phase process for ef fecting thermal conversion of hydrocarbon oils, which comprises intimately mixing the material to be converted with hot gas and thereby heating the hydrocarbons to a predetermined converting temperature, conducting the mixture of gas and hydrocarbon vapor through a reaction chamber where conversion is eiected, then immediately quenching the mixture sufficiently so that the reactions are definitely arrested, this being accomplished by spraying the mixture with cool oil, collecting the liquid oil part of the materials that proceed from the quenching step, circulating this hot oil and introducing it in intimate contact with the gases and vapors passing from the quenching operation, and only after this passing the clean vapors and gases to a reflux fractionation treatment.

3. A continuous vapor-phase process for effecting thermal conversion of hydrocarbon oils, which comprises intimately mixing the material to be converted with hot gas and thereby heating the hydrocarbons to a predetermined converting temperature, conducting the mixture of gas and hydrocarbon vapor through a reaction chamber where conversion is ed'ected, then immediately, by

direct and intimate contact with cool oil. quenching the mixture sudiciently so that the reactions are denitely arrested, then thoroughly spraying the eiiluent from the quenching step with hot oil and thereby wetting any particles of lampblack present in the emuent, then conducting the mixture of gases, vapors and unvaporized quenching liquid in a tortuous course until fog particles present in the vapors and gases have been agglomerated and wetted carbon particles have been caught in the liquid, then separating the vapors and gases from the liquid, and only after these steps passing the vapors and gases treatment.

4. A continuous vapor-phase process for effecting thermal conversion of hydrocarbon oils, which comprises intimately mixing the material to be converted with hot gas and thereby heating the hydrocarbons to a predetermined converting temperature, conducting the mixture of gas and hydrocarbon vapor through a' reaction chamber Where conversion is effected, then immediately quenching the mixture sudiciently so that the reactions are definitely arrested, this -being accomafter the spraying with hot oil following the quench, cooling it and re-circulating it to serve as additional quenching medium in the foregoing quenching step.

5. A continuous vapor-phase process for effecting thermal conversion of hydrocarbon oils, which comprises intimately mixing the material to be converted with hot gas and thereby heating the hydrocarbons to a predetermined converting temperature, conducting the mixture of gas and hydrocarbon vapor through a reaction chamberv Where conversion is effected, then immediately quenching the mixture to a temperature at which the reactions are definitely arrested, supplying the entirety of the charging stock, previously uriheated, to serve as part of the quenching medium, passing the quenched gases and vapors to a redux fractionating treatment, collecting the hot liquid oil that proceeds from the quenching step, deriving from this oil the feed of material to be converted, withdrawing redux from the reflux fractionating treatment, cooling this redux andrecirculating it to serve as additional quenching medium in the foregoing step.

6. A continuous vapor-phase process for effecting thermal conversion ot hydrocarbon oils, which comprises intimately mixing the material to be converted with hot gas and thereby heating the hydrocarbons to a predetermined converting temperature, conducting the mixture of gasand hydrocarbon vapor through a reaction chamber where conversion is effected, then immediately quenching the mixture sudiciently vso that the reactions are definitely` arrested, this, being M' to a redux fractionating complished by spraying the mixture with oool oil, then spraying the quenched gases and vapors with hot oil the temperature of which approximates that resulting from the quench, after which the gases and vapors are passed to a redux fractionating treatment, supplying charging stock to serve as part of the quenching medium, collecting the liquid oil that proceeds from the hot spraying step, vwithdrawing a portion of this oil, cooling it and recirculating it to serve as additional quenching medium in the foregoing quenching step, and deriving from the redux from the fractionating treatment the feed of material to be converted.

'1. A continuous vapor-phase process for effecting thermal conversion of hydrocarbon oils, which comprises intimately mixing the material to be converted with hot gas and thereby heating the hydrocarbons to a predetermined converting temperature, conducting the mixture of gas and hydrocarbon vapor through a reaction chamber where conversion is effected, then immediately quenching the mixture to a. temperature at which the reactions are definitely arrested, supplying the entirety of the charging stock, previously unheated, to serve as part of the quenching medium, passing the quenched gases and vapors to a redux fractionating treatment, collecting in an accumulator stock the liquid oil that proceeds from the quench, delivering the entire reflux from the fractionating treatment to this accumulator stock, deriving from this stock the feed oi' material to be converted, and recirculating a portion of this stock, after cooling, to serve as additional quenching medium in theforegoing quenching step.

8. A 'continuous vapor-phase process for effecting thermal conversion of hydrocarbon oils. which comprises intimately mixing the material to be converted with hot gas and thereby heating the hydrocarbons to a predetermined converting temperature, conducting the mixture of the quench, cooling this oil, passing it as an absorption agent through the absorption zone, and utilizing this oil, enriched with volatile hydrocarbons taken fromthe gases, as additional quenching medium in the foregoing quenching,v

step, wherein porized.

9.. A continuousvapor-phase process for effecting thermal conversion of hydrocarbon oils,

the volatile constituents are vawhich comprises intimately mixing the materiallv to be converted with hot-gas and thereby heating the hydrocarbons to a predetermined converting temperature, conducting the mixture of gas and hydrocarbon vapor through a reaction chamber where conversion is effected, then immediateby quenching the mixture to a temperature at which the reactions are dednitely arrested, utilizing as part of the quenching medium thecha'rging stock from which the feedolmaterial to be f converted is ultimately derived, passing the quenched mixture oi vapors and gases to a redux quenching step, wherein the volatile constituents fractionating treatment, condensing and recovering light vapors that pass from this treatment, passing the gases through anvabsorption" zone,

withdrawing reflux oil from the fractionatingr treatment, cooling this reilux oil, passing it asy an absorption agent through the absorption zone, and utilizing this enriched liquid as additional quenching medium in the foregoing lquenching step, wherein the volatile constituents taken from the gases are vaporized.

10. A continuous vapor-phase process for effecting thermal conversion of hydrocarbon oils,

which comprises intimately mixing the material to be converted with hot gas and thereby heating the hydrocarbons toa predetermined converting temperature, conducting the mixture of gas and hydrocarbon vapor through a reaction chamber where conversion is effected, then immediately quenching the mixture to a temperature at which the reactions are definitely arrested, utilizing as part of the quenching medium the charging stock from which the feed of material to be converted is ultimately derived, passing the quenched mixture of vapors and gases to a reux fractionating treatment, condensing and recoverlng light vapors that pass from this treatment, passing the gases through an absorption zone, collecting the liquid oil that proceeds from the quenching step, and recirculating at least a portion of this oil, after cooling, through the absorption zone, where it absorbs volatile constituents from the gases and thence to the vforegoing taken from the gases are vaporized.

I- 1l. A continuous vapor-phase process for effecting thermal conversion of hydrocarbon oils,

which comprises intimately mixing the material to be converted with hot gas and thereby heating the hydrocarbons to a predetermined converting temperature, conducting the mixture of gas and hydrocarbon vapor through a reaction chamber where conversion is eiected, then immediately quenching the mixture to a temperature at which the reactions are definitely arrested, utilizing as part of the quenching medium the charging stock from which the feed of material to be converted is ultimately derived, this charging stock containing low-boiling hydrocarbons, passingthe quenched mixture of vapors and gases to a reflux fractionating treatment, condensing `and recovering the light vapors that pass from this treatment, passing the gases through an absorption zone, withdrawing oil from a stage of the process after the quench, cooling this oil, passing it as an absorption agent through the absorption zone, and utilizing this oil enriched with volatile hydrocarbons taken from the gases as additional quenching medium in the foregoing quenching step, wherein said volatile hydrocarbons, together with the low-boiling hydrocarbons contained in the charging stock, are vaporized and blend with the conversion products coming from the reaction chamber. y

ERNEST WAYNE REMBERT.

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