US2209973A - Process and apparatus for treatment of fluids - Google Patents

Description

Patented Aug. 6, 1940 PROCESS AND APPARATUS FOR TREAT- I MENT OFFLUIDS Eugene J. Houdry, Rosemont, Pa., Raymond 'C. I

Lassiat, Woodbury, N. J., and GeorgeKelso,

Chester, Pa., assignors to Houdry-Process Corporation, Dover, 'Del., a corporation of Delawaren' Application January 2'7, 1936, Serial No. 61,024 20 Claims. (Cl. 196-52) other origin, natural or artificial. By way of illustration, the invention is particularly useful in the treatment of heavy hydrocarbons, such as tars and other distillation residues and gas oils, and particularly heavy or high-boiling. gas oils, which are difilcultly, vaporizable and, when vaporized, may contain entrained therewith unvaporized material such as tars, asphalts or the like,

in the form of finely divided liquid dropletsor mist. However, the invention in its broader aspect contemplates. the. treatment orv conversion of hydrocarbon fluids generally and various other fluids, especially thoselof a composite nature,

whether of similar or higher or lower boiling points or ranges.

Heretofore various methods have been pursued in thehandling and treatment of such. heavy, high-boiling materials as the residua', etc., referred to above. One method has been to pass such material at suitable superatmospheric temperature, e. g. 750 to 975 F., through a vaporizing mass which often resulted in the making of a product which is desirable as a charging stock for a cracking operation for the production of gasoline. Among the vaporizing masses employed were contact materials which are porous and absorbent and which may be practically catalytically inert or may possess mildor very slight catalytic activity, including silicates of alumina or relatively inert clayey materials of thetype'and in the molded form disclosed in PatentNo. 1,818,403 issued to 'Alfred Joseph on August 11, 1931. The charging material, such as high boiling hydrocarbon fluid, with or without a preliminary fractionation, has sometimes 5 been subjected to thermal or catalytic treatment to produce gasoline. Another method hasbeen to subject such heavy material'to a mild thermal cracking operation and then subject the resultant product to a further thermal or catalytic con- 5 version. Some such processes .have met with more or less success, but, in many instances, large formations or deposits of carbonaceous'material have commonly been encountered which tended to render inoperable the contact mass or plug 55 up the equipment; also two or more major pieces of equipment have beencommonly required in such operations We have found in our present invention that such materials "can be handled favorably with a minimum amount of equipment and without causing large or excessive deposits 5 of carbonaceous materials or other'solids,

It is an object of this invention to provide a simpleand improved process and apparatus for the treatment and conversion of fluids. Other objects and advantages of a more specific or di'f- 10 ferent nature include: (1) the separation of heavy orentrained material from fluid charging stock in the same unit of apparatus which contains the treating ,or conversion zone, ,or stated differently, in a zone through which a regeneratl5, ing mediglm' will passon its Way to or from the treating or reaction zone; (2) the reduction of thev magnitude of thejpressure'drop caused in'the passage of fluid into and through the"re'action chamber and/or the contact mass con 2 V tained. therein; (3) the maintenance of substantially uniform and predetermined temperatures throughout the depth or volume of the mass; (4) the convenient removal of condensate and/or unvaporized liquid. from the reaction zone or cham- 25 .ber Where treatment or conversion is conducted in the vapor phase; and (5) "the efficient and convenient recovery of desirable lighter fluids from heavy fluids where heavy or entrained fluids are separated fromthe stream of charging 30 stock preceding its entrance into the reaction zone, These and other objects and advantages will be further understood from the detailed, discussion which follows. l

An aspect of our invention involves intr'odu'c 35 ing a partly vaporized heavy or composite .fluid such as hydrocarbons, or a vaporized fluid having liquid entrained therein, into a reaction zone which may contain a contact mass or catalyst capable of effecting the desired treatment or transformation thereof into diflerent or lower boiling materials. Immediately preceding the advent of suchfluid into .the rea'ctionzone, it may be subjected to astep of deentrainment to remove. liquid mist therefrom, for example, in a zone subjacent to the reaction zone. In.certain cases, an inert fluid heated to a suitable temperature, e.',g. superheated .stearhfmay be introduced into the vapors,after jthe deentraining step and before they enter the reaction zone. Liquid may be withdrawn from the subjac'ent zone'or equivalent and alsoliquid condensate may be withdrawn continuously from the reaction zone, and both may be conducted to a common separator, receptacle or the like. These operations are carried out in a manner so as not to upset or deleteriously affect temperature conditions within and throughout the bed of contact mass, as will appear from the description subsequently given.

To illustrate the invention, concrete embodiments thereof are shown in the accompanying drawings, in which:

Fig. 1 is an elevational view, partly in section, of a converter or casing having a reaction chamber, together with conduits, a heater or other auxiliary equipment;

Fig. 2 is an enlarged isometric or perspective view of an element shown insideof but adjacent the lower end of the converter shown in Fig. 1;

Fig. 3 is a sectional elevation of a modification of the converter or reaction apparatus shown in Fig. 1, with the top of'the converter broken oil and showing provision for removal, of liquids which may accumulate, during operation, above the lower tube sheet of the ..cohverter;

Fig. 4 is a detail view of aportion of the lower part of the converter shown in Fig. 3;

Fig. 5 is a sectional elevation of a further modification of the converter or reaction apparatus shown in Fig. 1, differing from the apparatus shown inf-Figs. 1 and 3 in the auxiliary apparatus for injection and in the provision made for removal of liquids from the reaction chamber above the lower tube sheet of the converter, for example;

Fig. '6 is an enlarged detail view of one of the conduits which extend within the reaction chamber of the converter shown, in Fig. 5;

Fig. 7 shows, in broken away elevation, a converter such as shown in Figs. 1, 3 or 5, with the auxiliary apparatus modified to provide for recovery'of desired'products which may separate out with liquids or'itars which are drained from the bottom ofv the converter; and

Fig. 8 shows a further modification of ap'-' paratus for the removal of tar or liquid from the converter.

Referring more in detail to the drawings, in the several figures of which like reference characters denote similar parts, a heavy composite hydrocarbon material, particularly a heavy or high boiling oil such as heayy petroleum gas oil' and/or bottoms, may be Eonsidered as being treated or converted .to produce asubstantial amount of light hydrocarbons in the gasoline boiling range, for the sake of a definite illustration. I is a converter surrounded by insulation 2, the converter providing a reaction chamber 3 containing a contact mass4 and having end manifolding chambers 5 and 6, respectively. Perforated inlet conduits 'I and outlet conduits 8 extend within the reaction chamber 3 of the converter and provide for a uniform introduction and withdrawal of fluid which may be subjected to treatment by contact mass 4.

During the on-stream or reaction portion of a complete cycle of operation, the reactants, such as the heavy oil above mentioned, may be forced by pump 9 through conduit, I 0, heater ,II and elbow duct I2 into chamber 5. and against the baiile or roof-shaped member I3, which is located above and adjacent the bottom'head of the converter. An inert gaseous medium such as steam may be introduced with the charge either through valve I4 or through valve I5, or both. Ordinarily, it would be preferred to introduce the steam into the charge throughvalve I4, unless some introduction of steam through valve I5 is necessary to prevent or minimize thermal cracking in the coils of heater II. Steam passed through valve I 4 may advantageously be introduced into the coil of heater H at a point where the oil passing through'such coil and the steam are at approximately similar temperatures.

The, fluids in the stream directed against baflle I3 ordinarily arev primarily in the vapor phase, but where a heavy or high-boiling material is being treated usually there is present in the vapors ahiifitfainment of mist or droplets of tarry materials. It is often better or eyen necessary to suffer some entrainment rather than to cause undesirable thermal cracking by going to higher temperatures in an endeavor to get substantially 100% vaporization. These droplets accumulate on the inner'surfaces of the baffle I3, drain down to the bottom head of the case, and pass from the converter through line I6, controlled by valve IT, to the tar separator I8. The uncondensed vapors emerge from the baflle through its open ends and through side openings I9 therein and pass upwardly into perforated conduits I, which may be plain pipes but which are usually of the double or nested variety having perforations or openings in the outer tube of each throughout its length. Vapors or fluids pass through and in contact with the mass or catalyst 4 and leave the reaction chamber through conduits 8, entering the same through the perforations distributed along the lengths thereof. From conduits 8 the fiuidreaction products or transformation products enter manifolding chamber 6 and thence leave the converter by passing through duct 20, controlled by valve 2I, to any preferred additional treating equipment or to storage, as desired;

To insure that the reactants are and'remain in the desired state of vaporization or superheat while passing through the contact mass, superheated steam,may be admitted into admixture with the vaporous reactants through conduit 22, being distributed from the conduit through suitable perforations or openings 22a within the manifolding chamber 5. The temperature of the superheated steam may, for example, be approximately that at which it is desired to feed the reactants'to the reaction or treating chamber, or higher or lower.

After treatment of such a heavy material has proceeded for a period of time, the contact mass becomes poisoned or reduced in activity by coky, tarry or other contaminants or deposits and it becomes necessary to regenerate the mass in order to restore the efficiency of the apparatus for treatment or conversion of the charging stock. To accomplish this, the flow of reactants is stopped and steam or other inert gas passed through the equipment to remove combustible or explosive hydrocarbons and then the flow of steam may be cut off or decreased and a regenerating medium, such as air, or other oxygencontaining gas, including a mixture of air and fiue gas, passed into the converter through conduit 23, controlled by valve 24. The products or fumes of regeneration may be withdrawn from the converter through duct 25, controlled by valve 26, and may be passed to any suitable heat exchangers, eccnomizers, or other equipment, as desired. The path of flow of the regeneration medium through the reaction chamber of the converter may be the same as the path followed by reactants during an on-stream period. When regeneration is completed, as can be told from experience or can be observed from an analysis showing a falling off in the carbon dioxide content of the regeneration gases, for example, the introduction of regenerating medium is interrupted, the apparatus purged of regenerating medium by the use of steam or other inert medium, and then reactants are again passed into and through the converter to undergo, trans formation in the course of their passage. Instead of using an inert mediunupurging may be effected by vacuum. f 1

Of course, valve 2|, .and usually'valve- 21, is closed during regeneration; whereasvalves 24 and, are closed during an on-streamor conversion step. I

The tar separator I8v is provided with a lower withdrawal line28 controlled by valve 28a, and

an upper duct or withdrawal line 29, controlled by valve 29a. There is also a duct 30, controlled by valve.3lla,"providing means for fluid communication between the top or the tarseparator and the manifofdingchamber 5 of the converter. This duct '30 serves to equalize pressures between the manifolding chamber 5 and the tar separator l8 and may also serve to permit the return of light materials which have been removedfrom the converter alongwith the vtar, for example, in a state'of solution or occlusion therewith.

In'Fig. 3 the converter la is very similar. to converter l shown in Fig. 1. The tar separator'is similar to that shown in'Fig. 1, but .a plurality of ducts 3|, two only of which 'appear in the draw,- ings, extendthrough the lower tube sheet32 of the converter and serve to drainofi' condensatetars, or'other liquid which may drainto thebottom of" thefreaction chamber, orv accumulate on the upper surface of tube sheet 32. Ducts 3| drain into a" common duct 3 l a which inturn drains, into duct IGa, leading to the tar separator l8. a

In the absence of ducts 3| or equivalent, small holes may be provided in the lower tube sheet or partition to permit tar oricondensatetofdrain from the reaction chamber during an on-stream or purging operation and may serve to admit a restricted amount of air or other regeneration fluid during regeneration.

In Fig. 5, converterlb is comparable to the converter shown in Fig. 1,.but there are certain important difierences, particularly in the auxiliary equipment. Provision is made for atomization of the charge to the converter. Apparatus to accomplish this comprises members 34 .and 35,

the former providing an orifice and" the latter having a Venturi throat atpoint 35a. Reactants or charge are introduced through duct Illa, heater Ha and valve Tim-against the outer circular periphery of member '34. Steam or other inert fluid for atomization may be passed through valve 36, heater 3,1, and valve 38 through the orifice of member 34, where it picks up the charge of heavy hydrocarbons and carries them through the Venturi throat at point 35a, thereby vaporizing and atomizing them. (In place of passing through the heater 31, the steam or equivalent or a part thereof may by-pass the heater by passing through valves 49 and 50.) The stream of hydrocarbons mixed with steam passes up through the elbow duct 35 and has heavy unvaporized, entrained materials or liquids removed therefrom by bafile I3'a. Liquid-free vapors then pass from the manifolding zone 5b upwardly through the inner members of double or nested conduits ID, from which fluid is distributed throughout the height and diameter of the mass by'the perforations or openings in the outer conduits thereof.- The reactants pass through and 3 in contact with the, contact mass lb an leave the reaction chamber through conduits 8b, entering the latter through the perforations or openings spaced from each'other along the length of each. Reaction products pass" to the manifolding chamber ;6b and thence leave the converter through the passages'shown, as'previously described in connection with Fig. l.

The inserts or inner conduits of the several nested conduits 1b are open at both ends and, in addition, have one or more holes or perforations ,39 in their side walls at the lower end ofeach, adjacent tube sheet 32b. These holes'oropenings have two major advantages in the operation of the apparatus. They permit a portion of the charge to enter the near end of the annular spacesor passages between the inner and outer concentric vmembers"O'Lconduit lb, thereby to reduce-theresistance or pressure drop'w hioh the reactants encounter when sent entirely to the far endof the unit with thenecesjsity of reverse movement before distribution into reaction 'chamber' 31).: The size of the opening or. openings 39 mayjbe'made so that 19 to7 5% of the re-' generating'medium or reactants which enter the annular passage of each conduit will enter it through the opening or openings 39. In addition,' these openings serve to permit tars or con- 1 densate to'drain ;from the contact mass-or reaction chamber of the converter, and, in this aspect, to some extent take the "place'of members'3l and 3m, shown in'Fig. 3.

' During purging as well as during the onstream reaction period (especially during the purging which follows the oi -stream period and precedes regeneratiomyitds important to have suitableprovision for the drainage of tar or condensate from the contact mass or reaction chamber, such asthe openingsorperforations 39 in the inner members of nested conduits lb, ducts 3| which are described in connection with Fig. 3, small openings in the lower tubesheet, or equiv'alent. Otherwise, durin purgin heavy material or liquids may collect in the bottomof the reaction chamber of'the converter and would tend to plug up or coke upthe lower part of the reaction chamber.

' Valves Mb and l5b may be controlled toadmit steam or equivalent fluid to the streamof hydro carbon charge at the point or points desired, for the reasons described in connection with Fig. 1. The feed lines andheating systemof Fig. 5 maybe employed in'various other ways from those discussed. For example, steam may be passed successively through .valves 36, 50 and Nb before introduction with the charge,,when it is desired to employ heater 3! to boost further the temperature of thesteam or the like; v

In the apparatus shown in'Fig. 7, a separation or fractionation of the tar or condensate which is.

withdrawn from the converter through duct 16c,

controlled by valve .l'lc, is made in separator I80. The heaviest material is withdrawn from the separator l8c through the valved duct 280 leading from the bottom thereo f while a somewhat lighter fraction of condensate is withdrawn from the separator through duct 40 and valve 400 and passed to the vaporizing chamber 4|.

Steam or other inert vaporizing fluid-may be passed'from heater 310 through duct 42, controlled. by valve 42a, and thence passedfrom a jet (not shown) into the vaporizing chamber 4|. The liquid 'material is' substantially vaporized or atomized due to the partial pressure supplied by'the steam and the mechanical vaporizing action thereof before the mixture of steam and hydrocarbons passes from the vaporizing chamher through duct 43, controlled by valve 4341 into the duct4v through which charge is being fed to the converter lc from the atomizer shown; or, where desired, the mixture may be passed, in wholeor in part, through branched duct 45, controlled by valve 45a, thereby entering the atomizer together with the charge, which is being fed thereto from heater llc. Duct 30c serves the same function in this apparatus as duct 30 shown in Fig. 1.

It will be seen that the apparatus just described provides means for carrying out an efflcient method of recovering .desirable dissolved or oceluded components from the separated .condensateand does this by making use of some of the steam or other inert fluid which, in addition to this use, provides other valuable functions by being present in the reactants while they are undergoing treatment or conversion.

In the modification of the converter shown in Fig. 8, the tar or condensate, which is separated out by the baffle member I3d or otherwise accumulates in the bottom of the converter, passes from the latter through the annular passage surrounding elbow duct 3511. To obviate the disadvantages caused by tars or heavy condensate getting into the valve 24d andhardening or coking therein,'the lower branch 46 of the fitting shown is set off center to the right, and lip 41 projects below the adjacenthorizontal wall of the fitting to cause all of the condensate or tar to pass into branch 46 and to be kept out of valve 24d andthe horizontal line leading thereto. A tar pot l8d is joined to the bottom of the branch 46 and tar or condensate is drained therefrom, continuously or intermittently by the valved duct 28d.

The fitting, as illustrated in Figs. 1, 5 and 8, through which reactants and regeneration fluid may be introduced into the converter, is of construction which requires special description. The fitting shown in Fig. 1 is T-shaped, and has elbow duct 12 therewithin; whereas, in Figs. 5 and 8, a similar fitting is shown having elbow ducts 35 and 3511, respectively, the former of the two having a Venturi throat in it. The upright portion .of each of the elbow ducts shown is spaced from the walls of the upright portion of the T-shaped fitting to provide a passage upwardly through which regenerative fluid may pass or downwardly through which (as in Fig. 8) tar or condensate may drain. However, in Figs. 1 and 5, the fitting. extends above the bottom of the manifolding chamber and separatedrains are provided 1 for the tar or other condensate.

While in the figures of the drawings a single bafile member is shown in each case for separating entrained liquids from vapors, it will be under- I stood that such showing, is illustrative only and any number or types of balile member may be used in lieu of those shown.

The temperatures which are employed in our treating or converting operation will depend upon the particular liquid being treated and the products desired. The same conditions will, in. a measure be determinative ofthecontact mass or catalyst which may be chosen for the reaction chamber. However, where our invention is applied to the treatment or conversion of hydrocarbons, temperatures-of the order of 750 to 950 F. will usually be employed. The temperature of the charge entering the converter, through the manifolding zone which contains the battle, will ordinarily be slightly higher, for example, to 50 F. higher than the temperatures desired in the reaction zone. Where heavy materials such as heavy gas oil or residua are being charged to the converter, a temperature of the order of 810 to 950 F..will often be suitable, as, for example, a temperature of about 840 or 850 F. Any contact mass capable of effecting or promoting the desired reaction may be utilized, preferably in the form of fragmentary or molded pieces to. facilitate regeneration in place. A suitable catalyst for these hydrocarbon treatments and. conversions isone such as described in Patent No. 1,837,971 issued to Alfred Joseph on December 22, 1931, or in the copending applications of Eugene J. Houdry, Serial No. 600,581, filed March 23, 1932 (Patent No. 2,078,945, issued May 4, 1937), and Serial'No. 35,101 filed August 7, 1935 (Patent No. 2,078,951, issued May 4, 1937), consisting of molded particles comprising, for example, blends of silica and aluminaof natural or artificial origin including activated hydrosilicate of alumina with or without admixture or other catalytically active materials including metals and metallic compounds. Contemplated contact masses include materials which are substantially inert or have any desired restricted degree of activity.

Where a heavy gas oilor similar heavy or residual material is being charged to the converter, a quantity of steam of the order of 5 to 20% by weight of the charge may be introduced therewith as and/or before it'goes through the heater, such as heater H or Ila and 5 to 20% of additional steam maybe added at the atomizer, in an embodiment where the atomizer is employed. In the case Where superheated steam is introduced with the charge in the inlet manifolding zone, the amounts of steam introduced at the heater oratomi'zer may be somewhat reduced. The use of superheated steam as just described, is advantageous in'the'case of heavy charging materials in that it keeps the reactants in a good state of vaporization during-their passage through and in contact with the catalyst or contact mass within the reaction chamber.

While'not definitely shown in all the figures of the drawings, it is to be understood that an atomizer or any equivalent equipment may be used with any of the modifications illustrated, especially where the apparatus is to be used to treat 'or convert 'a high-boiling material such as heavy bottoms from a distillation of hydrocarbons, or the like. When an atomizer is employed, the inert fluid such as steam, or at least part of it, is preferably used to assist in the atomization but, even in this case, it is often desirable to introduce further steam, in superheated state, in the manifolding zone. Practically always, it ispreferred to have the atomizer positioned as close as possible to the inlet to the converter.

The preferred direction and circuit of the purging medium through the'converter is obvious from the drawings, especially Fig. 5 thereof. No provision is shown for purging the apparatus of Fig. 1 but it is intended that it be effected in a similar manner. The openings 39 in the inserts or other conduits of double or nested members lb, as shown in Fig. 5 or in duct 3|, shown in Fig. 3, function as well to drain condensate, tars or liquids from the reactionchamber during the intervening purging operations as to drain condensate therefrom during the reaction or on-stream period. Inaddition to introducing purging mediumfrom'the topof the convertenas shown in Fig. 5, steam or other inert medium may be passed into the converter from the bottom through heater 3'! and valve 38, thereby topurge out the bottom connections; or all of the purging medium may be supplied from the bottom connections, if desired. It is also contemplated to employ vacuumpurging. w W A It is tobe observed that by efiecting separation of condensate or tar in a manifolding chamber of the converter, the advantages received by the conversion or reaction-zone during regeneration are also available tothe tar separation zone in the manifolding chamben I l While our invention 'isespecially applicable to the treatment of heavy or high boiling composite w fluids, such as composite. hydrocarbon fluids, it

fill

will be apparent that it has application inthe treatment or conversion of fluids broadly, particularly where a contact mass or-catalyst is to be employed. t I

Where herein or in the appended claims the term composite fluid or composite hydrocarbon fluid or the like is employed it will be understood that a fluid having a boiling range, i.'e. made up of a number of'materials each having at least a slightly different boiling point than the other, is contemplated. Fluids such as petroleum or fractions thereof coal tar orfractions thereof, iusel oil or other mixtures of alcohols, etc. are commonly spoken of among'engineers, as com-. posite fluids.

What we claim is: t 1.

1. In e chemicahconversion-of a composite liquid having a substantialboiling'range into a vaporous product comprising "lower boiling components in the presence of a catalytic mass, the steps of process which comprise heating and substantially vaporizing said liquid except for a portion of said liquid which" comprises thehighest boiling components. thereof which remain liquid and are carried with the vapors as finely divided entrained particles, continuously passing a' stream of the heated and substantially vaporized fluid into a manifolding zone, situate adjacent to and having direct fluid communication with' a "reaction zone through a plurality of passages, thelatter containing a bed'ofsolid adsorptive catalyst, separating unvaporized entrained liquid from the vapors of said stream of :fluid within said manifolding zone, withdrawing the-separated liquid from said manifolding zone, passing'the substantially liquid-free vapors, without substantial loss of heat, directly from said manifolding zone in a multiplicity of streams intosaid adjacent reaction zone, wherein the desired treatment takes place, and continuously withdrawing reaction products from said reaction zone.

2. In the conversion or cracking of a heavy,"

high-boiling, normally liquid hydrocarbon fluid to produce lower boiling hydrocarbons therefrom" in which vaporized fluid is passed into contact with a catalytic mass, the steps of process which comprise heating and substantially vaporizing said fluid, continuously treating a stream of'said fluid so as'to atomize liquid contained therein,

continuously passing a stream of the resultant vapors and atomized liquid into a manifolding zone, situate adjacent'to'and having fluid com- I munication with a reaction zone through a mul tiplicity of openings, said reaction zone containing a mass of solid adsorptive cracking catalyst,

separating unvaporized entrained liquid from the vapors of said stream of fluid within-said manifolding zone, withdrawing the separated liquid-from said manifolding zone, passing the substantially, liquid-free hydrocarbon reactant .vapors. without, substantial loss of heat, directly from said manifoldingzone into said adjacent reaction zone. through the aforesaid multiplicity ofopenings and introducing them directly into said reactionzone in contact with said catalyst ata multiplicity of spaced pointaand withdrawing reaction products from said reaction zone. 7

3. In theconversion or cracking of acomposite hydrocarbon fluid having" a substantial boiling range to produce a hydrocarbon product ofdifferentiboilingrange comprising lowerboiling hydrocarbons, the steps ,of process which comprise heatingvand substantially vaporizing the liquid except for, a portion of said liquid whichcomprises the 'highest boiling components thereof which remain-liquidand are carried with the vapors as finely divided entrained particles, continuously passing a stream of the resulting heated fluid'into a manifolding zone, situate adjacent to andhavingqfluid communication with a reaction zone througha plurality of passages,- saidreacheated steam into said liquld-free'vapors-precedingxtheirentry into said reaction zone, withdrawingreactionproducts from said reaction zone atv a plurality of points distributed throughout its volume, and withdrawing condensate from said reactionzona '4 In the transformation or cracking of a heavy, high boiling-composite hydrocarbon liquid above the gasoline boiling 'range and substantially in the-boiling range of heavy gas oils and residua to produce therefrom lower boiling hydrocarbons, in which vaporized fluid is passed into contact with a catalytic materiaL-the steps of the process whichcompriseheating and substantially vaporizing said fluid without any substantial pyrolyti'c cracking thereof, a small "portion of said fluid which comprises highest'boili'ng components I thereof remaining liquid and being carried in the: vapors as entrained'particles;said vapors being" raised to a' temperature at which the desired catalytic cracking will take place, continuously passing a stream of the'heated and substantiallyvaporized reactant hydrocarbon fluid into a manifolding'zone, situate adjacent to 'andhaving fluid communication with 'a reaction zone, said reaction zone containing a mass of solid, adsorptive cracking" "catalyst, separating unvaporized entrained" liquid from the vapors or; said stream of fluid within said manifoldi'ng zonefwithdrawing,

the separated liquid from said'm'anifolding zone, passing the substantially liquid free vapors,

without substantial loss of" heat, "directly from said, manifolding zonein a' plurality of streams into said adjacent reaction zone and through and in contact with the aforesaid catalyst located thereirl introducing superheated steam into said liquid f'ree vapors preceding their entry into the said reactionzone, and continuously withdrawing reaction products from said reactionzone.

5. In the conversion or cracking of a heavy, high boiling composite hydrocarbon liquid, having a boiling range substantially above that of gasoline to produce therefrom a substantial proportion of components within the gasoline boiling range, the steps of process which comprise passinga confined stream of said hydrocarbon fluid through a heating zone to vaporize and raise the temperature of said fluid to the range in which catalytic conversion or cracking will occur, a small portion of said fluid which comprises highest boiling components thereof remaining liquid and being carried in the vapors as entrained particles, introducing steam into said stream of hydrocarbon fluid during its passage through said zone at the point at which said fluid is approximately the temperature of said steam, introducing a smaller amount of steam into said confined stream prior'to the entry of said stream of hydrocarbons into said heating zone to prevent substantially any pyrolytic cracking of said hydrocarbons, continuously passing a stream of the heated fluid with admixed steamto a manifolding Zone, adjacent to and having fluid communication with a reaction zone through a multi plicity of passages, said reaction zone containing an adsorptive cracking catalyst, substantially completely separating unvaporized entrained liquid from the vapors of said stream of fluid within said manifolding zone, withdrawing the separated liquid from said manifolding zone, returning lower-boiling components, which are withdrawn with said separated liquid, back to said manifolding zone, passing the substantially liquid-free vapors, without substantial loss of heat, directly from said manifolding zone to said adjacent reaction zone and through and in contact with the aforesaid catalyst located therein, introducing superheated steam into said substantially liquidfree vapors preceding their entry into the said reaction zone, and continuously withdrawing reaction products from said reaction zone.

6. In the conversion or cracking of a high boiling composite hydrocarbon liquid, having a substantial boiling range and composed predomi-* nantly of components higher boiling than gasoline, into a lower boiling hydrocarbon product composed to substantial extent of components within the gasoline boiling range, the steps of process which comprise heating and substantial.- 1y vaporizing the liquid except for aportion of said liquid, which comprises the highest boiling components thereof, which remains liquid and is carried with the vapors as finely divided entrained particles, continuously passing a stream of the resulting heated fluid into a manifolding zone, situate adjacent to and having fluid communication with a reaction zone containing an adsorptive regenerative cracking catalyst, adapted to be employed alternately on-stream to eflect the desired conversion of hydrocarbons and in regeneration to restore said catalyst to active, adsorptive condition, separating unvaporized entrained liquid from the vapors of said stream of fluid within said manifolding zone, withdrawing the separated liquid from said manifolding zone, continuously passing the substantially liquid-free reactant hydrocarbon vapors, without substantial loss of heat, directly from said manifolding zone into said adjacent reaction zone in a multiplicity of streams and through and in contact with the aforesaid catalyst located therein',;and withdrawing fluid products of reaction therefrom;

after a period of time on-stream stopping the introduction of said hydrocarbon vapors into said reaction zoneand purgingsaid reaction zone preliminary to the introduction into said catalyst of an oxygen-containing regenerating medium, said purging being effected in the reverse direction to the feeding of hydrocarbons so that purged material including hydrocarbon vapors leave said reaction zone through the aforesaid manifolding zone. I 1

7. In the conversion or cracking of a composite hydrocarbon liquid composed predominantly of components abovethe gasoline boiling range to produce a hydrocarbon product comprising lower boiling hydrocarbons in which vaporized fluid is passed into contact with an active catalytic material, the steps of process which comprise passing a confined stream of said hydrocarbon liquid through a heating zone substantially to vaporize said liquid and to raise the temperature thereof substantially to the range desired for catalytic cracking, a small proportion of said fluid which comprises the highest boiling components thereof remaining liquid and being carried in the vapors as entrained particles, introducing steam into said stream of resulting heated and substantially vaporized hydrocarbons and continuously passing a stream of the resulting heated hydrocarbons and steam into a manifolding zone, located adjacent to and having direct fluid communication through a multiplicity of passages with a reaction zone containing a body of adsorptive, regenerative cracking catalyst, separating unvaporized entrained liquid from the vapors of said stream of fluid within said manifoldingzone, withdrawing the separated liquid from said manifolding zone, passing the substantially liquid-free reactant vapors, without substantial loss of heat, directly from said manifolding zone through the aforesaid passages into said adjacent reaction zone and introducingsaid vapors directly into said body of catalyst at a multiplicity of points distributed throughout the same, and continuously withdrawing cracked fluid hydrocarbon products from said that purged fluids leave said reaction zone through the aforesaid manifolding zone.

8. In the transformation or cracking of a composite hydrocarbon liquid composed predominantly of components boiling above the gasoline boiling range to produce therefrom hydrocarbons of lower boiling points in which vaporized fluid is passed into contact with a catalytic mass, the steps of process which comprise passing a confined stream of said hydrocarbon fluid through a heating zone to vaporize substantially all of said fluid, exceptior a small amount thereof which remains as entrained liquid particles in'the vapors, and to raise the temperature thereof substantially to the'rangeinwhich the desired catalytictransformation will occur, introducing steam into said stream of hydrocarbon fluid, a portion prior toand another portion during its passage through said heating zone, continuously passing a stream of the heated, substantially vaporized fluid from said heating zone into a manifoiding w ttszone, situate beneath andcontiguous to andhav ing fluid communication with a reaction zone containing a deep bed of'adsorptive, regenerative; cracking catalyst the latter being adapted, pe-v riodically to be regenerated in situto remove combustible contaminants therefrom, separatingrun vaporized entrained liquid mm thel vapors of said stream of fluid withinsaid manifolding zone, withdrawing the separated liquid from said manifolding zone, passing the substantially, liquid free vapors, without substantial lossv of heat, in a multiplicity of confined streams directly from said,

manifolding zone upwardly into said reaction zone and distributing such vapors from said confined streams into contact withthe'aforesaid cracking catalyst at a multiplicity of points fspaced throughout the depth and cross-section of said bedthereof, continuously withdrawing fluid prodnets of reaction from said reaction zone, periodicallystopping the flow of said. hydrocarbons to affect a regeneration-of said catalyst, and inter-, mediate the steps of conversionofhydrocarbons and regeneration purging said reactionzone, said purging being effected so that purged fluids'leave said reaction zone through the aforesaid manifolding zone located therebeneath.

9. In the conversion or cracking of a composite, higher boiling hydrocarbon liquid with a contact fluid product mass to produce a more volatile therefrom,'in which the contact mass gradually becomes contaminated and is consequently a1- ternately on stream and in regeneration,-the

steps-of process which comprise heating and substantially vaporizing said liquid except for, ,a smallproportion thereof. comprising thehighest boiling components thereof which is carried with the vapors. as finely divided entrained particles,

' continuously passing a stream of the heated, subreaction zone through the aforesaid plurality of, passages and through and in Contact with the.

aforesaid catalyst located therein, withdrawing fluid products of reaction from said reaction zone,

periodically interrupting the passage of the aforesaid hydrocarbon fluid. subsequently in an alternate regenerative step passing a regenerating fluid through both said manifoldingzone and said reaction zone, thereby-to free said manifolding zone of deposits simultaneously with theregeneration of said contact mass; and, intermediate the steps of cracking hydrocarbons in the afore-i said reaction zone and regeneration of saidcon,- tact mass. purging said reaction zone and bed of catalyst ina mannerjsothat purged vapors leave said reaction zonejthrough the aforesaid manifolding zone.

10.- Apparatus for the treatment or" conversion of fluids which comprises a converter having a. re I action chamber and a manifolding chamber. an; adsorptive contact materialwithinsaid reaction,

chamber, a partition betwcen said manifolding chamber and said reaction chamber, said partttion having passages to permit flow. of fluid to be treated from the former to the latter, means for conducting condensate outof s'aidreaction' chamber from the lower part thereof, means for in- I action chamber.

of passages, said reaction zone containstream of fluid within said mani-.

trodu'cin'g a vaporized fluid to be treated into said manifoldingchamber including a conduit open ing thereinto, means located within taidf mani-, folding chamber for separating entrainedliouid from the entering vapors,;means for, passing separated entrained liquid oncondensate from said manifo'lding "chamberfandfmeans providing passageswithinsaid contact material through which treated fluid may bewithdrawn from said rell. Appaiat'us for reaction chamber, a partition within said converter separating'a manifolding chamber from said, reaction ,chamber but having openings permitting .communication between said chambers,

means 'fort introducing a vaporized fluid to be treated into the manifolding chamber of said converter including a; co'nduit opening into said manifolding chamber, means located within, said manifoldi'n'g chamber for separating entrained liquidfrom, the entering vapors, a pluralityof v theltreatn ent or conversion of fluids which" comprises. a converter having. a:

ducts co'r'nmunicating with said reaction chamber,

through thebottom thereof andbeing adapted to drain I condensate or ta'r therefrom, means for withdrawing separated; entrained ,liq'uid from said manifolding chamber a "receptacle for said se parated entrained liquid having a vent line tosaid nianifolding chamb'er to equalize pressure, {and passages communicating with said reaction zone through which :treated fluid maybe withdrawn therefrom. l

1 2.- Apparatus for the treatment or conversion V of heavy compositafluids which comprises a converter having a reaction chamber with an outlet connection?therefrom, -a partition withinisaid converter separating a manifolding chamber from said reaction chamber, means providing fluid communication between said chambers, means for introducing a vaporized fluid to betreated into the .manifolding chamber of said converter including a conduit opening into said manifolding chamber, meansdocated within said manifolding chamberofor separating entrainedliquid from the entering vapors, a tar separator exterior to said manifolding chamber and convertcr, a duct for passing ,the separated entrained liquidfrom said manifolding chamber to said tar separator,- a duct connected to said tanseparator. for with-: drawinga heavy, high-boiling tarry fraction of liquid therefrom, a vaporizing means, a second duct leading from said tar separator to said vaporizng means,and means including a pipeleading from saidvaporizing means to conduct fluid to the aforesaid manifolding chamber.

l3. Apparatusfforthe treatment orconversion.

of a heavy compositefluid whichcomprisesa converterproviding a reactlonchamberand a manifolding chamber, :a partition separating said reaction chamber from said manifolding chamber,

a plurality of passages through said partition to.

permit fluids to be treated to enter said reaction chamber, a heater, a duct for supplying fluid to said heater, an atomizer, a" connection leading from said heater to said atomizer, bafile means from said atomizer to said manifolding' chamber within saidm anifolding chamber, a connection I of said converter, said connection being positioned to direct entering vapors against said baffle means thereby to separate out entrained liquid and to prevent it from "entering said reaction chamber, meansfor withdrawing separated entrained liquid from said manifolding chamberfand passages communicating with said reaction chamber through which treated fluid may be withdrawn therefrom.

1 Apparatus for the treatment or conversion of a heavy composite'fluid which comprises a converter providing a reaction chamber and a manifolding chamber, a partition separating said reaction chamber from said manifolding chamber; a plurality of passages throughsaid' partition to permit fluids to be treated to enter said reaction chamber, bafiie means within said manifolding chamber, means for introducing a vaporized fluid into said manifolding chamber of said converter including a conduit opening into said manifolding chamber and positioned to direct entering vapors against said baffle means, a fluid carrying I element extending into said manifolding chamber and positioned irgfcircuit between said baffle beans and said partition and being adapted to introduce superheated steam thereinto, and passages communicating with said reaction chamber through whichtreated fluid may be withdrawn therefrom.

'15. Apparatus for thetreatment or conversion of a heavy composite fluid which comprises aing chamber and positioned to direct entering vapors against said baffle means, a larger duct surrounding the last-mentioned conduit and spaced therefrom to providera passage for separated tar or condensate to drain fromsaid manifolding chamber, an end of said larger duct being approximately flush with theinner surface of the aforesaid head of the converter, a valved branch through which regeneration fluid is adapted to be introduced into the converter extending from said larger duct, a duct forming a continuation of said larger duct butpositioned with its axis shifted away from that of said larger duct inthe direction of said lateral valved branch, and passages communicating with said reaction zone through which treated fluid may be withdrawn therefrom.

16. Apparatus forthe treatment or conversion of fluid which comprises a converter providing a reaction chamber, a contact mass within said chamber, said mass being adapted tobe periodically regenerated in situ by passing a regenerating medium therethrough, said converter accordingly being adapted to be alternately on-stream and in regeneration, a fitting through which reactants and regenerating medium may be introduced to the converter having at least three branches, one of which is connected to said converter at a point where it is desired to introduce fluids thereinto, a second branch thereof being connected to a pipe, having a valve therein, through which regenerating medium may be passed to the converter, and a third branch thereof being joined to a conduit connected .to a source of reactants, an .elbow duct extending through the first-mentioned branch and said third branch and being joined to the latter adjacent its extremity so that reactants must pass through'said elbow duct and not therearound, the exterior dimensions of said elbow duct being less than the internal dimensions of said first-mentioned branch throughout the respective section of length of the duct which passes therethrough, so as to have a passage for regeneration fluids or other fluids therearound, said elbow duct preventing reactant fluids from lodging around the valve in the said pipe for'introducing regeneration fluid. 17. Apparatus for the treatment or conversion of fluids which comprises a converter having a reaction chamber, a partition within said c'onverter separating a manifolding chamber from said reaction chamber, means for introducing a vaporized fluid to be treated into the manifold-' ing chamber of said converter including a conduit openinginto said manifolding chamber, ports or openings through the aforesaid partition, a unit comprising inner and outer nested conduits joined to-said partition adjacent one of-sald ports and in registering relation therewith and'extending within said reaction chamber, saidunit having openings in the outer conduit thereof along its length and having a perforation or opening in the inner conduit adjacent the end thereof adjacent said partition, and passages communicating with said reaction zone'through which treated fluid may be withdrawn therefrom. 18. Apparatus for the treatment or" conversion of fluid which comprises a converter providing a reaction chamber and a subjacent chamber, a partition separating said reaction chamber from said subjacent chamber, and having an opening therein, and a member for distributing or co1- lecting fluid adapted to extend within said reaction chamber with one end thereof 'joined to said partition to register with said opening therein, said member comprising inner and outer nested conduits having the inner conduit spaced from the outer one and open at both ends, said outer con-- duit having perforations or openings through its wall along its length and said inner conduit having at least one opening through its wall adjacent the end of the member which is adapted to be joined to saidpartition, and means for conducting-fluid to be treated to one of said chambers and for withdrawing treated products from the other of said chambers.

v 19. Apparatus for the treatment or conversion of fluids which comprises a converter having a reaction chamber and a manifolding chamber therebelow, a partition having perforations or openings therein separating said manifolding chamber from said reaction chamber, distributing members, each having inner and outer nested 'or telescoped conduits spaced from each other to provide a passage therebetween, fitted into said openings in said partition and extending upward ly into'said reaction chamber, the said exterior conduits having perforations or openings along their lengths and said interior conduits being open at both ends of each and having at least one perforation or opening adjacent the lower end of each adjacent the aforesaid partition, said lastmentioned opening or openings permitting condensate or tars to drain from said reaction chamber and being of such size as to permit a part only of the fluid being introduced into the said reaction chamber from said manifolding chamber to pass therethrough, means for introducing a vaporized fluid to be treated into said manifolding chamber including a conduit opening into said manifolding chamber, means located within said manifolding chamber for separating entrained liquid from the entering vapors, a receptacle for condensate or tar exterior to said manifolding chamber and converter, and means tor-passing separated entrained liquid from said inaniiolding chamber to'said receptacle.

20. A distributing unit to; "fluids which is adapted to be embedded in a cjontact mass which comprises a unit having inner and outer nested conduits spaced from each other, to provide a passage therebetween as well as withinthe inner conduit, saidouter conduit having perforations or openings spaced from each other along its length and said inner conduit-being openat both ends, one open end thereof being the inlet opening for the introduction of fluids and the other open end thereof facing a closed end'of the said outer conduit to efiectreversal of fluid flow. the said inner conduit having at least one opening or perforation adjacent its said inlet opening which provides direct communication between the said inner conduit and the said passage between the said outer and inner conduits.

EUGENE J. HOUDRY. 'RAYMOND c. LASSIAT.

GEORGE mo,

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