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Dern 17, 1946. T. P._‘.:`«IMF’SON- EVAL 2,412,917 METHOD FOR CATALYTIG CONVERSION Filed sept. 19, 1942 /7 D 2 [email protected] Dec. l?, 1946. fr. F'.l SIMPSON Er AL 2,412,917 METHOD FOR CATALYTIC CONVERSION Filed> Sept; 19, 1942 2 Sheets-Sheet 2 52% 4.3 ¿y 4,0 ‘ MM 42 5a NVENTOR BY _ ATTORNEY 2,412,917 Patented Dec. 17, 1946 linurl-:n [STATES PATENT. orrlcs N ,y METHOD FOR CATALYTIC CONVERSION ì Thomas'P. Simpson, `John W. Payne, and John . A. Crowley, Jr., Woodbury, N. J., assign Socony-Vacuum Oil Company, Incorporated, a. ' ' corporation of New York ¿ i Application September 19, 1942, Serial No. 458,926 ~ . - A . l 14 Claims. f 'I'his invention is directed to (ci. 19e-_52) n A methods of con- . ' ’ Y . stream oi.' catalyst for the accomplishment of conversion, in which the catalytic material is used only at a high level of eillciency, and in which the catalytic material is continuously re ducting reactions in the presence oi.' a contact mass, such- as, for example, the catalytic conver sion of hydrocarbons. " 2 Y , It is known that many operations for the con lCII generated and returned to the conversion step, both operations being conducted under controlled version of hydrocarbon materials to other hydro carbon materials> of differing ~physical and/or This invention has for a major object the chemical properties may be carried out catalyt- » establishment of proper control factors for the ically. Most of these are carried out by contact . ing the hydrocarbon, usually in vapor form and 10 eillcient operation of such a process. This invention is based. upon the principle ot at high temperature, with a contact mass com carrying out -catalytlc reactions by flowing a posed of particles which themselves have a cata stream4l oi’ reaction mixture in physical contact lytic eilect, or which are impregnated with or conditions. ' . with a ilowing stream of catalytic material. act as a support i’or other catalytic material of In order that this invention may be understood, a nature appropriate to the result desired. Such 115 reference is made to the drawings attached to operations may contemplate, for example, the and made a part of this specification. In these conversion of hydrocarbons of high boiling point drawings, Figure 1 shows in diagram form a re -to those of lower boiling point, or the polymer ization of light or gaseous hydrocarbons to hy drocarbons of higher boiling point. Other oper action and regeneration apparatus suitable for 20 use in this process, Figures 2, 3,4, 5 and 6 are concerned with internal details of such cham# bers, and Figure 7 shows in' diagram form a set up of apparatus suitable for the conversion of ations of like nature are catalytic dehydrogena tion, hydrogenation, desulphurizing, partial oxi dation and similar conversions of _hydrocarbon hydrocarbon oils. materials. The method ot operation herein dis closed is applicable to all such conversions. Of 25 In Figure 1, character 8 denotes a regenera tion chamber, 9 a purging section, I0 a, reaction these operations, the vapor phase cracking- of chamber, II a second purging section, and I2 an heavy hydrocarbons to gasoline is typical, and this specification will hereinafter discuss such ‘ elevator for catalyst particles. Regeneration chamber 8 and _reaction chamber I0 are similar in 4operation as exemplary, without, however, in tending to be limited thereby or thereto except « construction and internal fittings and consist (referring now to 8) of an exterior shell 8, which may be cylindrical or rectangular in cross-sec tion, with a convergent sealed top I3 and a con by such limits as may appear in the claims. Such catalytic processesgenerally make use of -reactlon chambers containing a fixed body of ' catalyst or contact mass, through which the re action mixture is passed, and in which, after the vergent bottomvii, and ?ltted with an interior~ . false bottom I5, which is perforate, the perfora reaction has slowed down to an uneconomic point, the contact mass is regenerated in situ. Such .processes are not continuous, andv only attain continuity by the provision of numerous reaction tions therein being too small for the passage of and on regeneration. Likewise, it is difiicult to wheel as shown, an intermittently operated valve set-up or other common' device of this nature'. Catalyst material introduced through I8 ñlls the catalyst particles but permitting the passage of liquid or gas.~ Bottom Il is iìtted ywith pipe I6, and top I3 with pipe Il. At the -top of I3 is a chambers which arev alternately placed on stream ~ 40 sealed feeding device I8, which may be a star maintain constant quantity and _quality of prod uct withoutnumerous chambers and intricate scheduling, due to the progressively- decreasing activity of catalyst.' This same feature, with ap paratus limitations,` prevents, lto a degree, the use of catalyst at a uniform high eillciency level. ' Mostv of these difñculties may be avoided bythe use of a method wherein the catalyst or contact mass is handled continuously as well. This in 50 vention is vspeciiìcally directed to'such a process. This invention has for its object the provision of a process of hydrocarbon oil conversion where in a continuously moving stream of hydrocarbon oil is contacted with a continuously moving interior of shell 8, passes down therethrough, 'is collected by false bottom' I5 and chuterïIB~ and is removed by a second intermittently‘operating device, such as star wheel 20.4 This~ arrangement effects a continuously moving stream of ‘catalytic material through shell 8. Reaction mixture, in this case air for an oxidizing regeneration, may be introduced through pipe I6 and products oi reaction, in this case flue gas, may be removed through pipe Il. This effects a continuously flowing stream of reaction material in physical contact with the continuously flowing stream of 2,419,917 3 , - catalytic material in shell 8. 'I'he flow shown is countercurrent. If desired, it may be made con current by reversing the func\tlonslof I8 and I1. Shell 8 is also internally iitted with a series of conduits 2l, equipped with ñns 22,l joined to b1 headers 23 and 24, through which a heat ex change medium may be passed by-means oi pipes l 4 In certain reactions, no heat transfer elements are required in the reaction chamber. Figure 2 shows a cross-section oi case 8 at the level 2-2 showing how the preferred longitu dinal passages may be formed by equipping each heat exchange tube with two diametrically op posed, longitudinally disposed axial fins. Figures 3 and 4 show other ways of arriving at the 25 and 25. The/liest exchange medium may be same result. The heat transfer tubes need not used to control the temperature of reaction by be arranged parallel to the flow of catalyst, but extraction of heat from or_addition of heat to .10. may well be transverse thereto, as shown in Fig ures 5 and 6, wherein transverse tubes 39, carry the concurrent, material countercurrent, within shell 8, and or, as its later ñow may shown,¿ be ing ilns.40, extend between header boxes 4I and transverse to the direction of ilow of catalytic A 42 in a shell 43, to exercise the same functions as material.- Shell I0 is similarly ?tted and simi corresponding parts in shells 8 and IIJ. larly operated. Reaction material, in this case 15 It will also be noted in Figures 5 and 6 that hydrocarbons, is introduced by 21, and removed the heat exchange elements 39-40 may be spaced by 28, catalyst movement is controlled by' 28 and apart -so as to provide within the regeneration 30, and heat exchange medium is circulated by chamber severalzones intermediate of its ends. pipes 3| and 32. Confined passage 9, maintained wherein combustion may take place without sub relatively full of catalyst by devices 20 and 29, ,is 20 stantial simultaneous removal of heat. fitted with pipes 33 'and 34, by means of which The heat exchange medium, if used, may be steam may be passed through‘the _catalyst for . any iluid suitable for the load and temperature purging. ` A similar purging passage I I lies below levels encountered, such as gases, liquids of vari shell I0, is controlled by devices 30 and 35, and 25 ous kinds, molten metals, or alloys, or fused salts. iìtted with steam pipes 36 and 31 for purging Preferably it should be possessed of a low vapor catalyst after reaction.` From `II- the catalyst pressure, low viscosity, and high speciñc heat at drops through 35 into boot\38 of elevator I2 by operating temperatures and non-corrosive to which it is elevated and discharged into bin 38a steel. above shell 8. Elevator I2 may be of the belt 30 Passages 8 and II, used for purging by passing and bucket type shown or of any other kind steam through the catalyst particles, should be so suitable for the physical properties of the cata proportioned that a suillcient contact of steam lytic materials. It will be seen that in apparatus and catalyst particles occurs to -remove the resid of the type shown in Figure 1 there is a controlled ual volatile products of the preceding reaction. gravity flow of catalyst ‘through shells 8 and ID 'Inrnlng to Figure 7, which shows an operating into the feed boot 38 of the elevator I2 which re turns spent catalyst to the inlet of shell I 0, there setup appropriate for a conversion of hydrocar bons, such as, for example, a vapor phase crack . by providing means for carrying out the continu ing, we find charge oil fed through pipe 44 by ous catalytic process contemplated herein with ' pump 45 to a vapor preparation unit` 46. Vapor a high degree of thermal eillciency because the 40 preparation unit 46 vwill consist essentially of a hot catalyst does not have an opportunity to cool heater, for which purpose any of the usual forms to atmospheric temperature during its movement of heater common in the art, say a pipe still, through the circuit. Obviously, arrangements may be used, to heat and vaporize the charge other than that described above may be employed and heat it to reaction temperature, and, if the to eil’ect the movement of catalyst successively charge- used is not wholly vaporized at the reac through _a conversion chamber and a regenerat tion temperature, a vapor separator to remove ing chamber without permitting it to cool to at unvaporized liquid'residue. Vapors from 46 move mospheric temperature. Customary devices for through pipe 41 into and through reaction cham the removal of -lines and the addition of makeup ber 48 (the same as I0, Figure 1), and therein may be inserted in the catalyst conveyor system. undergo catalyticA reaction. Reaction products Special attention should be given to the arrange- d pass through pipe 49 .to product puriñcation ment of heat exchange tubes within the shells 8 and recovery equipment denoted by 50. 50 may and I0. These should be so arranged as to pro-- ' be made up of any of the usual fractionation, mote the passage of catalytic material and reac separation and disposal devices currently in com tion material longitudinally through the shell . mon usel for handling products of cracking re in such manner that the ñowing material is at al1 times in heat exchange relationship with the [email protected] If desired, product fractions boiling above theV desired low-boiling product may be returned to the system forretreatment, either heat exchange medium whilein the zone of heat . exchange elements. It will be seen from Figure separately or in admixture with fresh charge. o0 Catalytic material ilowing from 48 is purged in 5I and elevated by 52 to be introduced into 53 ywhich the temperature is independent of con Jwherein it is regenerated by burning with air trol other than temperature of reactants and ' supplied by blower and pipe 54, the products of nature of -the reactions taking piace. »The con regeneration being disposed' of_ through pipe 55, duits may be unñnned, but better results are ob~ (55 after which the regenerated catalyst is purged in tained if the external heat transfer surface of 551and returned to 48. The temperature level 1, regenerator 8,- that a zone above. and a zone below the heat exchange tubes provide space in ~ the heat exchange tubes is augmented by the addition of fins thereto.v These fins, primarily added for heat transfer reasons may be taken ad vantage of to assist in control of the flow of cata lyst and reaction fluid and contact therebetween of the reaction in 48 may be controlled and latent heat of reaction added thereto by a heat ex change medium introduced through pipe» 51 and removed through pipe 58. In the arrangement tubes, divide the space within the shell into a shown in Figure rI the same heat exchange me dium used in 48 may also be used to control the temperature of regeneration in 53. In the oper series of longitudinal passages of substantially .ation described herein, where the regeneration is constant cross-section throughout their length. an exothermlc reaction, the function of the heat by being disposed so that they, together with the ,.f„_ 2,412,917 -- e - . . » catalyst, no detectable> deterioration in quality` ~ exchange :mediumrinthe 'intermediate region of being found. chamber 53 is to prevent the temperature of re generation reaching a point which would cause _ The control of several features of the operation is oi considerable importance. In both the re heat damage to the catalyst and at the -same generator and reactor, the particle-form solid catalyst is moved down through the operation time permitting combustion of the carbonaceous deposit thereon. . Thus the heat exchange medium in l! acts to adjust and maintain the .temper in the form of a solid moving. column while the reactants (oxidizing gas in one case and hydro ' ature of the moving mass in the intermediate carbons in. the other), are passed countercur region thereof, between a minimum temperature below which burning of the carbonaceous deposit 10 rently therethrough. In order to c_ifectively se in the presence of oxidizing gases at an appre siable rate cannot occur and almaximum tem perature above which the catalytic material would _ be damaged by heat. For example, the temper ature for regeneration of a spent clay type cata lyst used. in cracking hydrocarbons may range from around the .cracking temperature (from ~ cure. contact of the reactants with all portions of the contact mass it is necessary that the re actants be passed therethrough at such velocity that the orderly and uniform progress of the contact mass is not impeded, and that channels wherein reactants might pass through rapidly without ~_adequate 'reaction be prevented from ' forming. It has been determined that the prei about 800° to about 950° F.) to a pealctemper erable upper limit for reactant velocity is some ature in the neighborhood of 1050° to-1100° F. Care should be exercised so that the regenerat 20 what below that at which active physical dis turbance or "boillng” of the contact mass will ing temperature does not rise substantially above occur. Of course, since various reactants may i200“v F. or serious damage to a catalyst of this be used. of varying densities and varying vis type may result.~1'n.the arrangement shown in cosities at the temperature of reaction, ranging Figure '1, the heat exchange medium is intro air to relatively heavy hydrocarbon, the duced into 53 by pipe 69 and removed by pipe 25 from actual linear velocities will vary for each re 60; The heat exchange medium is circulated by actant. Also, for particles of various sizes, the resistance of a given depth ,of bed isgreater in uses may be controlled by use of _various combi some cases, giving rise to another variation in _ nations of heat exchangers 82 and 83 and by passes 64, $5 and 86 in a manner obvious to those 30 the actual linear velocity of the reactant.. How ever, it has been determined that all of these skilled in the art. In many cases if the reactions variables merge in auch a manner that it can be taking place in chamber I8 have a relatively small stated that the maximum flow of any reactant, heat of reaction’ or where maintenance of closely through any particle form solid catalyst of clay controlled temperatures is not essential it is un type, should not be greater than that which will necessary to circulate the heat transfer medium 35 produce a pressure drop of about 6 inches of through the chamber. and a satisfactory heat water per foot of path through the contact balance and temperatures can be attained by bal mass, measured between the most nearly adja ancing the temperatures of the entering re-‘ pump Si andthe temperature for the several _ cent points of inlet and exit. actants and catalyst,... _ ' a _ As an example of one operation successfully 40 ` conducted in such apparatus. according to the process herein disclosed, coastal gas oil with which was admixed steam to the extent of about . This limiting value of pressure drop will vary with the apparent density of the contact mass material in the solid moving column. That is, Vfor contact mass materials which have a greater' weight per unit of volume in the state of packing . they attain in the solid moving column, the optimum pressure drop will be higher. It will, for example, range from somewhat less than 6" of (cold volumes), at a temperature of 800° F. was water per foot of path for materials having an contacted with a catalyst of activated clay gran ‘apparent density of 0.6 to somewhatless than ules at a rate of one volume of oil (cold) to tour volumes of clay in a chamber through which the 50 11" of water for materials having an apparent clay passed at such a rate that it remained in _ density of 1.1. Since fuller's earth, "uitrol," acid treated natural clays. and_most synthetic ma the reaction zone about 20 minutes... with the fol ’ `-'ioogl lowing resultsz;...gy4v „ u vi» 1». ~ . _ __ Yield 'ofno" E. PÍ essonne (including iso A terials now in use and of this general type have apparent densities ranging from about 0.6 to 55 0.8 a pressure drop of about 6" to 8" of water-per ^ butane and heavier in gas) _vol. per cent-- 67.4 ' foot of path is optimum for such catalytic ma»v Y _ Yield _or _dry gas (lighter-,_ than isobutane) _, wt. per cent_à VYield of -corel ______ __ terials of clay type. vHowever, other 'catalytic 4.0 .».-wt. per cent-- 2.5 ___.;_voL per cent-.. 35.0 _In this runthe catalyst was passed through the _ Yield 'of recycle stock.' materials which are also useful will include ma terials of higher apparent density, such as cer tain synthetic associations of alumina and silica, or may include materials of the clay-type. or of synthetic origin carrying a suilicient amount of regeneration chamber (of the same size as the reaction chamber) at the same rate„and was _ other catalyst, such as certain well known cata lytic metals carried by clay type carriers. With burned with a suillcient volume of air to main 65 these, the upper limits of optimum pressure drop tain above 10% CO: in the exit flue gas. are indicated. . _ ' The temperature of the reaction was held by The limits so far discussed are optimum and use of the heat exchange medium at 800° F., and preferred limits, as will be understood from the in the same manner the temperature of the re generation was not allowed to rise above 1100° F. The gasoline _produced was of excellent qual ity, high in anti-knock rating, and the recycle stock was clean. light in color, and of about the same boiling range as the charge. No high boil following. Obviously. greater economic useful ness results from greater use of each unito! reaction space installed. that is from greater thruput- of reactant_ per cubic foot of installed contact mass volume. Also, particularly in cra;k- ing of hydrocarbons, the laydowh of carbonaceous ing, dirty, liquid cracking tar was produced. The regenerated catalyst was equal in eñlciency to new 75 >matter'on the contact mass does not increaser ' 2,419,917 proportionately vwith increases in reactant thru put per unit volume o! contact mass. Reaction can, of course, be attained above these preferred , limits, up to rates of reactant thruput which are actually disruptive of the contact mass; but we have found that with contact masses of the general nature of clay that the rate should not be greater than one giving 7 to 10 inches of water pressure drop- per foot of path through 1 the contact mass and preferably not greater 10 than one giving about 6 to 8 inches of water pressure drop per _ foot of path through the contact mass. - « « . ~ sults may be obtained to an operable degree by burning olf, in each such combustive regeneration ~, stage without substantial removal of heat, from . about 0.05 per cent to about '0.60 per cent by weight of coke, based on contact mass weight. The controls herein set forth cooperate to per ` mit the establishment of a highly useful cyclic commercial process. The control set forth for the conversion reaction -accomplishes high rates of converted product production per unit of catalyst> volume employed, while at the same time permit- - ting relatively low rates of coke deposition. For this optimum conversion operation, it is .highly For »the heavier contact mass materials the desirable to provide a catalytic contact mass of optimum pressure drop will range upward to about 11 inches oi' water per foot of path, with the maximum pressure drop ranging upwardly to about 13 inches of water per foot of path. controlled activity. The regeneration control set forth permits of attaining such controlled re generation of spent catalysts in proportion .to . 0f similar interest and importance is the con _ the amount of coke deposited thereon. It is to be understood that the specific exam trol of burning in the regenerator, particularly 20 ples and numerical data herein disclosed are ex in those portions of the regenerator where burn planatory of the invention, and that it is not to ing may take place without simultaneous removal be limited thereby or thereto except as such lim of heat. The required temperature limits for itations are expressed in the claims. This application is a continuation-impart -of combustive regeneration are, as a minimum, the temperature whichv will support combustion, 25 our copending application Serial No. 361,440, filed namely about '150° F. as a practical minimum and October 16, 1940, which, in turn, is a continuation 800° F. as a preferred minimum temperature in-part of our application Serial No. 162,541, filed level in regeneration. The maximum is that temperature at which the contact mass will be damaged or reduced in eiiiciency by heat. As a matter of practical operation, the operating max imum will be about 950° F. to about 1100° F., with September 4, 1937. We claim: 1.l The method of converting a hydrocarbon oil Í which comprises passing the oil in vapor phase and at conversion temperature into contact with 1200°A F. set as an operating maximum which a substantially compact downwardly moving mass of particle-form` clay-type, solid catalytic mate should not be exceeded. « In order- to attain the control necessary to 35 rial in which conversion is eiiected, the vapors being introduced thereto at a flow rate not in avoid these maximum temperatures and at the same time assure complete control of carbona excess 0f sufficient to produce about seven to ceous deposit, the operation should preferably be ten inches of water pressure drop per foot of varied in accordance with .the amount of irn vapor path through said mass, effecting substan~ purity, usually spoken of as “coke” If the coke 40 .tially complete separation of hydrocarbons from to be burned oi! is large in amount, say above said mass, transferring contaminated contact mass to a regeneration zone and moving it there about 3 per cent by weight of the contact mass, ~ the exothermic heat generated by its burning is through as a substantially compact moving mass, so great relative to the heat capacity of the cata supplying oxygen containing gas thereto to burn lyst and combustion' gases that a generally si ' contaminant therefrom and removing heat suf ñcient to prevent the temperature of regenerat multaneous burning andremoval of heat is ad vantageous. If the coke to be removed is below ing contact mass from rising above .that which will damage the contact mass` and returning the about 3 per cent and particularly if it is below 1 regenerated contact mass in heated condition to per cent by weight of the contact mass, a consid A `erably better burn on’ or regeneration may be 50 the conversion zone. . 2. The method of converting a hydrocarbon oil obtained by permitting periods of burning with which comprises passing the oil in vapor phase out substantial simultaneous removal of heat in order to permit of more cleanly removing dini-_ ’ and at conversion temperature into contact with a substantially compact, upright column of gravi cultly ignitable coke. These conditions of rela tively small coke burnoii! are typical of the regen 55 .tating particle-form, clay-type, solid catalytic ma eration of contact- mass material spent in crack- ' terial in which conversion is effected, the vapors being introduced thereto at a iiow rate not in ex ing, and for this reason, when working with such a .process it ispreferred to use a regenerator A cess of sufñcient to produce about six =to eight `inches of water pressure drop per foot of vapor equipped as shown in Figures-5 and 6 where re gions of burning without substantial simultane: 00 path through said column, effecting substantially complete separation of hydrocarbons from said ous removal of heat are alternated- with heat ' column, transferring contaminated catalytic ma removal regions. ïHowever, control of maximum terial to a regeneration zone and moving it there temperature is necessary in these combustion regions without heat removal means and this can through as a substantially compact column of be provided by so adjusting the intensity of com-l 05 moving particles, supplying oxygen containing bustion in these regions as to provide a burn-off gas thereto to burn contaminant therefrom and positively removing heat sufiiclent to prevent the which is not suiiicient in intensity to raise the temperature of regenerating catalytic material contact mass therein to damaging temperature from rising above that which will damage the levels. It has been found that burning off up .to about 0.6 per cent by weight of coke (based upon 70 catalytic material, and returning the regenerated contact mass), in each stage of burning without contact mass in heated condition to the con version zone. substantial heat removal will achieve good re generation and permit adequate protection of the 3. The method of converting a. hydrocarbon oil which comprises passing the oil in vapor phase contact mass v material. Dependent upon the usual variables of combustion control, these re 75 and _at conversion temperature into contact with anaal? tinuously passing said material as a substantially compact column through Aa plurality of zones a'substantially compact moving mass of gravi tating particle-form,_ clay-type, solid catalytic in which combustion occurs without substantial material in which conversion is effected. the simultaneous removal of heat, said combustion « vapors being introduced thereto at a iiow ‘rate zones alternating with cooling zones in whichv substantially below~ that- which causes ïphysical heat is removed by indirect heat exchange with disturbance of themovingmass, eiîectlng sub- 4 stantially Icompleteiseparation 'of hydrocarbons _ a iluid heat exchange medium, the tempera ture at all times being maintained between a.' minimum- temperature at which combustion will tact mass to_ a regeneration zone and moving ` it therethrough as a substantially compact down 10 take place and a maximum temperature at which the catalytic material begins to suffer heat dam wardly moving mass'. supplying omgen contain age, the amount of burning in each combustion ing gas thereto to burn contaminant therefrom, zone being limited to the burning ofi ci from said'gas being supplied at a flow rate not in 0.05 per- cent to about 0.60 per cént by weight excess of suilicient to produce about seven to ten inches of water pressure drop per foot of 15 of carbonaceous material based on catalytic ma terial weight. ' gas path through said mass, and removing heat 7. The method of regenerating a particle form suiilcient to kprevent- the temperature of regen solid, clay-type, catalytic material contaminated erating contact mass from rising above that by a carbonaceous deposit which comprises con which will damage the .contact mass, and return ing the regenerated contact mass in heated con 20 tinuously passing said material as a substantially compact column through a plurality of zones in'dition to the conversion acuer,A :1, " _' 'A ' which combustion occurs without substantial 4. The method of converting a hydrocarbon oil simultaneous removal of- heat, said combustion which comprises passing the oil ln vapor phase zones alternating with cooling zones in which and at conversion temperature into contact with a substantially compact downwardly moving mass 25 heat is removed by indirect heat exchange with a ñuid heat exchange medium, the temperature of particle-form solid catalytic materialof clay at all times being maintained between a minimum type in which conversion is eilected, the vapors temperature at which combustion will take place being introduced thereto at a flow rate substan from said mass. transferring contaminated con tially below that >which causes physical disturb ance of the moving mass. effecting substantially .complete separation of hydrocarbons from said ' and a wmaximum temperature at which the cat alytic material begins to suiîer heat damage, the 30 amount of burning in each combustion zone being limited to the burning oiî of 0.60 per cent by weight of carbonaceous material based on cat mass, «transferring contaminated contact mass to a regeneration zone and moving it downwardly therethrough as a substantially compact mov ins Supplying engen containing gasÄ thereto to burn contaminant therefrom, said gas alytic material weight. 35 being supplied at a ilow rate not in excess of suiliclent to Aproduce about six to eight inches of _water pressureI drop per foot of gas path ' through said mass, while removing heat suf clay type solid adsorbent material contaminated by a‘carbonaceous deposit which comprises con tinuously passing said material as a substan tially compact column through a plurality of. ' zones in which combustion occurs without sub 40 stantial rsimultaneous removal of heat. said com ficient to prevent the temperature of regenerating ‘ contact mass from rising above' that which will .damage the contact mass. and returning the regenerated contact mass in heated condition to ' 8. The method of regenerating a. particle form busticn zones alternating with cooling zones in which heat is removed by indirect heat exchange « » tating particle-form solid catalytic material of with a fluid heat exchange medium, „the tem perature at-all times being maintained betweenv a miniinum temperature at which combustion will take place and a maximum temperature at which the adsorbent material begins to suiIer heat damage, the amount of burning in each 50 combustion zone being limited to the burning clay type in which conversion is effected, the per cent by weight of carbonaceous material based ' the conversion zone. ‘ ~ A 5.' 'I'he method of converting a hydrocarbon oil which comprises passing the oil in vapor phase and at conversion temperature into contact with a substantially 'compact moving mass of gravi oiî of from about 0.05 per cent to about v0.60 vapors being introduced thereto at a flow rate on adsorbent material weight and the flow rate _ ' substantially below that which causes turbulence of the moving mass, effecting substantially com--` plete separatlonof hydrocarbons from said mass; 55 'transferrlng':;contaminated' contact mass to a regeneration'zone and moving it“ therethrough as a substantially = compact downwardly movingv of regeneration gases therethrough being not over sufficient to produce a pressure drop of about i? seven to ten inches of water'per _footof gasif path through said material. 9. The method of regenerating a particle form clay type solid adsorbent material contaminated ï" . massï‘supplying‘ oxygen containing gas thereto by a carbonaceous deposit which comprises con.-- '5 f ¿ to burn' contaminant therefrom, said gas being 60 tinuously passing said material as a substantially ~ ` supplied 'at a'ilow rate‘substantiallyvbelow that compact column through a plurality of zones in which causes turbulence of the moving mass, and which combustion occurs without substantial removing heat sumcient to prevent the tempera simultaneous removal of heat, said combustion . ture of regenerating contact mass from rising above that which will damage the contact mass, 65 zones alternating with cooling zones in which ` ~ t and returning the regenerated contact mass in heated Vcondition to- the conversion zone, the ilow rateol’ vapors ln the conversion section and heat is removed by indirect heat exchangel with a . iluid heat exchange medium, the temperature at all times being maintained between a minimum temperature at which combustion will take placeKY _. 'K to an amount giving not in excess of about six 70 and a maximum temperature at which the ad sorbent material begins to suiîer heat damage, to eight‘inches ci water pressure drop per foot the amount of burning in each combustion zone - of `path-of vapor or gas through said mass. being limited to the burning oiî of 0.60 per cent ‘6.2’ The _method of regenerating a particle form ` of gas vin the-'regenerator both being limited . . ' solid, clay'type, catalytic material contaminated by weight of carbonaceous material based'pn ad by a carbonaceous deposit which comprises con 75 sorbent material weight and the flow rate oi re- « 2,412,917 . generation gases therethrough being not over suf ‘ ilcient to produce a pressure drop of six to eight inches of water per toot of gas path through said material. . f 12 . vertedfproducts made per unit volume of catalyst employed and still at an amount not suilicient to produce a pressure drop in excess of about seven toten inches of water per foot of path 0f vapors through said- material, flowing> the rela- y _ 10. The ¿ method of converting a hydrocarbon oil which comprises passing the oil in vapor phase tively low contaminant content contact mass ma- ` and at conversion temperature into contact with , , terial therefrom into'aríd through a regeneration a a substantially compact moving mass of particle-A.' zone in' which 'said material flows" as a substan- ’ form solid clay-type catalytic material at al1 times at amoving temperature column high andenough is‘maintained to sup-f " f which co‘nversion is effected, the vapors being in-„r 10 tiallyeompact troduced thereto at a flow rate substantially lie-.fi port combustion and below a'temperature high low that which causes turbulence oi the moving „ enough to eil’ect heat damage to said material, mass, effecting substantially complete separation, 'burning contaminant from said material in a of hydrocarbons from said mass, transferring plurality of regenerative steps in each of which contaminated contact mass to a regeneration~ „. 15 no more than about 0.05 per cent to 0.60 per cent ' zone, supplying engen containing gas thereto> by weight of contaminant, based on contact mass to burn contaminant therefrom, said burning be- p , weight. is removed from said material and in each ing accomplished by passing said material as a of which no substantial removal ofvheat is ef substantially compact column through a plurality" fected. between said burning zones removing heat t of zones in which combustion occurs without sub 20 from said material by indirect heat exchange stantial simultaneous removal of heat, said com- f with a iiui‘d heat exchange medium, the iiow rate bustion zones alternating with cooling zones inv >of regeneration gases being high to effect good which heat is removedby indirect heat exchange penetration of said material but not suilicient to with a fluid heat exchange medium, the tempera produce a pressure drop in excess of about seven ture at all times being, maintained between a 25 to ten inches of water per foot lof path of gas minimum temperature at which combustion will through said'material and returning the regen take place and a maximum temperature at which erated contact mass in heated condition »to the the catalytic material begins to suiTer heat'dam reaction zone. , `. age. the amount of burning in each combustion - 13. A unitary process for conversion of heavy zone being limited to the burning „oil of from 30 hydrocarbons to lighter hydrocarbons in the pres about 0.05 per cent to about 0.60 per cent by ence of a catalytic contact mass oi’ particle form, weight of carbonaceous material based on cata-V clay type, solid adsorptive material comprising lytic material weight, and- returning the regener-_` the steps of ñowing the contact mass material as ated catalytic 'material in heated condition into ' a substantially compact moving column through contact with oil vapor. ' f . 35 a reaction‘zone, flowing a stream of hydrocarbons 1l. The method of converting a hydrocarbon heated to conversion temperatures therethrough oil which comprises passing the oil in vapor phase at a high flow rate conducive to relatively low de and at conversion temperature into contact with posits of contaminant on catalyst relative to con-. a substantially compact moving mass of particle ' verted products made per unit volume of catalyst form solid clay-type catalytic material in which 40 employed and still at an amount not suiñcient conversion is eii'ected, the yvapors being intro to produce a pressure drop in excess of about six duced thereto at a ñow rate substantially below` to eight inches of water per ioot of path of vapors l. that which causes turbulence of the moving mass, . through said material, ilowing the relatively low ‘ eil’ecting substantially complete separation of hy- _ Y contaminant content contact mass material drocarbons fromV said mass-transferring con 45 therefrom into and through a regeneration zone taminated contact mass to a regeneration zone, in which said material ilows as a substantially compact moving column and is maintained at all times at a temperature high enough to support supplying oxygen containing gas thereto to burn contaminant therefrom, said burning being ac complished by passing said material as a substan- . combustion and below a temperature high enough to effect heat damage to said material, burning tially compact column throughs plurality~of zones in which'combustion occurs without sub contaminant from said material in a plurality of regenerative steps in each of which no more than bustion zones alternating with cooling zones in ' _ 0.60 per cent by weight of contaminant, based which heat is removed by indirect heat exchangey on contact mass weight, is removed from said with a iiuid heat exchange medium, the tempera 55 material and in each of which no substantial re stantial simultaneous removal of heat, said com ture at all times being maintained between a minimum temperature at which combustion will take place and a maximum temperature at which the catalytic material begins tosuffer lheat dam age. the amount of burning in each combustionf 60 zone being limited to the burning off of 0‘60 per cent by weight of carbonaceous material based on . catalytic material weight and returning the re generated contact mass in heated condition into contact with oil vapor. i medium, the ñow rate of regeneration gases being high to eiîect good penetration of said material but not suilìcient to produce a pressure drop in excess of about six to eight inches of water per foot of path of gas through said material and returning the regenerated contact mass in heated 65 condition to the reaction zone. 12. A unitary process for conversion of heavy ‘ hydrocarbons to lighter hydrocarbons in the pres ence of a catalytic contact mass of particle form, clay type. solid adsorptive material comprising > the steps of ilowing the contact mass material as 70 a substantially compact moving column through moval of heat is effected, between said burning zones removingpheat from said material by. indi- rect heat` exchange with a fluid heat exchange ’ , 14.»The method Aof converting a hydrocarbon oil which comprises passing the oil in vapor. phase and at conversion temperature into con tact with a substantially compact moving mass of downwardly flowing particle-form solid clay~type catalytic material in which conversion is effected. a reaction zone, flowing a stream of hydrocarbons the vapors being introduced thereto at a iiow rate heated to conversion temperatures therethrough substantially below that which causes physical at a high flow rate conducive to relatively low de- „ ` of the moving mass, the iiow rate posits of contaminant on catalyst relative to con 75 disturbance being such as to give a pressure drop of not over 2,412,917 14 therethrough as asubstantialiy compact moving n seven 'to thirteen inches of water per foot of path of vapor through contact mass for contact mass materials of` apparent densities in the reactor ranging from» about 0.6 to about 1.1, the pressure drop,\within the indicated range being propor tional to the said apparent density, effecting Vsub stantially complete separation ofhydrocarbons from said mass, transferring contaminated con tact mass ‘to a regeneration zone and moving it mass, supplying oxygen' containing gas thereto to burn contaminant therefrom and returning -the regenerated contact mass in heated condition to 5 the conversion zone. ' v THOMAS P. SIMPSON. JOHN W. PAYNE. ‘ JOHN A. CROWLEY, JR.