US2452569A

US2452569A - Process of treating hydrocarbons in presence of hot contact masses

Info

Publication number: US2452569A
Application number: US695921A
Authority: US
Inventors: Eugene J Houdry
Original assignee: Houdry Process Corp
Current assignee: Houdry Process Corp
Priority date: 1946-09-10
Filing date: 1946-09-10
Publication date: 1948-11-02
Anticipated expiration: 1965-11-02

Description

E. J. PROCESS OF TREATING HYDROCARBONS IN Nov. 2, W48? HOUDRY PRESENCE OF HOT CONTACT MASSES Filed sept 1o, 194e J M m n.

Fal/ww a! qu al mENroR.

Patented Nov. 2, 1948 PROiCESS 0F TRETHNG HROCARBNS m PRESENCE 0F HUT CONTACT MASSES Eugene 3. Hendry, Ardmore, lia., assigner to i-lloudry Process Corporation, Wilmington, Del., a corporation of Delaware application' september 10,1946, serai No. 695,921

18 Claims.

My invention relates to the art of treating hydrocarbon material in a converter containing at least one pair of contact zones containing contact material and having between them a mixing zone or mixing chamber utilizable in the manner hereinafter described.

With the contact material in the respective mixing zones at conversion temperature, hydrocarbon material is charged continuously into the converter shell and hydrocarbon products are continuously Withdrawn therefrom. In accordance with the invention, the temperature of the charge of hydrocarbon material is elevated in response to passagethereof through one of the contact zones. The converted products enter a mixing zone or mixing chamber as aforesaid where they are cooled prior to admission of all or a part thereof to the succeeding contact zone wherein the contact material, in turn, elevates the temperature of the hydrocarbon material passing therethrough. In said mixing zone, the

converted products may be cooled in various ways as hereinafter described. Preferably, however, a stream of suitable hydrocarbon material is charged continuously into this mixing zone, the temperature of this hydrocarbon material' being suitably lower than that of the converted products with which it mixes. Accordingly, the temperature of the incoming hydrocarbon material is elevated for subsequent conversion in the succeeding contact zone into which it passes along with some or all of the converted products as cooled byexohange of heat effected during the described mixing operation. In accordance with one aspect of the invention, the aforesaid mixing zone or mixing chamber may serve as a coolin zone.

In one application of the invention, the aforesaid' contact zones comprise catalytic contact material in the presence of which a selected conversion operation may proceed as hereinafter described. In another application of the invention, the contact material in said contact zones is substantially inert in a catalytic sense and, in the presence thereof, vapors are produced, by vaporization and viscosity-breaking, from heavy hydrocarbon materials such as entire, reduced or topped crudes, residual or heavy bottoms, distillation residuums, etc., all of which contain heavy, difcultly vaporizable fractions.

(Gl. 19H- 49) stored in said contact material is in excess oi that y required for supplying vreaction heat. such excess heat being utilized for conducting the described heat-exchange operation in the mixing zone which intervenes between the contact zones. More particularly, this excess heat is utilized for elevating the temperature of hydrocarbon material passing into said mixing zone whereby such hydrocarbon material is prepared for subsequent conversion in the succeeding contact zone.

'Various other objects, advantages and features filed October 6, 1943 (now abandoned).

In order to conduct the desiredreactions or y conversions, it is necessary for the aforesa.id con tact material in the contact zones to have heat stored therein. In accordance with an important feature of the invention. the heat which is thus For an understanding of my invention and for an illustration of various arrangements with which the invention may be practiced, reference is to be had to the accompanying drawing, in which:

Figure l is a diagrammatic transverse sectional view showing a converter;

Fig. 2 is a similar view showing a modification of the converter;

Fig. 3 is an enlarged, partly diagrammatic. fragmentary vertical sectional view showing a modified arrangement for insuring vaporization of added charge between sections of a converter;

Fig. d is a vertical sectional view similar to Fig. 3 showing another modification; and

Fig. 5 is a fragmentary partly diagrammatic sectional View of a vertically disposed converter showing still another modication.

Although as hereinafter described, the invention is not to be so limited, the following detailed description relates to contact masses of the fixed bed type. Thus, referring to Fig. 1, I have shown a converter or conversion arrangement comprising three contact zones each containing contact material or contact masses a, b and c supported individually by suitable apertured partitionslaly and arranged in a series within a shell 3 which should be suitably insulated against heat losses by any suitable means, not shown, the pressure within the shell 3 being selected in view of the type of reaction which is conducted therein. A charge of hydrocarbon material of the character hereinafter described is sent into one end'of the shell 3 by line 4 and reaction products are removed from the other end thereof by line 5. Be-

' tween contact masses a and b, 'there is a mixing zone, space or chamber d and. between contact masses b and c. there is a mixing zone, space or chamber e. Into each of such mixing zones or chambers, an additional charge of hydrocarbon material is admitted by a line 6 having valved branches 8d and 3e opening into chambers d and e, respectively. When the hydrocarbon material last named is either partially or entirely in the liquid phase, each of these valved branches may terminate, if desired, in a suitable nozzle Gf by which the incoming liquid hydrocarbon material is atomized. In lieu of the nozzles 8f, any other suitable atomizing arrangement may be utilized, Alternatively. a plurality of separate shells may be provided, each defining a contact zone and each containing contact material. These separate shellsmay be connected together in communicating relation and one' of the aforesaid branch lines may be connected between each pair of contact zones.

When the arrangement of Fig. 1 is to be utilized for cracking the aforesaid hydrocarbonmaterial, each of the contact masses a, b and c, to suitable extent, should be formed from silica-zirconia catalytic material, silica-alumina catalytic material of natural or synthetic origin or from `other suitable catalytic contact material capable of effecting the desired reaction. If the catalytic material itself does not have sulcient density and heat-absorbing capacity to retain the requisite amount of heat to support the operation, it may have added thereto or mingled therewith a suitable amount of inert material having the requisite heat-absorbing characteristics as described in U. S. Letters Patent 2,414,812. With respect to the foregoing, theY proportion of catalytic material to inert heat-absorbing material may range from 1:4 to 53:1 or otherwise as desirable. Further different proportions of`such materials may be utilized for different contact masses. A number of suitable inert materials are mentioned in U. S. Letters Patent 2,423,865. Fused alumina and fused alumina silica (refractory material in the proportion of about 70% alumina and the remainder largely silica) have been found to be particularly suitable for this purpose.

Assuming that the temperature of the contact masses a, b and c has been elevated to suitable extent toward the upper level of a conversion range such, for example, as '750 F. to 1200" F. which is is cracked and the resulting hydrocarbon products leave the shell 3 by way of the line 6. During the on-stream period, a definite quantity of heat is withdrawn from thecontact masses to crack the hydrocarbon material passing therethrough and also to varporize liquid phase hydrocarbon material, if any, undergoing reaction in said contact masses. The described on-stream period is terminated before the temperature of the contact masses a, b and c reaches the lower level of the aforesaid conversion range.

The amount of carbonaceous material deposited in or on contact material during an on-stream period is controllable within wide limits 4by increase or decrease in severity of reaction conditions, this applying particularly to the contact time and to the temperature of the contact mate rial during such an on-stream period. Hence, by selecting the proper conditions, a suiiicient amount of carbonaceous material may be deposited in or on the contact masses a. b and c during the onstream period first named to insure production,

when the carbonaceous material is burned during a regenerating operation, of a quantity of heat which is stored in said contact masses in excess of the aforesaid definite quantity of heat which is withdrawn therefrom for the purpose stated. During this regenerating operation, air or other oxidizing medium is passed through the contact masses in the direction indicated or in the opposite direction and the temperature of such air or equivalent should be 750 F. or higher in order to prevent the temperature of local areas of said contact masses from going below an acceptable combustion level.

As a result of such a regenerating operation, the temperature of the contact masses a, b and c is -elevated toward the upper level of the described conversion range. In the event that the carbonaceous material which was deposited during the 'effective as regards catalytic cracking of hydrocarbon material of the character described immediately below and, with the valves shown in Fig. 1, positioned for on-stream operation, a charge of suitable hydrocarbon material such, for example, as heavy bottoms, which may be partly vapor, partly liquid or totally liquid, or totally vaporized gas oil may be passed continuously into the shell 3 by way of the line 4. Simultaneously, additional charges of hydrocarbon material of the same character as that traversing the line 4, or of other suitable character as desired, may be passed continuously into the respective chambers d and e by way of the respective branches 6d, 6e of line 6. The hydrocarbon material admitted to the shell 3 by way of the line 4 passes through the contact masses a. b and c in succession. The additional hydrocarbon material admitted to the shell 3 by way of the branch line 8d passes through the. contact masses b and c in succession` whereas the additional hydrocarbon material admitted to the shell 3 by way of the branch -line 6e passes through the single contact mass c. While passing through the contact masses a, b and c, the aforesaid hydrocarbon material from al1 sources on-stream period first named is suiiicient, when burned during the regenerating operation, to store in the contact masses moreexcess heat than re quired or desired, the desired proportion of the heat generated during the burning operation may be removed from the contact masses by the regenerating medium, for example, air or a mixture of air and flue gases, or by other suitable heat exchange.

In explanation oi. my invention, it should be noted that, ordinarily, the temperature of the hydrocarbon material traversing the line 4 is lower than the temperature of the contact mass a. Accordingly elevation in temperature and simultaneous cracking of such hydrocarbon material occurs as a result of passage thereof through said contact mass a and, at this elevated temperature, the resulting cracked hydrocarbon products pass continuously into vthe chamber d. It is a distinct feature of the invention that the temperature of the hydrocarbon material which is continuously entering the chamber d by way of the branch line 6d is lower, to suitable extent, than the aforesaid elevated temperature of, the aforesaid cracked hydrocarbon products entering said chamber d from the contact mass a. Accordingly, heat is transferred from said cracked products to the Y hydrocarbon material last named and, at an inin temperature, pass continuously from the conannate@ tioned, the resulting mixture. at a temperature' lower than that of the contact mass'c, entering and traversing the latter with consequent elevation in temperature thereof toward that of said contact vmass c. The finalv cracking operation occurs in the contact mass c and, thereafter, the

cracked products pass from the shell 3 by way of the line ii.

In view of the foregoing, it will be understood that, as regards the heat stored in the contact masses a, b and c as a result of the described regenerating operation, a large part thereof was withdrawn from said contact masses during the on-stream period last named in order to crack the hydrocarbon material passing therethrough. In addition, the hydrocarbon material last named withdrew from the contact masses a and b heat which ln the chambers d and e, was utilized in a Within the purview of the invention, the hydrocarbon material which is charged into the shell 3 either by the line 4 or by the branch linesl 6d and 6e may be recycle stock. If so, it is desirable that fresh stock be charged into the shell 3 simultaneously with the passage of recycle stock thereinto. Thus. recycle stock may be charged through the line t and fresh'stock by way of the branch lines Bd and 8e. Or, if desired, recycle stock may be charged by way of the branch lines last noted and fresh stock by way of theline For cracking of hydrocarbons, overall rates for the entire series of contact masses will range from l/2:1 (one-half volume of charge measured as liquid to one volume of catalyst per hour) up to 3:1 with flow rates in the individual sections of from 11/2:1 to 10:1.

In accordance with a detailed feature of the invention, each of the contact masses may surprise, in addition to the contact material having high heat-absorbing capacity, a catalyst having low cracking activity either with or without any suitable desulphurizing catalyst such as the oxides of nickel, cobalt, etc.von a suitable inert support. Or, suitable 'catalytic contact material such as is formed from metals and compounds of chromium,

useful manner to heat the incoming hydrocarbon material traversing the branch lines 6d and de. By adjustment of the valves in the branch lines ed, Se or by. temperature control of the hydrocarbon material traversing these branch lines, the temperature off the hydrocarbon mixtures in the respective chambers d and e may be selected so that the hydrocarbon mixtures last named withdraw desired amounts of. excess heat from the respective contact masses b and c as they pass therethrough.

Accordingly, at the end of said last named onstream period, the heat (including excess heat) previously stored in the contact masses a, b and c has been withdrawn therefrom as described above. During this on-stream period, carbonaceous material was again deposited in and on said contact masses. The amount of this carbonaceous mate-1 rial is sumcient so that, when burned, during a properly controlled subsequent regenerating operation, a quantity of heat is stored in the contact masses in excess 'of the endothermic reaction heat of the succeeding ori-stream cracking reaction, such excess heat being utilized in the manner described for elevating the temperature of hydrocarbon material entering the chambers d and e by way of the respective branch lines @d and te. In accordance with my invention, then, ori-stream and regenerating operations of the character referred to proceed alternately for the useful purposes described in the specication.

In order to improve the octane rating of the resulting crackedv products and to minimize cracking of charge and deposition of carbonaceous material in any heating equipment traversed by the hydrocarbon material priorto admission thereof to the chambers d and e by way of the respective branch lines 6d and 6e, it is desirable for such hydrocarbon material to be maintained under conditions such that it is substantially in the liquid phase and any prior substantial cracking thereof into lower boiling hydrocarbons of the gasoline type is avoided, the temperature of this liquid phase hydrocarbon material being at least somewhat lower than the temperature of the hydrocarbon products passing from the respective contact masses a and b, and substantially lower than that of the respective contact masses b and c.

vanadium or the like may be utilized for dehydro-v genating hydrocarbons. When the contact mass? es are formed from catalytic contact material of the character described immediately above, it will be understood that the process of my invention is operative in the manner previously described.

It was hereinbefore stated that the hydrocarbon material traversing the. line and the branch lines y 6d, 6e may be totally -vaporized or, alternatively,

. that the aforesaid hydrocarbon material may be partly liquid and partly vapor or totally liquid. If the chambers d and e receive hydrocarbon material. at least partially in the liquid phase, complete or incomplete vaporization thereof may be effected in said chambers d and e, as desired. The extent of such vapori'zation depends upon known factors such as the efficiency of the heatexchanging operation, the Weight ratio of the materials which are subjected to heat exchange therein, the relative temperatures and character of these materials, etc. i

As previously described, heat is transferred, in the chambers d and e, from the hot converted products leaving the respective contact masses a and b tc cooler hydrocarbon material entering said chambers by way of the respective branch lines dd and te. The invention, however, is not to be thus limited, Thus, for the purpose stated.

cooler material such as steam may be admitted to said chambers d and e or, alternatively, a suitable coil, or equivalent, may' be disposed in each of said chambers, each coil being traversed. by cooling material having temperature lower than that of the hot converted products which issue fromv the contact masses a and b. Accordingly, as the 'oper- In accordance with the invention, the arrangement of Fig. 1 may be utilized to vaporize andy viscosity-break heavy hydrocarbon material of the character hereinbefore described which is introduced (into the shell 3 while at least partially in the liquid phase. If so, each of the contact masses a. b and c should be 'formed entirely or substantially so from pieces of any suitable material which is substantially inert catalytically such, for example, as hereinbefore described, heat resistant quartz and quartz pebbles, fused silica, etc, The aforesaid pieces of material should have approximately uniform surface area and volume. They may be of any suitable shape and the size thereof may be selected as desired. If desired, they may have approximately spherical or chunk-like configuration and the major dimension thereof may range between 1/4 to 3A of an inch, for example.

When the arrangement of Fig. 1 is to be utilized for vaporizing and viscosity-breaking purposes as described above, the contact masses a, b and c should have stored therein heat for effecting the subsequent on-stream reaction together with excess heat for elevating the temperature of the incoming hydrocarbon material traversing the branch lines 6d, 6c. In addition, the temperature of the contact masses should be in a range, forA example, 800 F. to l100 F., which is effective as regards vaporizaticn and viscosity-breaking of liquid phase, heavy hydrocarbon material passed into engagement therewith. In connection with the foregoing, the upper level of the aforesaid range should be such, for example 110l F. so, that, at the contact time employed, for example, not exceeding fifteen seconds and preferably not in excess oi about five seconds, there is no substantial cracking of the hydrocarbon material into lower boiling hydrocarbons of the gasoline type, the contact time being the time required for passage through the contact masses a, b and c of those vapors which are introduced thereto or produced therein.

Assuming that the valves shown in Fig. l are positioned for on-stream operation, that the contact masses a, b and c have stored therein reaction and excess heat, and that the temperature thereof has been elevated toward the upper level of the described vaporizing and viscosity-breaking range, a stream of suitable material such for example, as heavy hydrocarbon material, either partially or entirely in the liquid phase together, if desired, with suitable vapors or hydrocarbon vapors alone is charged continuously into the shell 3 by way of the line 4. Ordinarily, the temperature of this stream of material is less than that of the contact mass a and, hence, when it passes therethrough, there is resultant elevation in temperature thereof toward that of the contact mass from which hot vapors pass into the chamberd. Simultaneously, streams of material consisting either entirely or partially of heavy uliquid hydrocarbon material are charged continuously into the chambers d and e by Way of the respective branch lines, the temperature of the streams of material last named being substantially lower than that of the vapors issuing from the contact masses a and b.

In a manner corresponding substantially with ized and converted, i. e. viscosity-broken,

Provided that the temperature of the contact masses a, b and c is within the proper range and that the contact time. as determined by known factors, is suillciently short as hereinbefore described, the heat transferred, during the operation described above, from the contact masses to the liquid phase hydrocarbon material effectively vaporizes and viscosity-breaks lthe difficulty vaporlzed components thereof. As a result, there is formed distillate hydrocarbon material which is principally higher boiling than gasoline, this material passing from the shell 3 by way of the line 5.

In accordance with the invention, the temperature and/or rate of flow of the hydrocarbon material traversing said branch lines 8d, 8e may be Avaried to change the temperature oi the aforesaid mixtures in the respective chambers d and e in a desired manner. To this end, suitable means. not shown, may be provided for jointly or individually varying the temperature of the material entering the shell 3 by way of the branch lines 6d, 6e. Or, the valves in the respective branch lines may be adjusted to vary the rate of flow of such material. Accordingly, by controls suitably effected, the operating temperatures of the contact masses b and c may be related to cach other and also to the operating temperature of the contact mass a in a desired manner. Preferably but not necessarily, by the aforesaid controls or equivalent, the temperatures of all of the contact masses are so maintained that, at any selected time. they are approximately at the same level.

It has been hereinbefore stated that the temperature of the hydrocarbon material charged into the chambers d and e by the respective branch lines 6d and 6e is lower to suitable extent than the vapors passing into said chambers from the respective contact masses a and b. In general, the temperature of such hydrocarbon material may be substantially lower, for example, 75 F. to 125 F., than that of the aforesaid vapors. In any event, it is important for the hydrocarbon material to be introduced into the chambers d and e under conditions such that approximately the entire quantity .of excess heat in the contact masses is absorbed thereby.

There may be any desired number of contact masses in the series and the depth oi' these contact masses may be such as is suitable and desirable, f'or example, from one foot to six feet, more or less. The depth of individual contact masses may differ so as to provide equivalent or modiiled tim'es of contact. Thus, when additional charge is admitted to a chamber d or e with no withdrawal of products therefrom, the succeeding contact mass may be of increased depth or volume to provide equivalency of contact vwith the preceding contact mass. Also, one or more ot the contact masses may be of increased depth or volume to compensate for increased refractoriness of partially converted charging stock.

It is desirable, in connection with the invention as herein described, for the cycle o! operation to be relatively short. Preferably, the duration of each on-stream period should not exceed about thirty minutes and, usually, the duration of each regenerating period is about the same as the on-stream period.

In a preferred application of the invention, but not necessarily, there is a balance, except for heat losses from the equipment, as by radiation, between the heat stored in the contact masses at the start of an on-stream period and the heat withdrawn from said contact masses for eifecting the on-stream reaction and elevating the temperature of the additional charges of material, this balance being controlled by theextent of deposition of carbonaceous material which; in turn, is readily controlled, for example, by adjusting the quantity of feed, the rate of flow to the various contact masses or of other conditions adecting the extent of conversion oi the charged hydrocarbon material in carbonaceous material.

In Fig. 2, I have shown an arrangement which, generally. is similar to Fig. 1 and, to common parts, the same reference characters have been applied. The variationin Fig. 2 consists in the provision of outlet line l with valved branches id and 'ie by which a portion of the reaction products may be withdrawn from one or both of the chambers or spaces d and e.v Line i may join outlet line Ei ifl desired and as indicated. With the arrangement of Fig. 2, products may be withdrawn from the chambers d and e by way of the respective branch lines ld and 'le in an amount approximately the same as the amount of the material which is admittedthereto by the including the chambers d, e thereof. It was also stated with respect to those forms of the invention wherein catalytic contact material is utilized that, in said chambers d and e, the operation may be alternative, namely, there may be either partial vaporization or complete vaporization of the liquid phase material. When complete vaporlzation is desired, provision should be made to insure completion of that operation before any of the liquid charge reaches the subsequent contact masses and any charge not completely vaporized should be removed or kept out of contact with the active contact material. Accordingly, a vapor space or chamber of adequate size may be provided between adjacent contact masses to insure complete vaporization, or means to intercept unvaporized charge may be provided. When the available vapors leaving a contact mass are passed countercurrently to additional charge entering as a ne spray or in atomized condition with vapor to liquid ratio of 6:1 by volume (liquidment of liquid particles issuing from feed line 6 through one .or more spray nozzles 8' by interposition of a layer 9 of highly porous inert material inthe form of grains, fragments or molded pieces such for example as the carrier material disclosed in U. S. Patent No. 1,818,403 issued .August 11, 1931 to Alfred Joseph.. Layer 9 is of suitable thickness, as i to 18 inches for exam- In Fig. 3 l

ple, depending upon the extent of the vapor space into which nozzles discharge and the quantity and character of liquid supplied by the latter. `This, porous layer will retain the liquid particles until vaporization on extended surfaces takes place. A part of the vapors issuing from contact mass a may be withdrawn by valved line 7'; a, baille lu in the form of reticulated material or a perforatedv plate may be mounted if de sired so as to divert a part of the reaction products from mass a toward outlet if and thus prevent or minimize the mingling oi additional charge from feed line 6' with the reaction products withdrawn by line l'.

In Fig. da reaction products from mass d pass into a chamber il'. having a vcentrally disposed outlet im in a dished bane plate i2 which serves to constriet such products as they move toward mass b. ibutlet 22a is preferably in the form of venturi nozzle into which, or adjacent to which, is located spray nozzle d for additional charge from line t". The mingled reaction products and additional charge impinge against an in p wardly dished baille member it which directs the mixture outwardly and bach toward baiiie l2 until themixture passes around the outer edges .of baiie member i3 into chamber id and thence into'the next contact mass b. This arrangement extends the path of flow of'the mingled reaction products and atomized charge and gives the latter time -to become vaporized before entering mass lz. Moreover, reaction products entirely free of any additional charge from line d" can be withdrawn from chamber Ui by line l". Steam or other vaporizing medium may be vmingled with charge issuing from nozzle d or steam may be added before or as the charge impinges on baille i3 (by means not shown) to assist in vaporizatlon o liquid nlm on the baiiie.

Fig. 5 shows a fragmentary section of a vertically disposed converter wherein reaction' products from contact mass ct' pass into a chamber against additional liquid charge issuing countercurrently from a series of nozzles l@ supplied by line it. Unvaporized liquid is intercepted by a layer of inert porous material ia of the same type as used for layer d of Fig. 3. Any liquid which makes its way through layer le is caught by a.` slanting plate 2@ mounted therebelow equipped with a valved drain pipe 20a. Plate 2!) has a multiplicity of vents provided by short pipes 2do extending above the upper surface of the plate, these pipes having their open ends bent over toward plate iii to exclude any liquid dropping fromporous layer i9 but to permit passage of gases and vapors to chamber 2i below'plate 2li and thence into contact mass b. Any burnabie deposits which accumulate on p0rous mass vQ in Fig. 3 or on mass i9 of Fig. 5 are burned away during subsequent regenerating operations with little @if any eect upon the cycle of operation.

Arrangements of the character described above may be `utilized when total vaporlzation is to be effected in a chamber between adjacent contact masses. However, it shall be understood that, except as set forth in the appended claims, there is to be no restriction of the invention to an operation involving total vaporization in a chamber as described above.

It is a feature of the invention that, as regards the various aspects of the invention, the material undergoing conversion in the series of contact masses is subjected to undulating or oscillating temperature conditions as it passes through l said contact masses. Thus, the material rises in temperature as it passes through each contact mass and fails in temperature in the chamber between each pair of contact masses. As stated, the converter of the invention may comprises. desired number oi' contact masses. If the number is small, as two to four, and if comparatively large amounts of additional charge are introduced between the contact masses, severe conditions may be selected to effect substantial conversion and to produce comparatively large quantities of deposited carbonaceous material. Under these circumstances, the temperature swing within the mass (diflerence between the average contact mass temperatures at the beginning and end, respectively, oi' the on-stream periods) may be wide, as up to 250 F. However, when the same extent of conversion is desired utilizing more contact masses, a greater number of smaller additions of additional charge can be made, and accordingly, less severe operating conditions may be required for the same total yield, thereby giving smaller quantities of carbonaceous material and narrow temperature swings (as from 40 F. to 120 F.) commensurate with the smaller increments of conversion in each mass. Operation of an increased number of contact masses is not limited to maintaining narrower temperature swings for, obviously, severe operating conditions may be employed to attain maximum conversion of a maximum quantity of charge.

In accordance with present preferred practice, the same type oi conversion occurs in all oi the contact masses disposed within a con- 'cipally by reason of the fact that the hydrocarbon material traversing the branch lines 6d and 6e, before conversion, is subjected to temperature elevation in the converter. When liquid hydrocarbon material traverses these branch lines, it may be heated to such extent as desirable and it may be entirely unheated if free-flowing at room temperature.

It was hereinbefore stated, with respect to various forms of the invention that, ordinarily, the material entering the shell 3 by way o! the line l has temperature lower than that of the contact mass a. Should the temperature of this material be higher than that of said contact mass a, it will be recognized that excess heat is not withdrawn therefrom. However, under the circumstances last recited, hydrocarbon material, by another branch of the line 6, may be charged into the chamber in advance of the contact mass a. If the temperature of this hydrocarbon material is suitably lower than that of `said higher temperature material, a resulting eficaces 12 yIn the preceding part of this speciiication, the specic description relates to converters of the fixed bed type. However, the invention is not to be so limited. As well, from some of its broadupon passage therethrough.

er aspects, the invention relates to converter arrangements wherein the contact material, as the 'reaction proceeds, may move through the sev-J eral contact zones, either separately through each zone or successively through several of such zones, amixing chamber being disposed between each pair of said zones for the purpose described.

For purposes of explanation and without limitation of the invention, the following examples are'included as a part of this specification.

Example I A three section converter conforming to that shown in Fig. 2 with contact masses two feet in depth composed 50% by volume of active adsorptive cracking catalyst in pelleted form and 50% by Volume of fused alumina and silica grain of approximately the same size as the catalyst pellets, the latter being synthetic silicaalumina, was utilized for the conversion of East Texas gas oil (boiling range 42o-'760 F.). At one end vaporized fresh charge at about 800 F. was admitted to the converter at an overall rate based on total volume of catalyst of 3:4 (liquid volume of charge per volume of catalyst per hour), the rate for each section of catalyst being 9:4. Product withdrawn from the opposite end oi the converter was-fractionated and'unconverted recycle stock was utilized as additional charge between the sections of the contact masses. Such additional charge having about the same boiling range as the fresh charge to the converter was sprayed into each of the vapor spaces d and e (12 feet long in this instance) counter-current to the reaction products issuing from contact masses a and b. The quantity oi additional charge admitted to each vapor space was approximately 1/3 of the original charge to the converter. From each of the *vapor spaces there was withdrawn approximately 1/3 of the reaction products issuing from the preceding contact mass, such vwithdrawals being added to the reaction products withdrawn from the said opposite end of the converter. On-stream periods were 10 minutes, followed by purging and burning or regenerating periods totalling 20 minutes, three converters being utilized in known manner to maintain continuous production. During the burning phase of regeneration (approximately 10 minutes) air preheated to about. 800 F. was admitted at one end of the converter, and additional air was admitted between the sections of contact mass. AThreughout the cycleno part of any of the contact masses reached a temperature in excess of about 1100 F., the average contact mass temperature at the beginning of on-stream periods being about 940 F. and at the end of these periods about 845 F. Thus the average on-stream temperature was approximately degrees below the average' regeneration temperature. The yield of condensed motor gasoline was approximately 47% by volume of the charge. Approximately '75% of the heat of combustion of catalyst deposit, exclusive of losses through fumes and converter walls, was utilized to supply heat ofreaction and to prepare the charges for conversion.

the boiling range of Example I.

13 Example II The cbnverter was made up of three sections in all `respects similar to the converter in Example I except that the vapor space between l adjacent sections of contact mass was six feet instead of 12 feet. The contact mass was similar to that set forth in Example I. The same feed stock for conversion was utilized and the same general method of operation. The fresh feed was sent into one end Aof the converter at an overall charge rate basedl on total quantity of catalyst of 1:1 (liquid volume of charge per volume of catalyst per hour) and additional The average contact mass temperature at the beginning of the on-stream periods was about 920 F. and at the end of the on-stream period about 845 F., giving an average spread of about 75 F. The yield of condensed motor gasoline was approximately 35% by volume of the charge of fresh feed.

Example III The operation was conducted in a three sectional converter conforming to that shown in Fig. 2 with six foot vapor spaces between contact masses. The general method of operation was as in Examples I and II except that the charge sent into one end of the converter was a mixture of recycle stock from the fractionator and fresh East Texas gas oil of the same boiling range as in Example I, the ratio of recycle to fresh charge being 2: 1. The mixture was charged to the converter at an overall feed rate of about 1:1 (liquid volume of charge per volume of catalyst per hour) based on the quantity of catalyst in the three contact masses. The additional charge between sections was fresh East Texas gas oil, the additions sprayed into vapor spaces d and e being each approximately 1/6 of the quantity of mixed feed charged to the converter. Withdrawals from the two vapor spaces were approximately 1/6 of the products from each preceding contact'mass. The average catalyst temperature at the beginning of the on-stream period was 970 F. and at the end of the on-stream period about 870 F., giving an average spread of about 100 F. 'The yield of motor gasoline based on total fresh East Texas charge to the operation was about 52%.

Example IV The operation was conducted in a two section converter of the type indicated in Fig. 1, each contact mass section being four feet in depth with a six foot central vapor 'space between the two sections. The contact mass was a 50-50 blend of active adsorptive silica-alumina cracking catalyst in pelleted form and fused alumina and silica-grain of approximately the same size. The charging stock was East Texas gas oil of Additional charge was sent into the converter between the two contact masses but there was no withdrawal of products from the central vapor space. Fresh .gas oil was charged partly to one,end of the being based on total amount ofA catalyst in both masses. The additional charge to the central vapor space was fresh gas oil in an amount approximately 20% by volume of the' total feedto therst section. For regeneration the regenerating medium was fed to the first section and withdrawal of fumes was from the opposite end of the converter.A The average temperature oi' the contact mass at the beginning of the on-streani period was 995 F. and at the end of the on-stream period 885 F., giving an average temperature spread of about 110. The yield of gasoline of 10 Reid vapor pressure was 65% by volume of the fresh charge.

28% by weight of fresh charge and had the following composition byweight.

. Per cent by weight. Hydrogen 0.5 Methane 7.0 Ethane ..--2 4.3 Ethylene 4.8 Propane 10.3 Propene 21.1 Isobutane 19.2 N-butane ...a- L--- 4.6 Isobutylene 4.1 N-butene 10.1 Isopentane 9.0 N-pentanes 0.6 Pentenes 4.4

Example V The operation was conducted in a'converter having four sections of 'contact mass, the depth of mass in each section being two feet with vapor spaces between adjacent sections of four feet. As in the other examples the contact masses were-5,0- blends of active silica-alumina cracking catalyst and fused alumina and silica grain.

The charge to the rst section of the converter was unconverted recycle stock from the fractionator (boiling range approximately 420 F. to 750? F.) The rate of charge to the first section was 11/2z1 (liquid volume of charge per volume of catalyst per hour) based on total amount of catalyst in all four sections. Additions of charg- Cil ing stock were made in the three vapor spaces between adjacent sections of catalyst, this addil charge sent into each vsuch vapor space. The op-4 erating periods were ten minutes on-stream and 20 minutes in regeneration. During regeneration fumes were vented from the central vapor space and from both ends of the converter while the regenerating medium, air, was admitted at 940 F. to the other two vapor spaces. The average oo ntact mass temperature at the beginning of the on-stream operation was about 975 F. and at the en d of the on-stream operation about 860 F., so that the average on-stream temperature was approximately F. below the average regenerating temperature. The yield of motor gasoline (of about 410 F. end point) was about 70% by volume of thefresh East Texas gas oi1.charged.

the gasoline having a Reid vapor pressure of 10 lbs. andoctane rating (C. F. R. research method) The gas produced amounted to' A 15 'of 91.` Inthis instance the gasoline yield -reprelsented the total'liquidmecovery from the operation. Additional liquid couldhave been produced by polymerization and alkylation' from-the remaining-ilxed gases which were high in unsaturates and iso-compounds.

Example VI A converter having three separate contact` masses formed from pieces of fused alumina and silica each having a major transverse dimension of about 1A to of an inch was operated as follows: .Cracked hydrocarbon vapors including cracked gasoline and fixed gas having temperature of approximately 935 F. were charged into one end of the converter under pressure of 23 pounds per square inchand at a rate, compared with the total vlume of contact material in said converter, of 2.1 volumes (liquid basis) per hour. Into the space in advance of each contact mass, there was admitted a stream of a heavy oil, together with 15% of steam by weight, which was the 43% through 100% cut of East Texas crude having the following boiling range characteristics as determined by vacuum assay:` at 486 F., 50% at 663 F. and 89% at 1005 F. The charging rate of each stream of heavy oil. compared with the total volume ot contact material in said converter, 'was 0.4 volume (liquid basis) per hour. e

At the beginning of the ori-stream period, the following temperature conditions existed with respect to the contact masses: The first contact mass at the respective entrance and exit sides thereof had temperature of 1000* F. and 910 FI;

perature of 920 F. At the termination of the on-4 stream period, the following`"`temperature conditions existed with respect to said contact masses: The nrst contact mass at the respective entrance and exit sides thereof had temperature of 865 F. and 870 F.; the second contact mass at the respctive entrance and exit sides thereof had temperature of 850 F. and 855 F.; and the third contact mass at the respective mid-point and exit sides thereof had temperature of 860 F. and 870 F. The heavy oil, while substantially in the liquid phase, was admitted to each of the aforesaid spaces at a temperature of 600 F. By action thereon of thestream of hot vapors, the heavy oil was vaporized to some extent and, therefore, in each space, a partially vaporized mixture was produced having temperature lower than that of the succeeding contact mass. Hence, a partially vaporized mixture was admitted to each contact mass with resultant vaporization and viscositybreaking ofthe liquid phase material, the totally vaporized mixture leaving each contact mass at gg temperature which had been elevated toward that of the contact mass. The contact time of the va-A pors in the first, second and third contact masses' was, respectively, 2.8 seconds, 2.3 seconds and 1.9

seconds. Y

Ofthe heavy East Texas bottoms admitted in advance of each contact mass, more than.,96% by weight was discharged from the converter as vaporized material admixed with the cracked vapors which were admitted to said converter. 70 The remainder, less than 4% .by weight of said heavy East Texas bottoms, was retained in the contact mass as a deposit of coke or carbonaceous i material containing substantially all of the. in-

organic salts and other non-volatile inorganic material present in said bottoms as well as the colte or carbonaceous material resulting from conversion of the diiilcultly yaporizable componentsof the bottoms.'

5 Example V11 A iight gas oil was passed through a heater in order to produce vapors which wereadmitted to a cracking converter ata temperature of 850 F.

The A. P. I. gravity of this light gas oil was 29.3, the initial boiling point was 480. F., the 50% boiling point was 558 F., and-the 95% boiling point was 723 F. The vaporized gas oil was thus charged to the cracking converter underspres- 7sure* of 23 pounds per square inc h and at a rate,

compared with the total volume of contact material in the cracking converter, of 0.75 volume (liquid basis) per hour. The cracking converter had six separate contact masses formed from equal parts of pieces of fused alumina and silica, as hereinbefore'described, and pieces of catalytic contact material having an activity index of as expressed in terms of the standard test described in Laboratory Method for Determining the Ac- 25 tivity of Cracking catalysts -by J. Alexander and H. G.` Shimp, page R537, National Petroleum News, Technical Section, August 2, 1944. The respective contact masses were formed from progressively increasing amounts of contact material. Thus, the contact massrst engaged by the aforesaid vaporized materiall was formed from 4.5 liters of contact material and the succeeding contact masses were formed, respectively, from 5.3 liters, 6.2 liters, 7.3 liters, 8.5 liters and 10.0 liters of contact material.

,Into the space in advance of each contact mass,

. with the exception of the first n(that contact mass `which is ilrst engaged by the vaporized gas oil) there was admitted, together with 10% oi' steam by weight. a heavy gas oil in the form of a bottom fraction from a fractionating zone. The charging rates oi' the respective streams of heavy gas oil, compared with the total volume of contact material in the cracking converter, which were admitted in advance oi' the second, third, fourth',

ilfth and sixth contact masses were, respectively, 0.11, 0.13, 0.15, 0.17 and 0.19 volume (liquid basis) per hour. The A. P. I. gravity of this heavy gas oil was 23.9, the initial boiling point was 476 F.. the 50% boiling point was 640 F., and the 93% boiling point was '162 n.

This heavy gas oil, while in the liquid phase, was admitted into each of the aforesaid spaces, except the iirst, at a temperature of 275 F. and,

by action thereon of the streams of vaporized materlal, it was substantially completely vaporized.

Therefore, in each of said last named spaces, a vaporized mixture wasproduced having temperature lower than that of the succeeding contact mass. From each spacelast referred to, then. a vaporized 'mixture passed into the succeeding contact mass with resultant elevation in tempera-'- ture and conversion thereof into hydrocarbon products. During the on-stream period, the av- 05 erage temperature of the vaporsentering and leaving each contact mass was substantially as follows: First contact mass, 850 F. and 950 F.; second contact mass 852 F. and 940 F.; third contact mass, 860 F. and 915 F.; fourth contact mass, 865 F. and 975 F.; fth contact mass 870 F. and 940 F.; and sixth contact mass, 870 F. and 1000 F.-

Example VIII A four section converter was employed wherein the depth of each of the nrst and second contact l? masses was two feet and that of the third and fourth contact masses was two and one half feet.

`each of the contact masses being composed, by

volume, of one-third active-cracking catalyst and two-thirds of fused alumina and silica grain The active cracking vcatalyst was formed from low alkali, silica-alumina material and the activity indices, as expressed in terms of the standard test described in Laboratory Method for Determining the Activity of Cracking catalysts, by J. Alexander and H. G. Shimp, page R537,National Petroleum News, Technical Section, August 2, 1944, of the rst, second, third and fourth con tact masses were, respectively, 28.7, 29.6, 34.0 and 35.8. The depth of the chamber between each pair of contact masses was two feet and seven inches. y

A hydrocarbon vapor phase mixture, composed of a 42-88% vfraction (32.1 A. P. I. gravity) of 4 A. P. I. gravity and boiling within the approximate range of 460 F. to 650 F.) derived from the aforesaid 42-88% fraction of East Texas crude, the rate of charge for each side streambeing approximately one third of the total side stream charge which was 0.75 volume (liquid basis) per hour per total volume ofthe active catalyst material in the converter.

Duringthe on-stream period, the average temperatures of the contact masses in the order named and approximately at the respective exit ends thereof were 885 F., 920 F., 935 F. and 938 F. The temperatures of the hot vapors, upon passage thereof from each of said contact masses in the order named, averaged approximately 870 F., 905 F., 890 F. and 910 F. respectively during the on-stream period. The side streams, while substantially in the liquid phase, were admitted into each of the aforesaid spaces at temperatures of 430 370 F. and 390 F., respectively. Heat was exchanged between the vapors and liquid material with resultant vaporization of the latter. The vaporized mixtures had average temperatures of approximately 790 F., 810 F. and 830 F. upon passage thereof into the respective second, third and fourth contact masses during the on-stream period.

The operation above described yielded 48.4% (by volume of the charge) of gasoline with a gravity of 57.5 A. P. I. The gasoline had an octane rating of 82.9 when tested by the CFR-Motor method and 93.0 when tested by the CFR-Research method.

lytic contact materlalan amount of heat substantially in excess of that required for effecting an on-stream cracking operation in the contact zones, burning-the deposited carbonaceous material from the catalytic contact material with resultant storage therein of an amount of heat as specified above,causing hydrocarbon material having temperature lower than that ofthe catalytic contact material in one contact zone to pass therethrough to remove stored excess heat therefrom with resultant elevation in temperature of the hydrocarbon material and substantial conversion thereof into cracked products which enter said cooling zone at such elevated temperature, introducing into said cooling zone a medium having temperature lower than that of said cracked products, heat being exchanged between While the invention has been described with respect to certain particular preferred examples l said cracked products and said medium to lower the temperature of the cracked products to a desired level below that of the catalytic contact material in the other contact zone, and passing at leasta portion of said cracked products, as the operation proceeds, into said last named contact zone with resultant elevation in temperature thereof, further substantial cracking conversion thereof and removal of stored excess heat from said last named contact zone.

2. The process of treating hydrocarbon material in the presence of contact materia1 adapted to affect conversion endothermically conducted in each of a pair of contact zones having a mixing zonev between them and thereafter to be subjected to a regenerating operation, the steps which comprise conducting a conversion operation of the character described below in the presence of such contact material with resultant deposition thereon of an `amount of carbonaceous material which, when burned during the subsequent regenerating operation, stores in the contact material an amount of heat substantially in excess of that required for effecting on-stream conversion in 'the contact zones, burning the deposited carbonaceous material from the contact material with resultant storage therein of an amount of heat as specified above, causing hydrocarbon material having temperature lower than that of the contact material in one contact zone to pass therethrough to remove stored excess heat therefrom with resultant elevation in ternperature of the hydrocarbon material and substantial conversion thereof into hydrocarbon 'products which enter said mixing zone at such elevated temperature, introducingI into said mixing zone hydrocarbon material having temperature lower than that of said vhydrocarbon products, heat being exchanged between said hydrocarbon products and said hydrocarbon material to produce a hydrocarbon mixture having temperature lower than that of the contact material in the other contact zone, and passing at least a portion of said hydrocarbon mixture, as the operation proceeds, into said last named contact zone with resultant elevation in temperature thereof, substantial conversion thereof and removal of stored excess heat from said last named contact zone.

aosaace 3. The process of claim 2 in which the contact material is a mixture formed from solid pieces of catalyst and inert material having relatively high heat-absorbing capacity.

4 T he process of treatlnghydrocarbon material in the presence of contact material adapted to aiiect conversion endothermically conducted in each of a pair of contact zones having a mixing zone between them and thereafter to be subjected to a regenerating operation, the steps which comprise conducting a conversion operation of the character described below in the presence of such contact material with resultant deposition thereon of an amount of carbonaceous material which, when burned during the subsequent regenerating operation, stores in the contact lmaterial an amount of heat substantially in excess of that required for effecting onstream conversion in the contact zones, burning the deposited carbonaceous material from the contact material with resultant storage therein of an amount of heat as specified above, causing hydrocarbon material having temperature lower than that of the contact material in one contact zone to pass therethrough to remove stored excess heat therefrom with resultant elevation in temperature of the hydrocarbon material and substantial conversion thereof into hydrocarbon products which enter said mixing zone at such elevated temperature, introducing into said mixing zone hydrocarbon material at least partially in the liquid phase and having temperature lower than that of said hydrocarbon products, heat being exchanged between said hydrocarbon products and said hydrocarbon material to produce a hydrocarbon mixture having temperature lower than that of the contact material in the other contact zone, and passing at least a portion of said hydrocarbon mixture, as the operation proceeds, into said last named contact zone with resultant elevation in temperature thereof, substantial conversion thereof and removal of stored excess heat from said last named contact zone.

5. The process of claim 4 in which said hydrocarbon mixture is in totally vaporized condition prior to passage thereof into said last named contact zone.

6. The process of claim 4 in which said hydrocarbon mixture is only partially vaporized prior to passage thereof into said last named contact zone. i

7. The process of treating hydrocarbon material in the presence of contact material adapted to aect conversion endothermica'lly conducted in each of a pair of contact zones having a mixing zone between them and thereafter to be subjected to a regenerating operation, the steps which comprise conducting a conversion operation of the character described below in the presence of such contact material with resultant deposition thereon of an amount of carbonaceous material which, when burned during the subsequent regenerating operation, stores in the contact material an amount oi heat substantially in excess of that required for effecting on-stre'am conversion in the contact zones, burning the deposited carbonaceous material from the contact material with resultant storage therein of an amount of heat as specified above, causing hydrocarbon material having temperature lower than that of the contact material in one contact zone to pass therethrough to remove stored excess heat therefrom with resultant elevation in temperature of the hydrocarbon material and substantial conversion thereof into hydrocarbon products which enter said mixing zone at such elevated temperature, introducing into said mixing zone hydrocarbon material having temperature lower than that of said hydrocarbon prod ucts, heat being exchanged between said hydrocarbon products and said hydrocarbon material to produce a hydrocarbon mixture having tem. perature lower than that of the contact material in the other contact zone, and passing at least a portion of said hydrocarbon mixture, as the operation proceeds, into said last named contact zone with resultant elevation in temperature thereof, substantial conversion thereof and removal of stored excess heat from said last named contact zone, the temperature of the contact material in said contact zones decreasing at approximately the same rate during continuance of the conversion period.

8. Process of effecting hydrocarbon conversion reactions in vapor phase by catalysis in a cycle of on-stream and regenerating reactions through the action of catalytic material mingled with heat absorbing material in a composite contact mass, the process comprising effecting the conversion of the charge by stage catalysis in a series of said composite contact masses maintained at temperatures in excess of 750 F., removing a portion of the products of conversion after each of said masses, mingling additional charge in liquid phase with the remaining products before they enter the next contact mass, and controlling operating conditions to produce suiiicient burnable deposit on each mass during on-stream reactions to store sumcient heat in each mass dur-V ing regeneration by burning of said deposit to supply the heat of reaction of the subsequent onstream reaction as well as sensible heat and heat of vaporization for additional charge when supplied intermediate said contact masses.

9. Process of effecting hydrocarbon conversion reactions by catalysis in a cycle of on-stream and regenerating reactions through the action of catalytic material mingled with heat absorbing material in a composite contact mass, the process comprising effecting the conversion of the charge at least partially irl vapor phase by stage catalysis in a series of said composite contact masses maintained at temperatures in excess of 750 F., removing a portion of the products of conversion issuing from at least one of said contact masses, mingling atomized liquid charging stock with the remainder of the products, utilizing the heat of said remaining products to vapcrize atomized liquid so added to said charge, and controlling operating conditions to produce suilicient burnable deposit on said masses during on-stream reactions to store sufficient heat in said masses during regenerating by burning of said deposit to supply heat of reaction and heat of vaporization of additional charging stock in subsequent ori-stream reactions.

10. Process of effecting hydrocarbon conversion reactions by catalysis in a cycle of onstream and regenerating reactions through the action of catalytic material mingled with heat absorbing material in a composite contact mass. the process comprising eilecting the conversion of substantially vapor phase charge by stage catalysis in a series of said composite contact masses maintained at temperatures in excess of 750 F., mingling additional charge comprising liquid in atomized condition with products leaving one of said contact masses before the prod-1 ucts enter the next contact mass, and controlling operating conditions to deposit suiilcient burnl able deposit on each mass during on-stream reactions to store suilicient heat in each mass during regeneration by burning of said deposit to succeeding contact ma supply the heat of reaction of the subsequent on-stream reaction as well as sensible heat and heat of vaporization for additional charge when supplied intermediate said contact masses.v

11. In use of contact mass alternately onstream to effect conversion of a hydrocarbon charge which produces burnable deposit on said mass and in regeneration by burning of said desmanes ss at approximately the level obtaining within the mass from which the product containing stream has issued, and withdrawing a portion of said stream of products and partially vconverted charge fromv` the converter prior to said mingling of additional.

. charge,

posit wherein heat required for said conversion 1 and supplied by said mass is stored in the latter during said regeneration, the proces.'J comprising effecting such a cycle in a plurality of separate contact masses through which a hot stream of said charge passes in succession while being maintained at a temperature suitable for effect- 'ditional charge to heat the latter.

12. Process according to claim 11 wherein the charge passed serially through the separate masses and the additional charge are hydrocarbons heavier than gasoline and the masses comprise active cracking catalyst maintained at cracking temperature.

13. In the operation of a sectional catalytic converter providing a seriesof separate contact masses in an operating cycle of alternating regenerating and on-stream periods wherein exothermic heat resulting from regeneration is stored within said masses to be released to the succeeding on-streamprocesses, the process of utilizing excess heat so stored and of maintaining said masses at desired operating temperatures during said on-stream periods comprising the steps of passing a hydrocarbon stream into and through the first of said masses with resultant withdrawal of heat therefrom, the resulting products and resulting partially converted charge passing serially through the balance of said masses, and mingling with reaction products from one mass comparatively cool additional hydrocarbon charge in quantity controlled to maintain thetemperature of the next succeeding contact mass at approximately the level obtaining within the aforesaid one mass.

14. In the operation of a sectional catalytic converter providing a series of separate contact masses in an operating cycle of alternating regenerating and on-streaxn periods wherein exothermic heat resulting from regeneration is stored within said masses to be released to the succeeding on stream processes, the -process of utilizing excess heat so stored and of maintaining said masses at desired operating temperatures during said ori-stream periods comprising the steps of passing a hydrocarbon stream into and through the ilrst of said masses with resultant withdrawal of heat therefrom, the resulting products and resulting partially converted charge passing serially through the balance of said masses, mingling with reaction products from one mass comparatively cool additional hydrocarbon charge in quantity controlled to maintain the temperature of the next 15. In effecting hydrocarbon conversion reactions in the presence of a series of separate contact masses employed in an operating cycle of i alternating regenerating and on-stream periods wherein exothermic heat resulting from regeneration is stored within said masses to be released to said reactions during the succeeding on-stream periods, the process of utilizing excess heat so stored and of maintaining said masses at desired operatingtemperatures during said onstream period comprising the steps of passing a stream of hot vaporized ordinarily liquid onstream hydrocarbon charge into and through the first of said masses, the resulting products and partially converted charge passing serially through'the remainder of said masses to withdraw heat from each of them, mingling with reaction products from one mass additional hydrocarbon charge comprising comparatively cool liquid to effect .vaporization of the latter by utilization of sensible heat content of said products, and controlling the quantity of additional charge so added to maintain the next succeeding contact mass at conversion temperature at least approximating that obtaining within the aforesaid one mass.

16. In use of a contact mass alternately onstream to eiect conversion of a hydrocarbon charge which produces burnable deposit on Said mass and in regeneration by burning of said de.- posit wherein heat required for said conversion and supplied by said mass is storedd in the latter during said regeneration, the process comprising effecting such a cycle in a plurality of separate vcontact masses through which a hot stream of said charge `passes in succession, while being maintained at temperature suitable for effecting the same type of conversion in each mass, eiectingsaid cycle under conditions such that the quantity of heat stored in said masses during regeneration is in excess of that required for effecting the on-stream reactions, admitting additional and comparatively cool hydrocarbon charge to said stream during its movement between at least one pair of adjacent contact masses to utilize excess storedheat by transferring sensible heat of said stream to said additional charge to heairthe latter, constricting said stream at one point in its movement from one mass to the next mass, and effecting the feeding of said additional charge at said point of constriction.

17. In' use of contact mass alternately onstream to effect conversion of a hydrocarbon charge which produces burnable deposit on said mass and in regeneration by burning of said deposit wherein heat required for conversion and supplied by said mass is stored in the latter during said regeneration, the process comprising effecting such a cycle in a plurality of separate contact masses through which a hot stream of said charge passes in succession while being maintained at temperature suitable for effecting the same type of conversion in each mass, effecting said cycle under conditions such that the quantity of heat stored in said masses during regeneration is in excess of that required for eiecting the ori-stream reactions, admitting additional and 23 comparatively cool hydrocarbon charge to said stream during its movement between at least one pair of adjacent contact masses to utilize excess stored. heat by transferring sensible heat of said stream to said additional charge to heat the latter, constricting said stream at one pointv in its movement from'one mass to the next mass,

effecting the feeding oi' said additional charge at said point of constriction, and withdrawing a portion of said stream after its issuance from a mass and prior to the feeding of additional charge between the masses.

18. In the art of treating hydrocarbon material involving engagement thereof with contact material which is substantially inert catalyticaiiy,

the process which comprises heating the contact material of a pair of contact zones, to cause such contact material to be in a temperature range which is effective as regards vaporization and viscosity-breaking of heavy hydrocarbon material in the liquid phase while .preventing any substantial cracking thereof, at the, contact time employed, intolower boiling hydrocarbons of the gasoline type, passing a charge of heavy hydro' carbon material while at least partially in the liquid phase into one contact zone at temperature lower than the temperature of the contact material therein with resultant vaporization and viscosity-breaking of .the liquid phase material and production of a vaporized mixture which, at

f temperature elevated toward that oi said last named contact material, enters a mixing zone between said contact zones, and introducing into said mixing zone another charge of heavy hydrocarbon material while at least partiallyl in the liquid phase and having temperature lower than that of said vaporized mixture, heat being exchanged between the hydrocarbon material last named and said vaporized mixture to produce a vpartially vaporized hydrocarbon mixture having temperature lower than that of the contact material in the other contact zone, said hydrocarbon mixture, as the operation proceeds, passing into said last named contact zone with resultant vaporizaticn and viscosity-breaking of the liquid phase portion thereof.

EUGENE J. HOUDRY.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS