US2921845A - Catalytic reforming of hydrocarbons - Google Patents

Catalytic reforming of hydrocarbons Download PDF

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US2921845A
US2921845A US560801A US56080156A US2921845A US 2921845 A US2921845 A US 2921845A US 560801 A US560801 A US 560801A US 56080156 A US56080156 A US 56080156A US 2921845 A US2921845 A US 2921845A
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shell
bed
catalyst
catalyst bed
heat storage
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Robert T Kyle
Nilsen Arve
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GAS MACHINERY CO
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GAS MACHINERY CO
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Priority to US560801A priority patent/US2921845A/en
Priority to GB11009/56A priority patent/GB803788A/en
Priority to DEG19564A priority patent/DE1056318B/de
Priority to FR1170712D priority patent/FR1170712A/fr
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G35/00—Reforming naphtha
    • C10G35/04—Catalytic reforming
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/30—Loose or shaped packing elements, e.g. Raschig rings or Berl saddles, for pouring into the apparatus for mass or heat transfer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
    • B01J8/06—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds in tube reactors; the solid particles being arranged in tubes
    • B01J8/065—Feeding reactive fluids
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
    • C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
    • C01B3/46—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using discontinuously preheated non-moving solid materials, e.g. blast and run
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G11/12—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with discontinuously preheated non-moving solid catalysts, e.g. blast and run
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
    • B01J2208/02—Processes carried out in the presence of solid particles; Reactors therefor with stationary particles
    • B01J2208/023—Details
    • B01J2208/024—Particulate material
    • B01J2208/025—Two or more types of catalyst
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/30—Details relating to random packing elements
    • B01J2219/302—Basic shape of the elements
    • B01J2219/30223—Cylinder
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/30—Details relating to random packing elements
    • B01J2219/302—Basic shape of the elements
    • B01J2219/30242—Star
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/30—Details relating to random packing elements
    • B01J2219/302—Basic shape of the elements
    • B01J2219/30296—Other shapes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/30—Details relating to random packing elements
    • B01J2219/304—Composition or microstructure of the elements
    • B01J2219/30416—Ceramic
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/30—Details relating to random packing elements
    • B01J2219/304—Composition or microstructure of the elements
    • B01J2219/30475—Composition or microstructure of the elements comprising catalytically active material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/30—Details relating to random packing elements
    • B01J2219/308—Details relating to random packing elements filling or discharging the elements into or from packed columns
    • B01J2219/3081—Orientation of the packing elements within the column or vessel
    • B01J2219/3085—Ordered or stacked packing elements
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02—Processes for making hydrogen or synthesis gas
    • C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
    • C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
    • C01B2203/0233—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a steam reforming step
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/08—Methods of heating or cooling
    • C01B2203/0805—Methods of heating the process for making hydrogen or synthesis gas
    • C01B2203/0811—Methods of heating the process for making hydrogen or synthesis gas by combustion of fuel
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/08—Methods of heating or cooling
    • C01B2203/0805—Methods of heating the process for making hydrogen or synthesis gas
    • C01B2203/0811—Methods of heating the process for making hydrogen or synthesis gas by combustion of fuel
    • C01B2203/0822—Methods of heating the process for making hydrogen or synthesis gas by combustion of fuel the fuel containing hydrogen
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/12—Feeding the process for making hydrogen or synthesis gas
    • C01B2203/1205—Composition of the feed
    • C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
    • C01B2203/1235—Hydrocarbons
    • C01B2203/1247—Higher hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/16—Controlling the process
    • C01B2203/169—Controlling the feed
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/10—Process efficiency
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/10—Process efficiency
    • Y02P20/129—Energy recovery, e.g. by cogeneration, H2recovery or pressure recovery turbines
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts

Definitions

  • 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.
  • 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.
  • process steam is fed through the heated checkerbrick in the heating chamber and thence into 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.
  • 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 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.
  • 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.
  • 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.
  • a gaseous vehicle such as steam
  • the catalyst bed in the first shell 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.
  • 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.
  • 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;
  • FIG. 1 successive cycles, each including a heat run and make run sequence, are performed alternately'in shells 11 and 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.
  • 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).
  • 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.
  • a suitable gaseous material such as low pressure steam
  • 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.
  • a suitable gaseous vehicle which may .be the same steam used for the purging operation
  • the conduit 26 is 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.
  • a suitable gaseous vehicle which may .be the same steam used for the purging operation
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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:
  • 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.
  • 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,
  • 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.
  • 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.
  • the shells 31 and 32 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.
  • 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.
  • 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.
  • 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.
  • the catalyst beds 40 supplement the effects ot the respectively associated checkerbrick structures 38 in storing and releasing heat as described.
  • 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.
  • 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.
  • 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.
  • 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.
  • FIG. 3 to 6 inclusive certain modifications of the apparatus of Fig. 2 are shown.
  • the features common to both forms of apparatus are identified by the same reference characters in Figs. 2 and 3.
  • 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.
  • 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.
  • 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,
  • 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 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 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.
  • 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 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
  • 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 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 steps of:
  • 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 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
  • 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 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
  • 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 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
  • 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 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
  • 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 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-
  • 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 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
  • 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 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-

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US560801A 1956-01-23 1956-01-23 Catalytic reforming of hydrocarbons Expired - Lifetime US2921845A (en)

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BE549232D BE549232A (enrdf_load_stackoverflow) 1956-01-23
US560801A US2921845A (en) 1956-01-23 1956-01-23 Catalytic reforming of hydrocarbons
GB11009/56A GB803788A (en) 1956-01-23 1956-04-11 Catalytic reforming of hydrocarbons and apparatus therefor
DEG19564A DE1056318B (de) 1956-01-23 1956-05-05 Verfahren und Vorrichtung zur katalytischen Veredlung bzw. Umbildung von fluessigen und gasfoermigen Kohlenwasserstoffen
FR1170712D FR1170712A (fr) 1956-01-23 1956-06-30 Procédé de transformation d'hydrocarbures et appareil pour sa mise en oeuvre

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3467504A (en) * 1965-03-15 1969-09-16 Chemical Construction Corp Apparatus for hydrocarbon reforming
US3607225A (en) * 1965-06-22 1971-09-21 Inst Cercetari Metalurgice Process and apparatus for the direct reduction of iron ores
WO2006000579A1 (fr) * 2004-06-25 2006-01-05 Jacques Ribesse Procédé et dispositif de production de gaz réducteur
US20070111055A1 (en) * 2005-11-16 2007-05-17 Katikaneni Sai P Reforming catalyst and method and apparatus for making and loading same
US20110114741A1 (en) * 2008-07-22 2011-05-19 Webasto Ag Mobile heating device

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB947165A (en) * 1961-06-01 1964-01-22 Power Gas Ltd Improvements in or relating to methods and apparatus for the production of combustible gas

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US1841201A (en) * 1932-01-12 Process fob making combttstibls gas
US2071286A (en) * 1933-04-25 1937-02-16 Combustion Utilities Corp Oil gasification process
US2205554A (en) * 1935-12-16 1940-06-25 Combustion Utilities Corp Method for generating oil gas
US2289922A (en) * 1939-10-30 1942-07-14 Universal Oil Prod Co Control of endothermic and exothermic reactions
US2311498A (en) * 1939-09-16 1943-02-16 Standard Catalytic Co Aviation fuel
US2592591A (en) * 1949-08-29 1952-04-15 William W Odell Manufacture of combustible gas
US2605176A (en) * 1949-09-02 1952-07-29 Allied Chem & Dye Corp Manufacture of combustible gas
GB693724A (en) * 1951-03-19 1953-07-08 Humphreys & Glasgow Ltd Improvements relating to the production of oil gas
US2665979A (en) * 1949-10-31 1954-01-12 United Gas Improvement Co Method of reforming gaseous hydrocarbons
US2714058A (en) * 1949-10-03 1955-07-26 Gas Machinery Co Method and apparatus for making oil gas
US2720450A (en) * 1950-08-23 1955-10-11 United Gas Improvement Co Process and apparatus for manufacturing gas rich in hydrogen
US2743171A (en) * 1950-08-23 1956-04-24 United Gas Improvement Co Method for making gas rich in hydrogen
US2829034A (en) * 1954-01-14 1958-04-01 Power Gas Ltd Manufacture of combustible gases

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Publication number Priority date Publication date Assignee Title
US1841201A (en) * 1932-01-12 Process fob making combttstibls gas
US2071286A (en) * 1933-04-25 1937-02-16 Combustion Utilities Corp Oil gasification process
US2205554A (en) * 1935-12-16 1940-06-25 Combustion Utilities Corp Method for generating oil gas
US2311498A (en) * 1939-09-16 1943-02-16 Standard Catalytic Co Aviation fuel
US2289922A (en) * 1939-10-30 1942-07-14 Universal Oil Prod Co Control of endothermic and exothermic reactions
US2592591A (en) * 1949-08-29 1952-04-15 William W Odell Manufacture of combustible gas
US2605176A (en) * 1949-09-02 1952-07-29 Allied Chem & Dye Corp Manufacture of combustible gas
US2714058A (en) * 1949-10-03 1955-07-26 Gas Machinery Co Method and apparatus for making oil gas
US2665979A (en) * 1949-10-31 1954-01-12 United Gas Improvement Co Method of reforming gaseous hydrocarbons
US2720450A (en) * 1950-08-23 1955-10-11 United Gas Improvement Co Process and apparatus for manufacturing gas rich in hydrogen
US2743171A (en) * 1950-08-23 1956-04-24 United Gas Improvement Co Method for making gas rich in hydrogen
GB693724A (en) * 1951-03-19 1953-07-08 Humphreys & Glasgow Ltd Improvements relating to the production of oil gas
US2829034A (en) * 1954-01-14 1958-04-01 Power Gas Ltd Manufacture of combustible gases

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3467504A (en) * 1965-03-15 1969-09-16 Chemical Construction Corp Apparatus for hydrocarbon reforming
US3607225A (en) * 1965-06-22 1971-09-21 Inst Cercetari Metalurgice Process and apparatus for the direct reduction of iron ores
WO2006000579A1 (fr) * 2004-06-25 2006-01-05 Jacques Ribesse Procédé et dispositif de production de gaz réducteur
BE1016102A3 (fr) * 2004-06-25 2006-03-07 Ribesse Jacques Max Stanislas Procede et dispositif de production de gaz reducteur destine, en particulier a la reduction de minerai.
US20070111055A1 (en) * 2005-11-16 2007-05-17 Katikaneni Sai P Reforming catalyst and method and apparatus for making and loading same
US7655196B2 (en) * 2005-11-16 2010-02-02 Fuelcell Energy, Inc. Reforming catalyst and method and apparatus for making and loading same
US20110114741A1 (en) * 2008-07-22 2011-05-19 Webasto Ag Mobile heating device

Also Published As

Publication number Publication date
DE1056318B (de) 1959-04-30
BE549232A (enrdf_load_stackoverflow) 1900-01-01
FR1170712A (fr) 1959-01-16
GB803788A (en) 1958-10-29

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