US2921845A

US2921845A - Catalytic reforming of hydrocarbons

Info

Publication number: US2921845A
Application number: US560801A
Authority: US
Inventors: Robert T Kyle; Nilsen Arve
Original assignee: GAS MACHINERY CO
Current assignee: GAS MACHINERY CO
Priority date: 1956-01-23
Filing date: 1956-01-23
Publication date: 1960-01-19
Anticipated expiration: 1977-01-19
Also published as: FR1170712A; BE549232A; DE1056318B; GB803788A

Description

Jan. 19, 1960 R. T. KYLE ETAL CATALYTIC REFORMING OF HYDROCARBONS Filed Jan. 23, 1956 2 Sheets-Sheet 1 LIQUID FUEL a A/R -L/QUID FUEL 8 AIR 13 j I! I2 1-4 EXHAUST l5 ,8 I6 AIR H 25 -14? V 25 M 3 22 26 VEHICLE Q VEHICLE Fig.

Q I I Q Q 2 c l 3 I t I 1 32 9 2 s 2 t r i I 39 e 1 x 1 1 s s 38 Q I I Q i t 1 53 54 x g t 1 o 7 Q 54 INVENTOR 3 36 55 48 3 56 ROBERT T KYLE t\\ t 42 6967 ATTORNEYS Jan. 19, 1960 KYLE ETAL I 2,921,845

CATALYTIC REFORMING OF HYDROCARBONS Filed Jan. 25, 1956 2 Sheets-Sheet 2 l /ll 1 11 INVENTOR. ROBERT T KYLE ARVE N/LSEN ATTORNEYS United States Patent CATALYTIC REFORMING 0F HYDROCARBONS Robert T. Kyle, Beachwood Village, Ohio, and Arve Nilsen, Shrewsbury, England, assignors to The Gas Machinery Company, Cleveland, Ohio, a corporation of Ohio Application January 23, 1956, Serial No. 560,801

Claims. (Cl. 48-214) The present invention relates to a new and improved process for catalytically reforming liquid and gaseous hydrocarbons and to apparatus for carrying out the process. Though particularly designed for and described herein as applied to the manufacture of oil gas from hydrocarbon oils, for purposes of illustration, it is to be understood that the process and apparatus are not so limited in their utility and may be advantageously used for catalytically reforming liquid and gaseous hydrocarbons to produce a variety of end products.

Heretofore, extensive developments in the pyrolytic reforming of gas oil to produce a relatively high specific gravity oil gas have been made and put into commercial use throughout the world. Examples of successful processes and apparatus for such operations are to be found in the United States patents to Hall Nos. 2,580,766 and 2,5 80,767; to Stookey ct al., No. 2,714,058; to Richardson, No. 2,746,850 (pending application Serial No. 382,116, filed September 24, 1953); and to Richardson et al., No. 2,746,852 (pending application Serial No. 441,996, filed July 8,1954).

Pyrolytic reforming, as carried out by the processes and apparatus of these several illustrative examples, produces an oil gas of relatively high specific gravity and relatively high B.t.u. value.

Because industrial fuel burning equipment in many areas of the World is not suited for use of such high B.t.u. oil gases, it has also been previously proposed to resort to a catalytic or combination catalytic and pyrolytic reforming process, employing, e.g., a nickel catalyst. This has been done by employing a fuel combustion chamber, a process steam heating chamber, and a catalytic reaction chamber interconnected in series by suitable conduits. Fuel oil is first burned in the combustion chamber with an excess of air, and the products of combustion are fed first through a checkerbrick structure in the heating chamber, then through a catalyst bed in the reaction chamber to heat the checkerbrick and the catalyst, and then to a stack or waste heat boiler. Immediately upon terminating combustion in the combustion chamber, process steam is fed through the heated checkerbrick in the heating chamber and thence into the reaction chamber. As the thus superheated steam enters the reaction chamber, make oil is introduced directly into that chamber in the direction of steam flow, and the steam and make oil pass together through the heated catalyst bed and out of the reaction chamber to a wash box and thence to storage. When the checkerbrick and catalyst temperatures have dropped to minimum temperature limits for satisfactory operation, the make run is terminated and a new heat runis started to prepare for the next make run.

The principal objections to such a catalytic system are lack of adequate temperature control and provision for removal of contaminating deposits from the catalyst bed, imperfect dispersion and distribution of the make oil over the area of the catalyst bed, too rapid deactivation of the catalyst from deposited carbon and tars, disintegration of the catalyst carrier material due to over-v alternately in one shell and then in the other.

Patented Jan. 19, 1960 heating, and a consequent overall inefiiciency of the process.

Briefly, the objects of the invention are to overcome the foregoing objections to the prior art catalytic processes and to provide an improved method and apparatus that is adapted for a wide variety of gas, as well as oil, cracking and reforming operations.

More specifically, the objects of the invention include the provision of a process and apparatus for catalytically reforming gaseous and liquid hydrocarbons in which a more uniform product is obtained and a greater con version of charge material to a fixed gas product is achieved, with a consequent reduction in the quantity of condensible by-products which must be separated'from the desired fixed gas product.

These objects are accomplished by utilizing a twin generator. set of the general character disclosed in the several patents mentioned above, and having a cross-over zone of relatively large cross-section connecting the top portions of the two generators or shells for free intercommunication; disposing a catalyst bed in each generator or shell intermediate the upper and lower. ends thereof; and carrying out successive heat and make run cycles, Each heat run is carried out in such manner that air to support combustion of fuel for heating the catalyst bed in one shell is heated while passing upward through the catalyst bed in the second shell, is mixed with fuel while enroute toward and through the cross-over and downward in the first shell to effect combustion of the fuel and heating of the catalyst in the first shell. Each make run is carried out in such manner that a gaseous vehicle, such as steam, is passed upward in the second shell, preferably through the catalyst bed therein, is mixed with the hydrocarbon to be reformed while enroute to the catalyst bed in the first shell for passage with said hydrocarbon downward through the catalyst bed in the first shell to effect the catalytic reforming therein. By repeating these steps in subsequent cycles with the relationship of the shells reversed from that of the preceding cycle, one of the catalyst beds is cleaned during each cycle by air, and preferably also by steam or other gaseous vehicle passed upward therethrough while the catalyst bed in the other shell is being heated and then used in the reforming reaction.

Preferably, at least below the catalyst beds in the two shells, and optionally above each catalyst bed as well, checkerbrick heat storing structures are provided in the paths of the various streams of gaseous materials just descibed. These checkerbrick structures serve several purposes. They supply heat to the air and to the steam while passing upward in one shell toward the other shell during heat and make runs in the latter, having received such heat from' combustion products of fuel and air and/or catalytic reaction products respectively passed downward therethrough during the preceding cycle. They maintain more uniform reaction temperatures durprolonged make runs. They assist in distributing the flow of gaseous materials more uniformly over the transverse cross-sections of the shells and thereby promote more uniform flow over the transverse cross-sections of the catalyst beds. Also, when disposed above the catalyst beds, as well as below them, they serve to protect the catalyst beds from direct impingement of a burning fuel during a heat run and minimize carbon deposits on the catalyst.

The above and various additional objects, characteristic features, and advantages of the invention will be more fully understood from the following detailed description of the invention and from the accompanying drawings,

'3 erator :set and associated conduits for carrying out the process of the invention; a

Fig. 2 is a somewhat diagrammatic representation similar to Fig. l, but showing-a twin generator set in vertical section and in somewhat more detail, as designed particularly for making oil gas; v V Fig. 3 is a view similar to Fig. 2 showing a modified form of twin generator set for making oil gas in accordance with the invention;

Fig. 4 is a perspective view of one of a number of catalyst carrier elements contained in the catalyst zone of each generator of vFig. 3;

Fig. 5 is an elevational view of a plurality of catalyst carrier elements of the kind shown in Fig} 4, stacked in a vertical column as they are employed in each generator 'of Fig. 3; and

catalyst bed of the kind employed in each generator of Fig. 3, showing how a plurality of columns of the catalyst carn'erelements of Figs. 4 and 5 may be packed in interfitting relationship over the cross-sectional area of a generator shell in the catalyst zone, the plane of the section being indicated by the line .6-6 in Fig. 3.

Referring first toFig. 1, successive cycles, each including a heat run and make run sequence, are performed alternately'in shells 11 and 12. Immediately following the completion of a cycle involving a heat run and make run in shell 12, a heat run in shell 11 is commenced by introducing a'fluid fuel into the system adjacent the upper end of either shell 11 or shell 12, or both, through one or both of

conduits

13 and 14, Preferably all or most of the fuel is introduced through conduit 14 into shell 12. Primary combustion air is introduced with the fuel, most conveniently at the same point or points, and atomizing steam may also be introduced with the fuel where a liquid fuel requiring such dispersion is employed. At the same time, secondary combustion air is introduced through a conduit 16 into the bottom of shell 12.

The secondary air from the conduit-16 is passed upward through the shell 12 at relatively high velocity and upward through a zone 18 therein containing a catalyst for the gas making reaction. Since the shell 12 and the catalyst in the zone 18 are still hot from the preceding make run in shell 12, the secondary air is heated as it travels upward through the shell 12. This air also serves to dislodge and carry upward with it accumulated carbon formed or deposited on the catalyst surfaces in the zone 18 during the preceding heat and make runs in shell 12.

The secondary air moving upward in shell 12 mixes with the fuel and primary air in the course of its travel from shell 12, through a connecting cross-over conduit 19, and downward in shell 11 toward a zone 17 therein containing a catalyst. The temperature of the secondary air, heated as described and the residual temperature in the system from the preceding make run are sufliciently I high to effect spontaneous ignition of the fuel as the air and fuel mixture travels toward the zone 17 in shell '11. The hot combustion products pass downward through the catalyst in the zone 17 for heating the same preparatory to the succeeding make run in shell 11, and then pass out of this shell at the bottom thereof through a conduit 21 to an exhaust conduit 23, and thence to a stack or 'a waste heat boiler (not shown).

When the desired temperature of the catalyst in the zone 17 has been achieved, the introduction of fuel and air are discontinued and'a suitable gaseous material, such as low pressure steam, is preferably introduced into shell 12 for a short time via a conduit 26, and is passed upward through the catalyst zone 18 in shell 12 through the cross-over 19, and downward in shell 11 through the catalyst zone 17 therein. This serves to purge the two shells of air, and the gaseous exhaust from the purging operation is passed through the

conduits

21 and 23 to the stack or waste heat boiler.

When the steam purging operation-is complete, the

make run in shell 11 is begun by introducing a suitable gaseous vehicle, which may .be the same steam used for the purging operation, through the conduit 26 into shell 12 while injecting a liquid or gaseous hydrocarbon to be reformed into the system adjacent the upper end of either shell 11 or shell 12, or both, through one or both of the

conduits

27 and 28. Preferably,.all or most of the hydrocarbon to be reformed is introduced through the conduit 28 into the top of shell 12 in a downward direction countercurrent to the flow of the steam or other gase ous vehicle. This flow is regulated to cause the steam or other gaseous vehicle to mix with the hydrocarbon and carry it along the same path through the catalyst zone 17 in shell 11. 1f the hydrocarbon to be reformed is a liquid, it should be dispersed as a spray by any suitable nozzle when introduced into the system. a

To the extent that the hydrocarbon to be reformed is introduced into shell 12 as described, thorough dispersion thereof throughout the steam or other gaseous vehicle is promoted by the countercurrent mixing thereof and by the relatively long path of travel of the mixture from shell 12, through the cross-over 19, and downward in shell 11 to the zone 17 therein. However, the other advantages of the invention described herein are not dependent on introduction of all or any part of the hydrocarbon in this manner, and it may be introduced into the system at any point or points along the path of flow of the vehicle between the two

catalyst zones

18 and 17 in any manner which will thoroughly disperse the hydrocarboninthe vehicle for entrainment therewith so that a uniform mixture of the hydrocarbon and vehicle passes downward through the catalyst zone 17 in shell 11.

The passage of the hydrocarbon in this manner through the zone 17 in shell 11 in intimate contact with the catalyst therein catalytically reforms the hydrocarbon and, in the case of gas oil, produces a relatively low specific gravity mixture of hydrogen and hydrocarbon gases. The gaseous products of this reaction are passed out of shell 11 adjacent the bottom thereof through the

conduits

21 and 23 to a wash box (not shown), and thence to storage. This make run is continued for as long as the temperature of the catalyst in zone 17 of shell 11 remains high enough for the described gas forming reaction to proceed efficiently.

At the conclusion of this make run, determined by the drop in temperature in the catalyst zone 17 of shell 11, the introduction of hydrocarbon is stopped, but, where steam is used as the gaseous vehicle, the flow of steam is preferably continued for a brief period to react with accumulated carbon in the catalyst zone 17 of shell 11 to produce additional gas and thereby assist in prolonging the activity of the catalyst as an incidental benefit.

Optionally, this make run may be briefly followed, to the extent required for more complete removal of carbon from the catalyst zone 17 of shell 11, by the introduction of regenerative air into shell 12 through the conduit 16. The oxygen of this air, which follows the same path from the top of shell 12, through the cross-over 19, and downward through shell 11, reacts with any carbon remaining in the catalyst zone 17 of shell 11 and will, at the temperature still prevailing therein, form C0 The resulting mixture of, primarily, CO and nitrogen may be exhausted through the

conduits

21 and 23 either to the stack or waste heat boiler, or through the wash box to storage as a diluent for lowering the heating value of an oil gas product.

This concludes one complete cycle of sequential heat and make runs, whereupon the same series of operations is performed with the relationship of the shells reversed by introducing the same gases, fuel, and hydrocarbon in the same order through symmetrically arranged conduits for carrying out identical heat and make runs in shell 12 while effecting upward flow of air and gaseous vehicle through the catalyst zone 17 of shell 11 to complete the removal of carbon therefrom to the greatest possible degree. For this purpose, an air injection conduit 15, a gaseous vehicle injection'conduit 25, and a fuel injection conduit 13 are connected to shell 11 and respectively correspond in location and function to the

conduits

16, 26, and 14 connected to the shell 12. Also, a conduit 22 leads from adjacent the bottom of shell 12 to the exhaust conduit 23 and corresponds in location and function to the conduit 21 leading from shell 11. A selector valve 29 may be placed at the junction of the

conduits

21, 22, and 23 for controlling the flow as will be obvious from the foregoing description. v

Optionally, when making oil gas, the above described make runs may be further modified, if desired, by bleeding some of the reformed gas from the shell in which it is produced, at any desired point below the

catalyst zone

17 or 18 therein, and reintroducing it into the system along with process steam to provide a more reducing atmosphere in the system and thereby enhance the reforming reaction. For this purpose, any desired form of injector or pump (not shown) may be used to move reformed gas from a low pressure zone at one end of the system into a higher pressure zone at the other end of the system or at some intermediate point. Also, if desired, some reformed gas may be introduced into the system at the conclusion of a heat run, e.g. adjacent the bottom of shell 12 at the conclusion of a heat run in shell 11, thereby using hydrogen in the reformedgas to reactivate the hot catalyst in the catalyst zone of the shell in which the succeeding make run is to be conducted.

Since the invention is not directed to any new catalytic reaction in the hydrocarbon reforming step of the process, but is essentially based upon the use of a new combination or arrangement of apparatus and new manipulative procedures for catalytically reforming liquid and gaseous hydrocarbons generally, it will be understood that the invention is not limited to the use of any particular catalyst, hydrocarbon to be reformed, gaseous vehicle, or temperature and other reaction conditions. However, the invention is especially suited for the production of relatively low specific gravity gaseous fuels by the catalytic reforming of higher molecular weight hydrocarbon compounds, and representative temperatures in the system for such'reactions are of particular interest in illustrating the operation and advantages of the invention:

In reforming a hydrocarbon oil, nickelous oxide .is the presently preferred catalyst, though other metal oxides have been successfully employed as is well known in the art. The temperature desirably employed in various parts of the system will depend to a considerable extent upon the composition of the particular make oil to be processed and the desired heating value and density of the gas product. In general, the catalyst temperature during a make run should be maintained in the range of about 750 to 975 C., and usually in the range of about 800 to 900 C. With this as an objective, the heat oil and secondary air introduced during a heat run should be regulated to heat the catalyst to be employed in the succeeding make run to a maximum of about 1000" C. The steam for purging the system at the end of a heat run and process steam employed as the gaseous vehicle and introduced during a make run should be saturated at about 14 to 16 lbs/sq. in. pressure and may be heated somewhat in the system to about 400 C. or so, depending upon the temperature and amount of heatstored in the parts of the system through which the steam flows enroute to the catalyst Zone. The above illustrative temperatures may be varied considerably, depending upon the particular catalyst, flow rates, make oil composition, character of product desired, and heat storing and releasing characteristics of the apparatus employed.

A suitable time cycle, in terms of parts of the total time from the end of one make run to the end of the next, may be approximately as set forth in the following table, although this also is subject to considerable variation to adjust the system to the make oil to be processed,

the gas product desired, and the several process variables discussed above.

To illustrate one form of apparatus particularly suited for reforming hydrocarbon oils by the above described procedure, reference is made to Fig. 2. As shown therein, a pair of refractory walled shells 31 and 32 are disposed side by side, and the upper ends of the shells merge into a refractory walled cross-over conduit 33 having a centrally disposed port 34 for introducing additional air during a heat run, if desired.

The lowest portion 35 of each of the shells 31 and 32 is open to substantially free movement of gas or vapor therethrough, but contains suitable supporting arches 36 for a grill-like floor 37 upon which a conventional checkerbrick structure 38 may be supported with relatively narrow spacing between the bricks. Each checkerbrick structure 38 supports an upper, grill-like floor 39 upon wihch a granular catalyst bed 40 is laid. The space 41 above each catalyst bed 40, together with the volume of the cross-over 33, serves as a m'ming and combustion chamber.

Adjacent their lower ends, the shells 31 and 32 may be connected by a conduit 42 which serves as an exhaust manifold and opens into a conduit 43 leading to a stack 44 having a closure lid 45.

Branch conduits

46 and 47 may respectively communicate with a waste heat boiler (not shown) and with a wash box and storage reservoir (not shown).

A selector valve 48 may be provided in the conduit 42 for selectively connecting either the shell 31 or the shell 32 in exhausting communication with the conduit 43.

Simple valves

49 and 50 may be provided in the conduits .46 and 47, respectively, for selectively directing products of combustion to the waste heat boiler during a heat run and gas reaction products to the wash box and storage reservoir during a make run, the stack cover 45 being closed for these purposes.

Liquid fuel and primary combustion air are introduced through a conduit 51 near the top of each shell with the aid of an atomizing burner 52. Secondary or regenerative air are introduced through a branch 53 and steam through a branch 54 of another conduit 55 adjacent the bottom of each shell, a selector valve 56 or other control means being provided for selectively admitting air or steam from these branches. Make oil may suitably be introduced into the shells as downward directed sprays from nozzles 57 on conduits 58 leading vertically downward into the upper ends of the shells.

The mode of operation of the system of Fig. 2 is essentially the same as that described in connection with Fig. 1, with certain additional characteristics inherently provided by the structural features incorporated in the apparatus design of Fig. 2. For example, the checkerbrick structures 38 perform conventional functions of alternately storing and supplying heat to the system and distributing the flow of gases more uniformly over the horizontal cross sections of the shells. Thus, during a heat run in shell 31, the checkerbrick structure 33 in shell 32 serves to preheat the secondary air passed upwardly therethrough from conduit 55 connected to that shell, and, to some extent, to raise the temperature of the purging steam and process steam which follows the same path from the same inlet conduit 55 before, during, and immediately following the make run in shell 31. Also, during the heat run in shell 31, the checkerbrick structure 38 in that shell is heated along with the catalyst bed 4i) therein, thereby acquiring and storing. the heat to be supplied to the secondary air and steam passed upward therethrough during the subsequent heat run and make run in shell 32. 7 Obviously, the catalyst beds 40 supplement the effects ot the respectively associated checkerbrick structures 38 in storing and releasing heat as described.

, By introducing make oil as a downward directed spray from nozzle 57 in shell 32 during a make run in shell 31,

this spray encounters the rising stream of process steam concurrently introduced into shell 32 from the associated conduit 55. This steam flow is regulated in volume to pick up and vaporize the make oil droplets and create catalyst bed 41) in shell 31 Where the reforming action takes place. For this reason, it is preferred that all or, atleast, a major part of the make oil (or any other liquid hydrocarbon to be reformed) be introduced as a downward directed spray adjacent the top of one shell countercurrent to the processsteam (or other gaseous vehicle) for mixing therewith before entering and moving downward through the other shell in which it is to be reformed. I

During a heat run in shell 31, the liquid fuel may be introduced entirely throughthe conduit 51 in shell 32, along with primary air, so that burning of the fuel will be largely complete before reaching the catalyst bed in shell 31. This protects the catalyst bed being heated from direct impingement of high temperature flame and minimizes disintegration of the catalyst carrier material and deposition of carbon on the catalyst. Alternatively, however, any desired portion of the fuel may be injected directly into the top of shell 31 during the heat run therein, through the associated conduit 51.

It will be understood, of course, that the foregoing discussion of the operations involved in carrying out successive heat and make runs in shell 3 apply in reverse in all respects when carrying out successive 'heat and make runs in shell 32 during alternate cycles.

Referring next to Figs. 3 to 6 inclusive, certain modifications of the apparatus of Fig. 2 are shown. For simplicity, the features common to both forms of apparatus are identified by the same reference characters in Figs. 2 and 3. Essentially, the apparatus of Figs. 3 to 6 inclusive differs from that of Fig. 2 by the substitution of so called core breaker elements as as catalyst carriers for the granular catalyst carrier material constituting the catalyst beds id in Fig. 2, and by the inclusion of a second checkerbrick structure 66 in each of the shells at and 62 above the catalyst zones therein.

As indicated in Pig. 3, the upper checkerbrick structures 66 are preferably made with a somewhat greater brick spacing than the lower checkerbrick structures '38, and may be supported on any suitable grill-like arch structure 67. These upper checkerbrick structures 66 respectively supplement the heat storing and supplying functions of the checkerbrick structures 38 therebelow. They also provide added protection of the catalyst ele ments; therebelow from direct impingement of high temperature flame during heat runs.

The catalyst zones 65) in the shells of Fig. 3 are filled with closely packed columns of stacked elements 65', each having the configuration shown in Fig. 4. The use of similar elements merely as core breakers is described and claimed in U.S. Patent No. 2,709,128, to Krause, granted May 24, 1955. These elements 65, made of porous, refractory, ceramic materials, may be thoroughly impregnated with finely divided catalyst, such as nickelous oxide by procedures well known in the art for impregnating simdar porous catalyst carrier materials. A large number of elements 65 may be disposed on end on the grill-like floor 39 and interfitted with each other over the entire horizontal cross-section of each

shell

61 and 62,

as illustrated in Fig. 6, to provide a large surface area of catalyst. impregnated, porous, ccramic'material'with ample free space between adjacent surfaces for passage ofgases therethrough'in vertical directions. To provide the desired total surface area of such material, additional elements 65 may be stacked'one above another on top of each such element in theilowermost horizontal layer to provide a large number of vertical columns of such elements to the required height over the entire horizontal cross section of each of the shells 31 and 32.

Except as noted above, the apparatus of Figs. 3 to 6 inclusive is the same as that of Fig. 2 and may be used in the same manipulative ways for carrying out successive cycles of heat and make runs, first in one shell and then in the other, as hereinbefore described. a

From the foregoing description of the process of the present invention and apparatus for carrying out the process, it will be apparent that the principles of the invention may be employed and the various advantages thereof may be obtained while making numerous changes in the specific procedures and structural designs disclosed herein for illustrative purposes. Accordingly, the invention is intended to embrace such changes'as would occur to those skilled in the art, within the spirit and scope of the appended claims.

What is claimed is:

1. A process for catalytically reforming liquid and gaseous hydrocarbons in a pair of shells having a cross-over zone connecting the top portions thereof and each having a porous catalyst bed intermediate its upper and lower ends and a separate, porous, refractory, heat storage bed below the catalyst bed, said process comprising the steps of: heating a first one of said shells and the catalyst bed and heat storage bed therein by passing air upwardly through the second one of said shells and the heat storage bed and catalyst bed therein to provide a gaseous stream flowing along a path through said cross-over and downward through the catalystbed and heat storage bed in said first shell, introducing a fluid fuel into said stream between the two catalyst beds for admixture and combustion with said air, and conducting combustion products of said fuel and air. downward through the catalyst bed and heat storage bed in said first shell to heat the same; passing a stream of a gaseous vehicle along said path from said second shell into said first shell, introducing the hydrocarbon to be reformed into said path for dispersion in and entrainment'with said gaseous vehicle, conducting the gaseous vehicle and entrained hydrocarbon downward through the heated catalyst bed in *said first shell for reforming the hydrocarbon, and conducting the gaseous vehicle and products of the reforming reaction downward through the heat storage bed of said first shell and out of said first shell at the bottom thereof to complete one heat-sun and make run cycle; and repeating said steps in. subsequent cycles with the relationship of said shells in each cycle reversed from that of the preceding cycle; whereby, during each cycle, one of said catalyst beds is cleaned, by air heated by the heat storage bed therebelow and passed upward therethrough in the course of heating the other catalyst bed preparatory to reforming said hydrocarbon therein.

, 2. A process for catalytically reforming liquid and gaseous hydrocarbons in a pair of shells having a cross-over zone connecting the top portions thereof and each having a porous catalyst bed intermediate its upper and lower ends and a separate, porous, refractory, heat storage bed below the catalyst bed, said process comprising the steps of: heating a first one of said shells and the catalyst bed and heat storage bed thereiniby passing air upwardly through the second one of said shells and the heat storage bed and catalyst bed therein to provide a gaseous stream flowing along a path through said crossover and downward through the catalyst, bed and heat storage bed in said first shell, introducing a fluid fuel into said stream between the two catalyst beds for admixture and combustion with said air, and conducting combustion products of said fuel and air downward through the catalyst bed and heat storage bed in said first shell to heat the same; passing a stream of a gaseous vehicle upwardly through the heat storage bed and catalyst bed in said second shell and along said path from said second shell into said first shell, introducing the hydrocarbon to be reformed into said path for dispersion in and entrainment with said gaseous vehicle, conducting the gaseous vehicle and entrained hydrocarbon downward through the heated catalyst bed in said first shell for reforming the hydro carbon, and conducting the gaseous vehicle and products of the reforming reaction downward through the heat storage bed of said first shell and out of said first shell at the bottom thereof to complete one heat run andmake run cycle; and repeating said steps in subsequent cycles with the relationship of said shells in each cycle reversed from that of the preceding cycle; whereby, during each cycle, one of said catalyst beds is cleaned by air and gaseous vehicle heated by the heat storage bed therebelow and passed upward therethrough in the course of heating the other catalyst bed and reforming said hydrocarbon therein.

3. A process for catalytically reforming liquid and gaseous hydrocarbons in a pair of shells having a crossover zone connecting the top portions thereof and each having a porous catalyst bed intermediate its upper and lower ends and a separate, porous, refnactory, heat storage bed below the catalyst bed, said process comprising the steps of: heating a first one of said shells and the catalyst bed and heat storage bed therein by passing air upwardly through the second one of said shells and the heat storage bed and catalyst bed therein to provide a gaseous stream flowing along a path through said crossover and downward through the catalyst bed and heat storage bed in said first shell, introducing a fluid fuel into said stream in said second shell above the catalyst bed therein for admixture and combustion with said air, and conducting combustion products of said fuel and air along said path into said first shell and downward through the catalyst bed and heat storage bed therein to heat the same; passing a stream of a gaseous vehicle upwardly through the heat storage bed and catalyst bed in said second shell and along said path from said second shell into said first shell, introducing the hydrocarbon to be reformed into said path for dispersion in and entrainment with said gaseous vehicle, conducting the gaseous vehicle and entrained hydrocarbon downward through the heated catalyst bed said first shell for reforming the hydrocarbon, and conducting the gaseous vehicle and products or the reforming reaction downward through the heat storage bed of said first shell and out of said first shell at the bottom thereof to complete one heat run and make run cycle; and repeating said steps in subsequent cycles with the relationship of said shells in each cycle reversed from that of the preceding cycle; whereby, during each cycle, one of said catalyst beds is cleaned by air and gaseous vehicle heated by the heat storage bed therebelow and passed upward therethrough in the course of heating the other catalyst bed and reforming said hydrocarbon therein.

4. A process for catalytically reforming liquid and gaseous hydrocarbons in a pair of shells having a crossover zone connecting the top portions thereof and each having a porous catalyst bed intermediate its upper and lower ends and a separate, porous, refractory, heat storage bed below the catalyst bed, said process comprising the steps of: heating a first one of said shells and the catalyst bed and heat storage bed therein by passing air upwardly through the second one of said shells and the heat storage bed and catalyst bed therein to provide a gaseous stream flowing along a path through said cross-over and downward through the catalyst bed and heat storage bed in said first shell, introducing a 10 fluid fuel into said stream in said second shell above the catalyst bed therein for admixture and combustion with said air, and conducting combustion products of said fuel and air along said path into said first shell and downward through the catalyst bed and heat storage bed therein to heat the same; passing a stream of a gaseous vehicle upwardly through the heat storage bed and catalyst bed in said second shell and along said path from said second shell into said first shell, introducing the hydrocarbon to be reformed into said path countercurrent to said gaseous vehicle for dispersion in and entrainment with said gaseous vehicle, conducting the gaseous vehicle and entrained hydrocarbon downward through the heated catalyst bed in said first shell for reforming the hydrocarbon, and conducting the gaseous vehicle and products of the reforming reaction downward through the heat storage bed of said first shell and out of said first shell at the bottom thereof to complete one heat run and make run cycle; and repeating said steps in subsequent cycles with the relationship of said shells in each cycle reversed from that of the preceding cycle; whereby, during each cycle, one of said catalyst beds is cleaned by air and gaseous vehicle heated by the heat storage bed therebelow and passed upward therethrough in the course of heating the other catalyst bed and reforming said hydrocarbon therein.

5. A process for catalytically reforming liquid and gaseous hydrocarbons in a pair of shells having a crossover zone connecting the top portions thereof and each having a porous catalyst bed intermediate its upper and lower ends and a separate, porous, refractory, heat storage bed below the catalyst bed, said process comprising the steps of: heating a first one of said shells and the catalyst bed and heat storage bed therein by passing air upwardly through the second one of said shells and the heat storage bed and catalyst bed therein to provide a gaseous stream flowing along a path through said cross-over and downward through the catalyst bed and heat storage bed in said first shell, introducing a fluid fuel into said stream between the two catalyst beds for admixture and combustion with said air, and conducting combustion products of said fuel and air downward through the catalyst bed and heat storage bed in said first shell to heat the same; passing a stream of a gaseous vehicle upwardly through the heat storage bedand catalyst bed in said second shell and along said path from said second shell into said first shell, introducing the hydrocarbon to be reformed into said path in said second shell above the catalyst bed therein and countercurrent to said gaseous vehicle for dispersion in and entrainment with said gaseous vehicle, conducting the gaseous vehicle and entrained hydrocarbon along said path into said first shell and downward through the heated catalyst bed therein for reforming the hydrocarbon, and conducting the gaseous vehicle and products of the reforming reaction downward through the heat storage bed of said first shell and out of said first shell at the bottom thereof to complete one heat run and make run cycle; and repeating said steps in subsequent cycles with the relationship of said shells in each cycle reversed from that of the preceding cycle; whereby, during each cycle, one of said catalyst beds is cleaned by air and gaseous vehicle heated by the heat storage bed therebelow and passed upward therethrough in the course of heating the other catalyst bed and reforming said hydrocarbon therein.-

6. A process for catalytically reforming liquid and gaseous hydrocarbons in a pair of shells having a crossover zone connecting the top portions thereof and each having, a porous catalyst bed intermediate its upper and lower ends and a separate, porous, refractory, heat storage bedbelow the catalyst bed, said process comprising the steps of: heating a first one of said shells and the catalyst bed and heat storage bed therein by passing air upwardly 'through'the second one of said shells and the heat storage bed and catalyst bed therein to provide a gaseousstream flowing along a path through said cross-over and downward through the catalyst bed and heat storage bed in said first shell, introducing a fluid fuel into said stream in said second shell above the catalyst bed therein for admixture and combustion with said air, and conducting combustion products of said fuel and air along said path into said first shell and downwardihrough the catalyst bed and heat storage bed therein to heat the same; passing a stream of a gaseous vehicle upwardly through the 'heat storage bed and catalyst bed in said second shell and along said path from said second shell into said first shell, introducing the hydrocarbon to be reformed into said path in said second shell above the catalyst bed therein and countercurrent to said gaseous vehicle for dispersion in and entrainment with said gaseous vehicle, conducting the gaseous vehicle and entrained hydrocarbon along said path into said first shell and downward through the heated catalyst bed therein for reforming the hydrocarbon, and conducting the gaseous vehicle and products of thereforming reaction downward through the heat storage bed of said first shell and out of said first shell at the bottom thereof to complete, one heat run and make run cycle; and repeating said steps in subsequent cycles with the relationship of said shells in each cycle reversed from that of the preceding cycle; whereby, during each cycle, one of said catalyst beds is cleaned by air and gaseous vehicle heated by the heat storage bed therebelow and passed upward therethrough in the course of heating the other catalyst bed and reforming said hydrocarbon therein. r

7. A process for catalytically reforming liquid and gaseous hydrocarbons in a pair of shells having a crossover zone connecting the top portions thereof and each having'a porous catalyst bed intermediate its upper and lower ends and a separate, porous, refractory, heat storage bed below the catalyst bed, said process comprising the steps of: heating a first one of said shells and the catalyst bed and heat storage bed therein by passing air upwardly through the second one of said shells and the heat storage bed and catalyst bed therein to provide a gaseous stream flowing along a path through said crossa over and downward through the catalyst bed and heat storage bed in said first shell, introducing a fluid fuel into said stream between the two catalyst beds for admixture and combustion with said air, and conducting combustion products of said fuel and air downward through-the catalyst bed 'and'heat storage bed in said first shell to heat the same; passing a gaseous vehicle upwardly through said second shell and the heat storage bed and cataiyst bed therein, along said path into said first shell, and downward through sai first shell and the catalyst bed and heat storage bed therein to purge the system; continuing the flow of said gaseous vehicle, introducing the hydrocarbon to be reformed into said pathfor dispersion in and entrainment with said gaseous vehicle, conducting the gaseous vehicle andentrained hydrocarbon downward through the heated catalyst bed in said first shell for reforming the hydrocarbon, and conducting the gaseous vehicle and products of the reforming reaction downward through the heat storage bed of said first shell and out of said first shell at the bottom thereof to complete one heat run and make run cycle; and repeating said steps in subsequent cycles eous hydrocarbons in a pair of shells having a cross-over zone connecting the top portions thereof and each containing a porous, refractor heat storage bed and a porous catalyst bed thereabove, said process'comprising the steps of: heating 'a first one of said shells and the catalyst bed and heat storage bed therein by passing a' stream of air'upward through the second one of said shells and the heat storage bed and catalyst bed therein to provide a gaseous stream flowing along a path through said crossover and downward through the catalyst bed and heat storage bed in said first shell, introducing a fluid fuel into said path above the catalyst bed in said second shell for admixture and combustion with said air, and conducting combustion products of said air and fluid fuel along said path and downward through the catalyst bed and heat storage bed in said first shell to supply heat thereto; introducing the hydrocarbon to be reformed into said path between the two catalyst beds, introducing steamvinto the bottom of said second shell and conducting it upward through the heat storage bed and catalyst bed therein and along said path into contact with said hydrocarbon to entrain and disperse the same in the steam, conducting the steam and entrained hydrocarbon along said path and downward through the heated catalyst bed in said first shell for reforming the hydrocarbon, and conducting the steam and the products of the reforming reaction downward through the heat storage bed of said first shell and out of said first shell at the bottom thereof to complete one heating and reforming cycle; and repeating said steps in subsequent cycles with the relationship of said shells in each cycle reversed from that of the preceding cycle; whereby, during each cycle, one of said catalyst beds is cleaned by air and steam heated by the heat storage bed therebelow and passed upwardly therethrough in the course of heating the other catalyst bed and reforming said hydrocarbon therein.

9. A process for catalytically reforming hydrocarbon oil in a pair of shells having a cross-over zone connecting the top portions thereof and each containing a porous catalyst bed intermediate its upper and lower ends and a separate, porous, refractory, heat storage bed below the catalyst bed, said process comprising the steps of heating a first one of said shells and the catalyst bed and heat storage 'bed therein by passing air upward through tie second one of said shells and the heat storage bed and catalyst bed therein to provide a gaseous stream flowing along a path through said cross-over and downward through the catalyst bed and heat storage bed in said first shell, introducing a fluid fuel into said path between the two catalyst beds for admixture and combustron with said air, and conducting combustion products of said air and fuel along said path and downward through the catalyst bed and heat storage bed insaid first shell to heat the same; introducing hydrocarbon oil to be reformed into said path as a spray, introducing steam into the bottom of said second shell and conducting it upward and through the heat storage bed and catalyst bed therein into contact with said oil spray to entrain and disperse the same in the steam, conducting the steam and entrained oil downward through the heated catalyst bed in said first shell for reforming the oil, and conducting the steam and the products of the reforming reaction downward through the heat storage bed of said first shell and out of said first shell at the bottom thereof to complete one heating and reforming cycle; and repeating said steps in subsequent cycles with the relationship of said shells in each cycle reversed from that of the preceding cycle; whereby, during each cycle, one of said catalyst beds is cleaned by air and steam heated by the heat storage bed therebelow and passed upward therethrough in the course of heating the other catalyst bed and reforming said hydrocarbon therein.

10. A process for catalytically reforming hydrocarbon oil in a pair of shells having a cross-over zone connecting the top portions thereof and each containing a catalyst bed intermediate its upper and lower ends and a separate, porous, refractory, heat storage bed below the catalyst bed, said process comprising the steps of: heating a first one of said shells and the catalyst bed and heat storage bed therein by passing air upwardly through the second one of said shells and the heat storage bed and catalyst bed therein, introducing a fluid fuel into said second shell for admixture and combustion with said air, and conducting combustion products of said air and fuel through said cross-over and into and downward through said first shell and the catalyst bed and heat storage bed therein to supply heat thereto; introducing the hydrocarbon oil to be reformed into the top of said second shell as a spray, introducing steam into the bottom of said second shell and conducting it upward therethrough into contact with said hydrocarbon oil to entrain and disperse the same in the steam, conducting the steam and entrained hydrocarbon oil from said second shell through said cross-over and downward through the heated catalyst bed in said first shell for reforming the hydrocarbon oil, and conducting the steam and the products of the reforming reaction downward through the heat storage bed of said first shell and out of said first shell at the bottom thereof to complete one heating and reforming cycle; and repeating said steps in subsequent cycles with the relationship of said shells in each cycle reversed from that of the preceding cycle; whereby, during each cycle, one of said catalyst beds is cleaned by air and steam heated by the heat storage bed therebelow and passed upward therethrough in the course of heating the other catalyst bed and reforming said hydrocarbon oil therein.

11. The process of claim in which said spray of hydrocarbon oil is introduced into said second shell as a downward directed spray.

12. The process of claim 10 in which a reducing gas is introduced into said second shell throughout the period of introduction of said hydrocarbon oil into said second shell, for maintaining a more reducing atmosphere in the system during the reforming reaction.

13. The process of claim 10 in which, at the end of each heating and reforming cycle, the introduction of steam is continued for a brief period to assist in decarbonizing the catalyst used to reform said oil during said cycle and to produce additional combustible gas.

14. A process for catalytically reforming hydrocarbon oil in a pair of shells having a cross-over zone connecting the top portions thereof and each containing a catalyst bed intermediate its upper and lower ends and a separate, porous, refractory, heat storage bed below the catalyst bed, said process comprising the steps of: heating a first one of said shells and the catalyst bed and heat storage bed therein by passing air upwardly through the second one of said shells and the heat storage bed and catalyst bed therein, introducing a fluid fuel into said second shell for admixture and combustion with said air, and conducting combustion products of said air and fuel through said cross-over and into and downward through said first shell and the catalyst bed and heat storage bed therein to supply heat thereto; passing steam upwardly through said second shell and the heat storage bed and catalyst bed therein, through said cross-over, and downwardly through said first shell and the catalyst bed and heat storage bed therein to purge the same; introducing the hydrocarbon oil to be reformed into the top of said second shell as a spray, continuing the introduction of steam into the bottom of said second shell and conducting it upward therethrough into contact with said hydrocarbon oil to entrain and disperse the same in the steam, conducting the steam and entrained hydrocarbon oil from said second shell through said cross-over and downward through the heated catalyst bed in said first shell for reforming the hydrocarbon oil, and conducting the steam and the products of the reforming reaction downward through the heat storage bed of said first shell and out of said first shell at the bottom thereof to complete one heating and reforming cycle; and repeating said steps in subsequent cycles with the relationship of said shells in each cycle reversed from that of the preceding cycle; whereby, during each cycle, one of said catalyst beds is cleaned by air and steam heated by the heat storage bed therebelow and passed upward therethrough in the course of heating the other catalyst bed and reforming said hydrocarbon oil therein.

15. A process for catalytically reforming hydrocarbon oil in a pair of shells having a cross-over Zone connecting the top portions thereof and each containing a catalyst bed intermediate its upper and lower ends and a separate, porous, refractory, heat storage bed below the catalyst bed, said process comprising the steps of: heating a first one of said shells and the catalyst bed and heat storage bed therein by passing air upwardly through the second one of said shells and the heat storage bed and catalyst bed therein, introducing a fluid fuel into said second shell for admixture and combustion with said air, and conducting combustion products of said air and fuel through said cross-over and into and downward through said first shell and the catalyst bed and heat storage bed therein to supply heat thereto; introducing the hydrocarbon oil to be reformed into the top of said second shell as a spray, introducing steam into the bottom of said second shell and conducting it upward therethrough into contact with said hydrocarbon oil to entrain and disperse the same in the steam, conducting the steam and entrained hydrocarbon oil from said second shell through said cross-over and downward through the heated catalyst bed in said first shell for reforming the hydrocarbon oil, and conducting the steam and the products of the reforming reaction downward through the heat storage bed of said first shell and out of said first shell at the bottom thereof; passing air upwardly through said second shell and the heat storage bed and catalyst bed therein, through said cross over, and downward through said first shell and the catalyst bed and heat storage bed therein to reactivate the catalyst in said first shell and to complete one cycle of operation; and repeating said steps in subsequent cycleS with the relationship of said shells in each cycle reversed from that of the preceding cycle; whereby, during each cycle, one of said catalyst beds is cleaned by air and steam heated by the heat storage bed therebelow and passed upward therethrough in the course of heating and reactivating the other catalyst bed and reforming said hydrocarbon oil therein.

References Cited in the file of this patent UNITED STATES PATENTS 1,841,201 Odell Jan. 12, 1932 2,071,286 Johnson et al Feb. 16, 1937 2,205,554 Brandegee et al Jan. 25, 1940 2,289,922 Mekler July 14, 1942 2,311,498 Voorhies Feb. 16, 1943 2,592,591 Odell Apr. 15, 1952 2,605,176 Pearson July 29, 1952 2,665,979 Taussig Jan. 12, 1954 2,714,058 Stookey et al July 26, 1955 2,720,450 Haugh Oct. 11, 1955 2,743,171 Janeway Apr. 24, 1956 2,829,034 Ruschin et a1. Apr. 1, 1958 FOREIGN PATENTS 693,724 Great Britain July 8, 1953

Claims

1. A PROCESS FOR CATALYTICALLY REFORMING LIQUID AND GASEOUS HYDROCARBONS IN A PAIR OF SHELLS HAVING A CORSS-OVER ZONE CONNECTING THE TOP PORTIONS THEREOF AND EACH HAVING A POROUS CATALYST BED INTERMEDIATE ITS UPPER AND LOWER ENDS AND A SEPARATE, POROUS, REFRACTORY, HEAT STORAGE BED BELOW THE CATALYST BED, SAID PROCESS COMPRISING THE STEPS OF, HEATING A FIRST ONE OF SAID SHELLS AND THE CATALYST BED AND HEAT STORAGE BED THEREIN BY PASSING AIR UPWARDLY THROUGH THE SECOND ONE OF SAID SHELLS AND THE HEAT STORAGE BED ABD CATALYST BED THEREIN TO PROVIDE A GASEOUS STREAM FLOWING ALONG A PATH THROUGH SAID CROSS-OVER AND DOWNWARD THROUGH THE CATALYST BED AND HEAT STORAGE BED IN SAID FIRST SHELL, INTRODUCING A FLUID FUEL INTO SAID STREAM BETWEEN THE TOW CATALYST BED FOR ADMIXTURE AND COMBUSTION WITH SAID AIR, AND CONDUCTING COMBUSTION PRODUCTS OF SAID FUEL AND AIR DOWNWARD THROUGH THE CATALYST BED AND HEAT STORAGE BED IN SAID FIRST SHELL TO HEAT THE SAME, PASSING A STREAM OF A GASEOUS VEHICLE ALONG SAID