US2548286A - Method and apparatus for conducting hydrocarbon conversion reactions - Google Patents
Method and apparatus for conducting hydrocarbon conversion reactions Download PDFInfo
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- US2548286A US2548286A US124463A US12446349A US2548286A US 2548286 A US2548286 A US 2548286A US 124463 A US124463 A US 124463A US 12446349 A US12446349 A US 12446349A US 2548286 A US2548286 A US 2548286A
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- 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
- B01J8/08—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with moving particles
- B01J8/12—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with moving particles moved by gravity in a downward flow
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C4/00—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms
- C07C4/02—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms by cracking a single hydrocarbon or a mixture of individually defined hydrocarbons or a normally gaseous hydrocarbon fraction
- C07C4/04—Thermal processes
Definitions
- This invention relates to a method and apparatus for conducting chemical reactions at very high temperatures in the presence offa moving particle form solid material. Particularly it relates to an improved continuous method and apparatus for conducting highly endothermic, high temperature conversions of hydrocarbons, supplying the heat therefor and quenching the usually unstable reaction products.
- Exemplary of the processes to which the method of this invention may be applied are the pyrolytic conversion of methane, propane and other light hydrocarbons to acetylene containing products at temperatures of the order of 2000-2600 F. and approximately atmospheric pressures.
- Another process is the manufacture of ethylene by the cracking of heavier hydrocarbons such as ethane, propane, butane or gas oils at temperatures of the order of 1450-1800" F. over an inert mass of granular material
- Another process is the conversion of powdered coal to CO and H2 by contact with steam or steam and oxygen at temperatures of the order of 200G-2500 F.
- Still another reaction is the pyrolytic conversion of gaseous or liquid hydrocarbons to aromatics at temperatures of the order of 1250-1800" F.
- Still another process is the preparation of thiophene and butadiene by reaction between n-butane and/or butene and sulfur vapors at temperatures of the order of 850-1400 F.
- Another process is the high tempcrature catalytic cracking conversion of hydrocarbons to high yields of aviation gasoline and C4 fractions.
- a majorobject of this invention is the provision of an improved continuous method and apparatus for conducting endothermic reactions atelevated tioned dniculties.
- a specific object is the provision in a process for conducting high temperature, endothermic conversions of hydrocarbon reactants of a method and apparatus wherein the heat maybe supplied, the reaction may be conducted and the reaction products may be quenched all within a single chamber.
- Another object is the provision of a method and apparatus for conducting high temperature reactions in the presence'of moving solids Without the necessity of heating the reaction housing and solid material handling equipment tothe elevated reaction temperature.
- this invention involves a process and apparatus for conducting high temperature conversions of reactants wherein a column of flowing granular solids is maintained in a coniined housing, which column is supplied exclusively at its upper end with solids existing substantially below the reaction temperature and from the lower end of which column solids are withdrawn existing substantially below the reaction temperature.
- a lhot nucleus is established in a region within the column spaced substantially away from the walls of the housing.
- the reactant in liquid, gaseous or powdered form isintroduced directly into the heated nucleus of gravitating solids whereby the desired conversion is effected.
- the conversion products in the gaseous phase may fan out into the mass of cooler solids which surround the hot nucleus and are thereby quenched to a level far below the reaction temperature so that further conversion of the product is substantially inhibited, after Which the products are withdrawn from the conversion chamber.
- the reaction products may be withdrawn directly from the hot reaction nucleus so that the surrounding mass of cooler solids serves the principal function of a shield between the reaction nucleus and the vessel walls.
- the solidmaterial is withdrawn from the bottom of the chamber separately of the gasiform conversion products.
- this invention is one wherein granular solids existing substantially below the hydrocarbon average reaction temperature are introduced into the upper section of a chamber and are passed downwardly through the chamber as a substantially compact column; A stream containing a combustible fuel and combustion supporting gas is introduced downwardly into the column at a location below ts surface and spaced away from the chamber walls to effect combustion in a corelike portion of the column which exists principally immediately below and adjacent the loca tion of the fuel introduction. This core is later ally surrounded by cooler solids which shield the walls of the chamber, and the hot core of solids is extended downwardly below the location of combustion due to the downward flow of the solids.
- the combustion gases are permitted to fan outwardly toward the cooler material while reversing the direction of gas ilow and are withdrawn above the level of fuel introduction.
- the hydrocarbon reactant is introduced into the hot core of solids below the level of the combustion reaction and is converted by means of heat contained in the solids.
- the gasiform reaction prode ucts are caused to pass outwardly into the cooler solids surrounding the reaction core and the direction of reactant flow is reversed so that the quenched gasiform products are withdrawn from the chamber below the level of reactant introduction.
- Solids from the reaction core and surrounding'cooler solids are withdrawn mixed together from the bottom of the chamber at a temperature substantially below the reaction temperature.
- Figure 1 is an elevational view, partially in section, of a system adapted for conducting this invention
- Figures 2 and 3 are elevational views, partially in section of a modified portion of the apparatus shown in Figure 1
- Figure 4 is an elevational view, partially in section of another modied form of the invention. All of these drawings are highly diagrammatic in form.
- FIG. l there is shown a chamber I of which the upper section is of somewhat smaller diameter than the lower section and fits thereinto so as to provide an annular gas receiving space II, provided with an outlet I2. It will be understood, however, that the chamber may be of uniform diameter throughout its length with other suitable means provided for gas withdrawal.
- a hopper I3 for solid material supply is positioned above chamber I and a gravity feed conduit I extends downwardly from the bottom of hopper I3 to a point within and below the top of chamber I0 so as to provide above the column or solids I5 a second gas receiving space I6.
- An outlet l1 connects through the vessel wall for withdrawal of gas from space I5.
- a solid material outlet I9 having a iiow control valve 20 thereon is connected into the bottom of chamber I0.
- Two vertically spaced partitions 2l and 22 are provided across the chamber IU above the outlet I9.
- the partition 2l has a plurality of uniformly spaced tubes 23 dependent therefrom and the partition 2'( has a smaller number of dependent tubes 24 which are staggered with respect tubes 23 so that each tube 24 receives flow from several tubes 23.
- the tubes 2 are symmetrically positioned horizontally with respect to the outlet I9. This arrangement promotes uniform withdrawal of solids from all portions of the vessel cross section.
- a flow control arrangement of this type is disclosed and claimed in United States Patent 2,412,136, issued to Evans et al. December 3, 1946.
- a purge gas inlet'25 is provided immediately below partition ZI.
- Inverted gas distributing troughs 26 of angular shape are positioned above the partition 2
- a vertical tube 23 extends down into the upper section of chamber I0 and terminates below the solids feed conduit I4 at a point located centrally with respect the chamber walls.
- An air inlet pipe 3U connects into the upper end of tube 28.
- a smaller tube 3l extends centrally downwardly with tube 28 and terminates above the lower end of tube 28. Fuel is supplied to the upper end of tube 3I through pipe 32.
- a reactant inlet tube 33 extends into the chamber Hl and terminates on itsupwardly facing end a short vertical distance below and directly in line with the tube 28.
- a perforated distributing cap 35 is provided on the end of tube 33.
- a ring type manifold 36 provided with spaced openings along its lower face is positioned within chamber I0 between the levels of the facing ends of tubes 28 and 33 and an inlet pipe 31 connects into the ring manifold.
- An external elevator Il which may be of conventional design is provided for transfer of solids from outlet I9 to a point above hopper I3 from which the solids ilow to the supply hopper via duct 4I.
- An inert refractory contact material such as granular carborundum, existing at about 700 F., enters the chamber IS from hopper i3.
- Fuel gas such as reiinery gas or in some cases fuel oil introduced from pipe 32 into tube 3
- Combustion of the fuel occurs in the substantially compact bed in a narrow zone close to the lower end of tube 28. This burning zone usually does not extend more than about 3 4 inches away from the outlet of tube 28.
- a hot nucleus of combustion in said column in which the solid material is heated to temperatures of the order of 2300 F. and higher.
- the solids flowing down in the portion of the chamber laterally surrounding the nucleus of combustion are at a much lower temperature so that the temperature along the vessel walls is of the order of 'ZOO-800 F.
- Flue gas formed by the combustion is caused to reverse its direction of flow so that it passes up through the annular bed around tube 2B into receiving space I6 from which it is withdrawn 5, 'via pipe il.
- Propane which may ⁇ or may not contain some preheat is introduced via tube 33 upwardly into the bed at a location above its lower end and directly below the location of introduction of the air and fuel mixture so that the propane is contacted with heated solids flowing down from the combustion nucleus into what may be called a reaction nucleus.
- the reaction nucleus existing at or above 2300" F., is surrounded laterally by solids existing at substantially lower temperature of the order of 'ZOO-800 F.
- the reaction. products which are unstable under the conditions in the reaction nucleus are caused to reverse in ilow direction and to--pass downwardly through the adjacent cooler contact material in the bed between the tube 33 and the vessel walls whereby the products are quenched to a level at which they are stable and do not undergo further reaction.
- the gasiform products pass on down through the bed of mixed solids in the portion of the bed below the reaction nucleus and are with drawn from gas receiving space il via outlet pipe l2.
- the hot solids from the reaction nucleus gradually become mixed with cooler surrounding solids at levels inthe bed below the reaction nucleus so that the mixed solids reaching the cooling section 50 may exist at a temperature of the order of 80G-900 F. or lower, depending upon the relative amounts of solid flow in the hot nucleus and in the surrounding portion of the bed.
- the solids are then cooled by introduction of a suitable cooling fluid such as steam or water or flue gas supplied via header 39.
- the cooled solids are transferred by elevator 50 to hopper I3 from which they again flow to chamber Ill.
- One method of accomplishing this is to introduce a seal gas such as steam or ue gas into the bed via manifold Se.
- the steam pressure is maintained sufficiently above that in the combustion and reaction nucleuses to cause steam to flow both upwardly and downwardly through the bed from its location of introduction.
- Further control is dictated by maintaining balance between the amount of oxygen introduced via pipe 30 and withdrawn in one form or another via pipe Il. When this is done, only gases from the combustion nucleus plus a very small amount of seal gas will be withdrawn via pipe il while only hydrocarbon conversion products plus a small amount of seal gas will pass down through the bed to outlet I2.
- This operation may be effected by providing a flow measuring tone 5
- the valve is controlled so as to maintain a nxed amount of air feed.
- the fuel feed may be similarly controlled in the proper flow measuring orifice 56 on the ue gas outlet pipe l1.
- the valve 54 may be located on pipe l1.
- reaction temperature in the above operation is of the order of 2300o F. and upwards
- thewalls of chamber IU are subjected only to the much lower temperature of they flowing bed surrounding the combustion and reaction nucleuses.
- the only structural surfaces exposed to the extreme temperatures are portions of the gas inlet tube 28, reactant inlet tube 33 and the steam manifold 3e.
- These members may be constructed of refractory material suitable for ywithstanding high temperatures.
- the remainder of the apparatus may be constructed of material presently used in conventional catalytic cracking' reactors and the like which operate at temperatures below l000 F.v
- the solids enter and leave the reaction chamber at temperatures far below the reaction temperature so that they can be practicably conveyed by means of mechanical conveyor equipment.
- V actual combustion and reaction Zones are very small in size and are positioned close together within the same chamber whereby a' great saving in material and in unit height is effected as compared with continuous conversion systems known heretofore. Further simplification of design and improvement of operation is effected due to the lateral placement of the quench Zone with respect the reaction zone Within the same chamber. This effects a reduction in unit height, eliminates a separate quench chamber and permits more accurate control of the period during which the reactant is maintained at the very high reaction temperatures. Many of the reactions of the type to which this method and apparatus may be applied require only a fraction of a second, after which the products should be quenched to slow or preferably to substantially stop further reaction or at least to prevent decomposition of the reaction products.
- the method and apparatus of this invention by providing a Very small reaction nucleus surrounded by a much larger mass of cooler solids is well adapted for accurate control of reactions of the type discussed above.
- a cylindrical tube 'l is supported by rods 69 concentrically around the upwardly extending portion of the reactant inlet 33.
- This tube may be constructed of a suitable refractory material such as fused alumina, carborundum, etc.
- the tube Hi extends upwardly a vertical distance above the level of the upper end of the pipe 33 and downwardly a somewhat greater distancev beyond the same level.
- the tube lll is narrowed in cross-section along a portion of its length at II below the outlet of pipe 33 so as to inhibit downward gas ow from the outlet of pipe 33 while permitting downward flow of solids.
- reaction Zone may be considered to be concentrated in that portion of the tube IIJ above the outlet from pipe 33 and in the bed a short distance directly above and in line with the tube 'ill where the gas fans out and reverses in its direction of flow.
- a second refractory tube I2 having substantially the same diameter as tube l is supported from rods 'i3 below and adjacent the lower end of the combustion gas inlet tube 28.
- the seal gas inlet arrangement is modified somewhat from that shown in Figure 1 and comprises a refractory cone T5 placed centrally in the chamber I and about midway between the lower end of tube 28 and the upper end of tube 33, an inlet pipe 74, insulated along part of its length, delivering uid under the cone 'I5 and a refractory tube 'I5 surrounding the cone l5.
- Vertical spaces are provided between tubes 'I2 and 'I6 and between tubes 'I5 and lo where the combustion gases and reactant gases respectively may fan out and reverse in flow direction.
- An annular shaped, perforated manifold IEB may be provided in the space between the vessel wall and tube 'I6 for seal gas supply to the portion of the vessel outside tube 16.
- An inlet pipe li connects into the manifold It for seal gas supply.
- a portion of the relatively cooled inert refractory solid material introduced into the upper end of the vessel I0 ows into the upper end of tube 'I2 and becomes heated by the fuel combustion occurring within the tube.
- the heated solid material ows down through tube 'I5 and into the upper end of tube 'I0 where it meets the reactant uid and supplies the heat for effective pyrolytic conversion thereof.
- the solid material cooled somewhat due to release of heat for the hydrocarbon reaction passes on through tube 'I0 and mixes with cooler material in the bed therebelow.
- cooler solid material ows down through the annular passage i8 formed between the walls of the chamber IIJ and the tubes 12, 'I6 and l0 and nally joins the stream of material flowing from the lower end of tube 10. Since the rate of downward now of solid material in the portion of the bed below tube 'Ill is maintained constant entirely across the horizontal cross-section of the bed by virtue of the flow control partitions 2l and 22 of Figure 1, the relative amounts of solid i'low by way of the tubes 12, 'I6 and 'I0 and by way of the annular passage Iiimay be accurately controlled by proper control of the relative areas of the annular passage I8 and of the tube 'It at the level of the lower end of tube 10.
- a suitable arrangement adjustable from outside the chamber I0 may be provided for varying the effective area for solid flow at the lower end of tube l0.
- the mixed fuel and air stream issuing from tube 28 flows for the most part down through the moving bed of solids within the confines of tube l2 while the fuel combustion occurs.
- the flue gas formed flows out from under tube l2, fans out into annular passage 18 and then passes upwardly to the receiving space I6 shown in Figure 1.
- a small part of the gas may by-pass the tube 'I2 and flow up through the bed around tube 28. The combustion of this gas will occur before it reaches the portion of the bed over the annular passage 'i8 so that the solids heated by combustion of this gas are principally solids which would enter tube I2 anyway.
- the tube 'I2 may be extended upwardly beyond the tube 28 and restricted in cross-section along a portion of its length similarly to tube 'I0 so as to further insure concentration of combustion heat supply to solids flowing down through tube l2.
- the ue gases will, of course, give up some sensible heat content to the cooler solids in the upper portion of the bed above the combustion zone but this constitutes only a minor portion of the total heat capacity of the mixed gas entering from tube 28.
- Hydrocarbon reactants supplied into tube IIJ either as a liquid or gas or as a powder suspended in gas soon become converted to gasiform products which ow out from the upper end of tube I0 and over into the cooler stream of solids in passage '18.
- the reactant is quenched to a temperature which may be controlled by controlling the inlet temperature of solids to chamber I0 and the amount of solid now in passage 'I8 relative to the amount of reactant introduction to chamber I0.
- a temperature which may be controlled by controlling the inlet temperature of solids to chamber I0 and the amount of solid now in passage 'I8 relative to the amount of reactant introduction to chamber I0.
- tubes l0, 'I2 and 'I6 shown in Figure 3 are provided simply as bailles to aid in guiding the flow when needed and not as insulators, they need not be of any greater thickness than dictated by structural strength requirements. In some operations these tubes may be constructed of alloys adapted to withstand high temperatures.
- the invention is not contemplated as being limited to the particular shape and form of the chamber shown in Figures l and 2 or to the particular details shown for the mixed combustion gas and reactant gas introduction and Withdrawal or to the described means for controlling uniformity of solid material now or for effecting its transfer outside the chamber I0. It is contemplated that in some forms of the invention the initial direction of the reactant introduction may be other than upward and that it may be withdrawn from the chamber at loca-'f tions transversely across the bed from the point of reactant introduction and on the same level therewith.
- the gasiform reaction products may be withdrawn directly from the reaction nucleus without passing through the surrounding insulating shield of cooler contact material.
- Figure 3 shows a modied arrangement of the heating and reaction portion of the apparatus shown in Figure 1. Like elements in Figures 1, 2 and 3 bear corresponding numerals.
- Figure 3 only a single cylindrica1 refractory tube I I0 is positioned within the vessel I0. This tube is so constructed as to provide gas collecting spaces II2 for reaction products. In operation the heating gases issue from tube 28 into the owing mass within tube I I0 and then pass upwardly through the passage between tubes I I0 and 28.
- the heated solids pass through the seal section in the vicinity of cone 'I5 and then into the reaction nucleus which is that portion of the mass within tube I I0 below the end of reactant inlet pipe I I5 and gas collecting space I I2.
- the reaction products are withdrawn from space I I2 via pipes I I6 and conduit I I8. It will be noted that in this arrangement the cool solid material 9 flowing in passage 18 is never contacted ⁇ bythe reactants.
- FIG. 4 An example ⁇ of an arrangement incorporating this embodiment is shown in Figure 4.
- a vessel comprised of a cylindrical upper section 8
- a partition 84 forms the bottom of thefintermediate section and a ring of spaced tubes 85 depend from the partition to provide passageway for solid flow from the intermediate to the cylindrical lower section of the vessel.
- the vessel diameter is increased just above the partition 84 andthe lower shell of larger diameter is connected to the smaller diameter upper shell above its lower end so that an annular gas receiving space 85 is provided.
- a row of gas distributing troughs of which one can be seen at 86 is provided at an intermediate level in the lower section 82. Gas may be supplied to these troughs via conduit
- a bell shaped member 89 open on its lower end, extends upwardly through a central portion of the top of section 8
- a cylindrical baflle El extends downwardly for a short distance from the top of member 8e so as to provide a central solids receiving space and an annular gas space shielded from the central receiving space and communicating with outlet 88'.
- extends down from the bottom of section 82 to a lift feed tank 82 positioned therebelow.
- An angular ring member S3 is attached around the inner wall of tanl; 92 to provide a gas inlet space 94 which communicates with a gas inlet pipe Q5 for secondary lift gas supply.
- Primary lift gas is supplied intov the tank through pipe t which extends vertically up through the bottom of the tank for a short distance.
- a vertical pipe 9'! extends upwardly from a point just above the end of pipe 36, through the conduit I3! and the reaction vessel into the separation chamber formed by member 89.
- rIhe pipe may be flared on-its upper end which terminates justshort of the space formed by baffle 9
- a lower portion of the annular section 83 there are provided a plurality of spaced refractory cylindrical tubes 99 arranged in a ring around the vessel.
- the tubes SQ are of smaller diameter thanthe width of the annular section and are positioned approximately midway between the walls forming the annular section so as to provide passage for fiow of solids through the tubes 93 and also passage for ow of solids between the tubes and adjacent vessel walls.
- Cylindrical baffle members llt are supported centrally within the tubes il@ to restrict the passage for solid flow along a portion of the lengths of tubes SS).
- seal gas inlets may be provided in place of members Il@ to provide a pressure seal against downward reactant flow in tubes 33.
- a ring manifold its to which is connected reactant inlet conduit itl.
- 82 are connected to the manifold it@ at spaced intervals around the vessel and one of such pipes passes into each of the tubes S9 and terminates centrally within the tube inter- 10 mediate its ends.
- a second plurality of tubes IM which are equal .in diameter to tubes 99 are supported by suitable means (not shown) in the upper portion of section 83 so that each one of said tubes EM is positioned a spaced distance above and directly in line with one of the tubes $9.
- a ring manifold les for air supply is positioned above the vessel and is provided 'with an air feeder inlet conduit
- a dropv tube lill depends from the manifold
- 38 extends into and -terminates short of the end of each tube-
- the tubes It connect on their upper ends to ring manifold
- a gas outlet Uil connects into vthe top of ,section iii.4
- a plurality of tubular sealj-gas distributors are positioned within sectiony83 between the tubes 99 and the tubes
- Each distributor i5 is formed of two concentrically arranged tubes of different diameter connected together by annular closure plates at opposite ends so as to provide an annular gas manifold.
- the tubes 9Sf may ybe replaced by two refractory rings of different diameter arranged concentrically in the annular section 83 so as to form between the rings a single annular shaped reaction nucleus to which reactant may be supplied at points spaced around the nucleus.
- 04 and the seal gas distributors may be similarly modified.
- reaction Zone which, in the modication shown in Figure 2 for example, can be considered as the portion of the bed within tube 18 beginning at the level of the reactant introduction and several inches of the bed above and in line with the tube l0 should be sized in consideration of the rate of reactant introduction to give the reactant residence time desired for the particular reaction involved.
- the rate of solid material flow into and through the tube 'Iii should be that which will supply the required heat for accomplishing the reaction.
- the diameter of the vessel I inrelation to the diameter of tube should be properly proportioned so that for a set temperature of solid material introduction to vessel l0, the solids flowing in the portion of the vessel between tube 'I0 and the vessel walls will be suillcient in amount to cool the reactant to the desired quench temperature.
- a reaction temperature within the range 2300 F.-3000 F.
- a pressure near atmospheric and a residence time of about 0.0001 to 1.0 seconds in the reaction nucleus are desirable.
- the products should be quenched to about 600 F. Ii desired, the products may be only partially quenched by the solid material to say about 900 F.1000 F.
- the conversion temperature may be of the order of 1800 F.2300 F.
- the feed may be a mixture of sulfur vapor and n-butane in the ratio of about one-half to four parts of sulfur per part of n-butane.
- the reaction temperature may be of the order of 900 F.-l300 F. for a reactant residence time of about 0.5 to 2.0 seconds.
- the pressure may be nearly atmospheric.
- the resulting thiophene containing product should be quenched to about '750 F.- 800 F.
- the ratio of solid material to reactant flow through the reaction nucleus will depend upon the specific heat of the solid material and of the reactant and the temperature and the heat of the reaction. In general, about 2-14 pounds o solid material per pound of reactant may pass through the reaction nucleus and the required amount of additional cooler solid material will flow between the reactor walls and the reaction nucleus to shield the walls from the high temperature and to quench the reaction products.
- the solid heat carrying material employed in conducting the process of this invention should be adapted to withstand the high reaction temperatures involved without fusion, decomposition or serious cracking of the particles.
- the material should be hard and rugged so as to 4withstand attrition.
- Typical of inert materials which may be employed are pieces or lspheres formed of high alloy steels, pumice, mullite, fused alumina, silica, ores consisting principally of zirconium silicate complexes, etc.
- Typical of catalytic materials are treated clays, bauxites, inert carriers containing deposited metallic oxides such as deposits of the oxides of molybdenum, chromium, or tungsten and also certain synthetic associations of silica, alumina or silica and alumina to which small percentages of other materials such as metallic oxides may be added for special purposes.
- the solid material may be in the form of spheres, pellets, rods or pieces of irregular shape and the term granular as used herein is intended to broadly cover material in any of these forms as opposed to powdered material.
- the solid particles should fall within the range 0.006 to 1.0 inches in average diameter and preferably within the range about 0.2 to 0.5 inches average diameter.
- a process for rapidly heating reactants to a desired reaction temperature at which said reactants undergo reaction and then rapidly cooling the resulting products below reaction temperature which comprises: passing a granular contact material as a substantially compact column downwardly through a conined zone, directing a stream containing a mixture of an oxygen containing gas and a combustible fuel downwardly into an upper portion of said column below its surface to provide a hot nucleus of combustion within said column, the contact material in said nucleus'being heated to a temperature suitable for the desired reaction, tanning the resulting gaseous combustion products out into the cooler portion of the column surrounding said nucleus while reversing the direction of gas flow and withdrawing said gaseous products from the upper section of said column, injecting a stream of reactant iiuid upwardly into said column at a location below and in alignment with said nucleus of combustion to provide a nucleus of reaction to which the reaction heat is supplied by hot contact material flowing downwardly from said nucleus of combustion, whereby said uid react
- a process for rapidly heating reactants to a desired reaction temperature at which said reactants undergo reaction and then rapidly cooling the resulting products below reaction temperature which comprises, maintaining a substantially compact column of downwardly flowing granular contact material in a conned zone, supplying contact material to the upper end of said column at an elevated temperature which is substantially below the desired reaction temperature, introducing a stream containing a combustible fuel and a combustion supporting gas into a core-like portion of said column below the surface thereof to effect combustion in said core-like portion and the heating of the contact material therein to the desired reaction temperature while leaving the portion of the column laterally surrounding said core-like portion at a temperature substantially below the reaction temperature, withdrawing the resulting gaseous combustion products from said column at a level above that of said stream introduction, introducing a stream of reactant feed existing below the reaction temperature into the heatedv core-like portion of said column below the level of said rst named stream introduction to eiect theheating ofsaid reactant fluid to the reaction temperature and to effect conversion of said reactant
- a process for rapidly heating reactants to a desired reaction temperature at which said reactants undergo reaction and then rapidly cooling the resulting products below reaction temperature which comprises: maintaining a substantially compact column of downwardly flowing granular contact material in a confined zone, supplying contact material to the upper end of said column at an elevated temperature'whicr.
- a process for rapidly heating reactants to a desired reaction temperature at which said reactants undergo reaction and then rapidly cooling the resulting products below reaction temperature which comprises: maintaining a' .substantially compact column of downwardly flowing granular contact material in a conned zone, delivering the total solid Vmaterial supply to said column onto its upper end at a temperature substantially below the desired reaction temperature, withdrawing contact material from the lower section of said column at a temperature below said reaction temperature, establishing a heated core of contact material at a temperature at least as high as the desired reaction temperature within said column below the surface thereof and above the lower end thereof, said core being surrounded by contact material existing substantially below the reaction temperature, introducing the reactant into said heated core to eiect its conversion to gasiform products, flowing said products from said core into contact with cooler contact material 'in said column to effect its quenching to a temperature below the reaction temperature and withdrawing the quenched products from said column.
- A- process for effecting high temperature conversions of a hydrocarbon charge to gasiforrn products which are unstable at the reaction temperature comprising: maintaining a substantially compact column of granular contact material in a coniined zone, replenishing said column solely by supplying granular contact inaterial to the upper end thereof at a temperature substantially below that reaction temperature required for eecting conversion ofthe hydrocarbon charge, withdrawing contact material eX- isting below said hydrocarbon-reaction temperature from the lower section of said column to eiect downward movement of the contact material in said column, establishing a heated nucleus of contact material heated to a temperature suitable for supporting said hydrocarbon conversion in a portion of said column located intermediate its ends, said nucleus being surrounded laterally and below by contact material existing substantiallyr below said reaction temperature, introducing a hydrocarbon charge directly into said heated nucleus to eiect its conversion to gasiform products, passing said products from said nucleusinto contact with adjacent cooler Contact material in said column to quench the products to a temperature at which
- a method for rapidly heating fiuid hydrocarbon reactants to a desired reaction temperature at which they undergo endothermic conversion to form gasiform products and then rapidly cooling the reaction mixture comprises: maintaining a substantially compact column of downwardly flowing granular contact material in a confined Zone, supplying contact material to the upper end of said column at an elevated temperature which is substantially below the desired reaction temperature, withdrawing Contact material fromv the lower section of said column, introducing a stream containing a combustible fuel and a combustion supporting gas into a restricted section of said column lying intermediate its ends and lateral boundaries to effect combustion in a restricted nucleus within said column, whereby the contact material flowing downwardly through the heated nucleus is heated to a temperature suitable for supporting the endothermic hydrocarbon reaction while the contactmaterial in the surrounding portions of said column remains substantially Ybelow the reaction ternperature, introducing a uid hydrocarbon reactant into said heated nucleus at a level spaced k below the level of introduction of said stream of combustible fuel and oxygen containing gas
- a process for eiecting high temperature conversions of a hydrocarbon charge to gasiforrn products which ⁇ are unstableat the reaction temperature comprising: maintaining a substantially compact column of granular contact material 1n a confined zone, replenishing said column solely by supplying granular contact material to the upper end thereof at a temperature substantially below that reaction temperature required for eifecting conversion of the hydrocarbon charge, withdrawing contact material existing below said hydrocarbon reaction temperature from the lower section of said column to effect downward flow of contact material in said column, introducing a restricted stream of heating fluid containing a combustible fuel and an oxygen containing gas downwardly into said column at a location intermediate its lateral and longitudinal boundaries to provide a restricted nucleus of combustion within a portion of said column in which the moving contact material is heated to a reaction supporting temperature while the contact material laterally surrounding said nucleus remains substantially below the reaction temperature, causing the gas to reverse in its direction of flow in said column and withdrawing the gaseous combustion products from the upper section of said column above the level
- a process for effecting high temperature conversions of a hydrocarbon charge to gasiform products which are unstable at the reaction temperature comprising: maintaining a substantially compact column of granular contact material in a conned Zone, replenishing said column solely by supplying granular contact material to the upper end thereof at a temperature substantially below that reaction temperature required for effecting conversion of the hydrocarbon charge, withdrawing contact material existing below said hydrocarbon reaction temperature from the lower section of said column to effect downward flow of contact material in said column, introducing a restricted stream of heating uid containing a combustible fuel and an oxygen containinggas downwardly into said column at a location intermediate its lateral and longitudinal boundaries to provide a restricted nucleus of combustion within a portion of said column in which the moving contact material is heated to a reaction supporting temperature while the contact material laterally surrounding said nucleus remains substantially below the reaction temperature, causing the gas to reverse in its direction of flow in said column and withdrawing the gaseous combustion products from the upper section of said column above the level of said stream introduction to said column, introducing
- a process for eiecting high temperature conversions of a hydrocarbon charge to gasiform products which are unstable at the reaction temperature comprising: maintaining a substantially compact column of granular contact material in a confined zone, replenishing said column solely by supplying granular contact material to the upper end thereof at a temperature substantially below that reaction temperature required for effecting conversion of the hydrocarbon charge, withdrawing contact material existing below said hydrocarbon reaction temperature from the lower section of said column to effect downward movement of the contact material in said column, establishing a heated nucleus of contact material heated to a temperature suitable for supporting said hydrocarbon conversion in a portion of said column located intermediate its ends, said nucleus being surrounded laterally and below by contact material existing substantially below said reaction temperature, maintaining said heated nucleus laterally separated and insulated from the surrounding cooler contact material along atleast the major portion of its length but open to the rest of the column at its ends, introducing a hydrocarbon charge directly into said heated nucleus at a level where it is laterally separated and insulated and causing it to flow upwardly a
- a process for rapidly heating reactants to a desired reaction temperature at which said reactants undergo reaction and then rapidly cooling the resulting products below reaction temperature which comprises: maintaining a substantially compact column of downwardly flowing granular contact material in a coniined zone, supplying contact material to the upper end of said column at an elevated temperature which is substantially below the desired reaction temperature, withdrawing ccntact material from the lower section of said column to promote downward flow of contact material in said column, maintaining a plurality of horizontally spaced apart heated cores of contact material at a temperature suitable for supporting the desired reaction within said .column at a common level intermediate its ends, each of said cores being surrounded by contact material existing substantially below the reaction temperature, introducing a fluid reactant stream into each of said heated cores to effect conversion of said reactant to a gasiform product, flowing said gasiform product from said heated cores into contact with the cooler contact material in said column to elfect its quenching to a temperature below the reaction temperature and withdrawing the quenched product from said column.
- a process for cracking a hydrocarbon charge at elevated temperatures comprising: maintaining a substantially compact column of granular contact material in a confined zone, replenishing said column solely by .supplying granular contact material to ther upper end thereof at a temperature substantially below that reaction temperature required for effecting oo nverslon of the hydrocarbon charge, withdrawing contact material existing below said hydrocarbon reaction temperature from the lower section of said column to effect downward flow of Contact material in said column, introducing a restricted stream of heating fluid.
- An apparatus for vconducting high temperature fluid reactions in the presenceiof a moying ⁇ granular material comprising in combination: an elongated upright Vessel adapted to conne a column of contact material, ⁇ means to supply contact material to the upper section of said Vessel and means to withdraw contact ma.- terial from the lower section thereof, inlet conduit for heating fluid introduction extending into an upper portion of said vessel and termi, nating on its downwardly facing, open lower end at a location substantialh7 spaced away ,from the confining walls of said Vessel and spfed ksubstantially below said means to supply contact material, an outlet for heating fluid connected near the upper end of said vessel above said 'inlet conduit, a reactant .inletextending into said ,vessel and terminating on its upwardly ,facing upper end at a location inlateral alignment with and spaced shortly below the .lower end yof said heating fluid inlet conduit, an outlet for reactant gasv connected into said Vvessel at a lower level than
- the lapparatus Vof claim 13 further char.- acterized by .a refractory tube open -on its .ends mounted vertically in said vessel and ⁇ concentrically with the upwardly facing upper .end .of
- said reactant inlet ⁇ said tube being of largendi 19 ameter than said reactant inlet but of substantially less diameter than said vessel and extending upwardly and downwardly beyond the level of the upper end of said reactant inlet but terminating short of the level of the lower end of said heating fluid inlet.
- An apparatus for conducting high temperature fluid reactions in the presence of a moving granular contact material comprising: a vertical vessel having contact material inlet means at its upper end and contact material outlet means at its lower end, a refractory tube positioned vertically within an intermediate portion of said vessel and spaced from the vessel walls, an inlet for fluid reactant extending into said refractory tube and terminating its upwardly facing delivery end centrally of the tube walls and a substantial distance from its upper and lower ends, a reactant outlet conduit connecting into said vessel below the reactant inlet, a heating fluid inlet conduit extending into said vessel and terminating on its downwardly facing delivery end along substantially the same vertical axis as the reactant inlet and a spaced distance above the upper end of said refractory tube, an outlet conduit for flue gas withdrawal connected into said Vessel substantially above the level of said last named inlet and an inlet for inert gas introduction connected into said vessel between the levels of said heating fluid and reactant inlets.
- An apparatus for conducting high temperature fluid reactions in the presence of a moving granular contact material which comprises: a vertical vessel having cylindrical-shaped upper and lower sections and an annular shaped intermediate section in communication at its upper and lower ends with said upper and lower sections; means defining a separation chamber said means comprising, a member of cylindrical cross section extending upwardly and centrally through the top of said vessel from an intermediate level within said upper section, closure means on the upper end of said member and a gas outlet near the upper end of said member; a gas outlet on said upper section of said vessel above said intermediate level; a closed chamber spaced centrally below said vessel; a vertical conduit extending downwardly from said vessel to said closed chamber; a vertical pipe open on its ends and substantially smaller in diameter than said conduit extending upwardly from an intermediate level within said closed chamber through said vessel to a location within said separation chamber intermediate the ends thereof; means to introduce a lift gas into said closed chamber below said pipe; a plurality of openended vertical, refractory tubes spaced in a ring around a lower part of said annular
- a process for effecting high temperature conversion of a hydrocarbon charge to gasiform products which are unstable at the reaction temperature comprising: maintaining a substantially compact column of granular solid material flowing through a confined housing, establishing a hot nucleus of solid material existing at a temperature suitable for the hydrocarbon conversion within a region of said column spaced substantially away from the housing walls, maintaining the flowing solid material between said hot nucleus and the walls of said housing at a temperature below that at which the hydrocarbon conversion will progress, introducing the hydrocarbon feed into said hot nucleus to effect its conversion to unstable gasiform products, passing the products from the hot nucleus over into the surrounding cooler solid material to effect the quenching of the products to a temperature at which further reaction of the formed products is substantially inhibited, and withdrawing quenched products from said housing.
- a process for effecting high temperature conversion of reactant charges to gasiform products comprising: maintaining a substantially compact column of granular solid material flowing through a confined housing, establishing a hot nucleus of solid material in a region within said column spaced away from the walls of said housing, maintaining the solid material flowing in said column between said nucleus and the walls of said column at a temperature substantially below that in said nucleus so that the temperature near the walls throughout the housing are substantially below that in said nucleus, in-
- a process for effecting high temperature conversion of reactant charges to gasiform products comprising: maintaining a substantially compact column of granular solid material flowing through a confined housing, establishing a hot nucleus of solid material in a region Within said column spaced away from the walls of said housing, maintaining the solid material flowing in said column between said nucleus and the walls of said column at a temperature substantially below that in said nucleus so that the tem- 21 perature near the Walls throughout the housing are substantially below that in said nucleus, passing reactant charge into said hot nucleus to contact the hot solids and become converted to gasiform products and passing said gasiform products from said hot nucleus.
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Description
April 10, 1951 E v BERGs'rRoM 2,548,286
METHOD ANO AIBPARATUS FOR CONDUCTING HYDROCARBON CONVERSION REACTIONS w INVENToR.
En? Fefgsm/f@ O l @5W/774 #Tram/EY Api w, 195 E. v. BERGSTROM METHOD AND APPARATUS FOR CONDUCTING HYDROCARBON CONVERSION REACTIONS .5 Sheets-Sheet 2 Y Filed Oct. 29, 1949 INVENToR. 'eggfsram T7 Nw mm HR MP '3 Sheets-Sheet 3 /aff/:s
INVENTOR. fr 'egs/fam /lrm/P/vfy if BY E. V. BERGSTROM METHOD AND APPARATUS F'OR CONDUCTING HYDROCARBON CONVERSION REACTIONS April l0, 1951 Filed oct. 29, 194s /NERT (7175 /lff/VT (fl/4R65 Patented pr. 110, 1951 METHOD AND APPARATUS FOR CONDUCT- ING HYDROCARBON CONVERSION REAC- TIONS Eric V. Bergstrom, Short Hills, N. J., assignor to Socony-Vacuum Oil Company, Incorporated, a corporation of New York Application October 29, 1949, Serial No. 124,463
This invention relates to a method and apparatus for conducting chemical reactions at very high temperatures in the presence offa moving particle form solid material. Particularly it relates to an improved continuous method and apparatus for conducting highly endothermic, high temperature conversions of hydrocarbons, supplying the heat therefor and quenching the usually unstable reaction products.
Exemplary of the processes to which the method of this invention may be applied are the pyrolytic conversion of methane, propane and other light hydrocarbons to acetylene containing products at temperatures of the order of 2000-2600 F. and approximately atmospheric pressures. Another process is the manufacture of ethylene by the cracking of heavier hydrocarbons such as ethane, propane, butane or gas oils at temperatures of the order of 1450-1800" F. over an inert mass of granular material- Another process is the conversion of powdered coal to CO and H2 by contact with steam or steam and oxygen at temperatures of the order of 200G-2500 F. Still another reaction is the pyrolytic conversion of gaseous or liquid hydrocarbons to aromatics at temperatures of the order of 1250-1800" F. Still another process is the preparation of thiophene and butadiene by reaction between n-butane and/or butene and sulfur vapors at temperatures of the order of 850-1400 F. Another process is the high tempcrature catalytic cracking conversion of hydrocarbons to high yields of aviation gasoline and C4 fractions.
Recently, it has been proposed to conduct such reactions in systems wherein a granular heat carrying material which may or may not be catalytic in nature is passed cyclicallyA through a heating zone wherein it is heated by hot combustion gases to a temperature above the .desired average hydrocarbon conversion temperature and then through a separate reaction Zone wherein it is temperatures which overcomes the above mencontacted with the hydrocarbon feed to effect the conversion thereof, the heat for the reaction being supplied as sensible heat in the solid heat carrying material. rIhe resulting reaction products are then quenched in` a separate quench Zone. In such systems it is usually necessary to position the separate heater for the granular solids above the reactor in order to maintain as low as possible the temperature of the solids passing to the conveying equipment. This in itself causes the unit to be of undesirable height. This height may be increased still more or the unit may be rendered more complex by addition of a separate quench vessel. In addition to this, the ex- 21 Claims. (C1. 7260-4566) ceedingly high temperatures required by some reactions make necessary the use of very expensive heat resistantalloys for the heater and reactor construction. This causes the cost of the comculties arising from the high temperatures in- Volved.
A majorobject of this invention is the provision of an improved continuous method and apparatus for conducting endothermic reactions atelevated tioned dniculties.
A specific object is the provision in a process for conducting high temperature, endothermic conversions of hydrocarbon reactants of a method and apparatus wherein the heat maybe supplied, the reaction may be conducted and the reaction products may be quenched all within a single chamber.
Another object is the provision of a method and apparatus for conducting high temperature reactions in the presence'of moving solids Without the necessity of heating the reaction housing and solid material handling equipment tothe elevated reaction temperature.
These and Vother objects of this invention will become apparent from the following description of the invention.
In one form, this invention involves a process and apparatus for conducting high temperature conversions of reactants wherein a column of flowing granular solids is maintained in a coniined housing, which column is supplied exclusively at its upper end with solids existing substantially below the reaction temperature and from the lower end of which column solids are withdrawn existing substantially below the reaction temperature. A lhot nucleus is established in a region within the column spaced substantially away from the walls of the housing. The reactant in liquid, gaseous or powdered form isintroduced directly into the heated nucleus of gravitating solids whereby the desired conversion is effected. The conversion products in the gaseous phase may fan out into the mass of cooler solids which surround the hot nucleus and are thereby quenched to a level far below the reaction temperature so that further conversion of the product is substantially inhibited, after Which the products are withdrawn from the conversion chamber.
In another form Vof this invention, the reaction products may be withdrawn directly from the hot reaction nucleus so that the surrounding mass of cooler solids serves the principal function of a shield between the reaction nucleus and the vessel walls. The solidmaterial is withdrawn from the bottom of the chamber separately of the gasiform conversion products. By the above method very high temperature reactions may be effected while the retaining walls of the chamber are maintained by the shield or curtain of cooler solids at a temperature far below that involved in the reaction nucleus. This invention is contemplated as being broad to the above procedure in its generic aspects irrespective of how the nucleus is heated. In its preferred form this invention is one wherein granular solids existing substantially below the hydrocarbon average reaction temperature are introduced into the upper section of a chamber and are passed downwardly through the chamber as a substantially compact column; A stream containing a combustible fuel and combustion supporting gas is introduced downwardly into the column at a location below ts surface and spaced away from the chamber walls to effect combustion in a corelike portion of the column which exists principally immediately below and adjacent the loca tion of the fuel introduction. This core is later ally surrounded by cooler solids which shield the walls of the chamber, and the hot core of solids is extended downwardly below the location of combustion due to the downward flow of the solids. The combustion gases are permitted to fan outwardly toward the cooler material while reversing the direction of gas ilow and are withdrawn above the level of fuel introduction. The hydrocarbon reactant is introduced into the hot core of solids below the level of the combustion reaction and is converted by means of heat contained in the solids. The gasiform reaction prode ucts are caused to pass outwardly into the cooler solids surrounding the reaction core and the direction of reactant flow is reversed so that the quenched gasiform products are withdrawn from the chamber below the level of reactant introduction. Solids from the reaction core and surrounding'cooler solids are withdrawn mixed together from the bottom of the chamber at a temperature substantially below the reaction temperature.
The invention may be most readily understood by reference' to the drawing attached hereto in which Figure 1 is an elevational view, partially in section, of a system adapted for conducting this invention; Figures 2 and 3 are elevational views, partially in section of a modified portion of the apparatus shown in Figure 1; and Figure 4 is an elevational view, partially in section of another modied form of the invention. All of these drawings are highly diagrammatic in form.
' Turning now to Figure l, there is shown a chamber I of which the upper section is of somewhat smaller diameter than the lower section and fits thereinto so as to provide an annular gas receiving space II, provided with an outlet I2. It will be understood, however, that the chamber may be of uniform diameter throughout its length with other suitable means provided for gas withdrawal. A hopper I3 for solid material supply is positioned above chamber I and a gravity feed conduit I extends downwardly from the bottom of hopper I3 to a point within and below the top of chamber I0 so as to provide above the column or solids I5 a second gas receiving space I6. An outlet l1 connects through the vessel wall for withdrawal of gas from space I5. A solid material outlet I9 having a iiow control valve 20 thereon is connected into the bottom of chamber I0. Two vertically spaced partitions 2l and 22 are provided across the chamber IU above the outlet I9. The partition 2l has a plurality of uniformly spaced tubes 23 dependent therefrom and the partition 2'( has a smaller number of dependent tubes 24 which are staggered with respect tubes 23 so that each tube 24 receives flow from several tubes 23. The tubes 2 are symmetrically positioned horizontally with respect to the outlet I9. This arrangement promotes uniform withdrawal of solids from all portions of the vessel cross section. A flow control arrangement of this type is disclosed and claimed in United States Patent 2,412,136, issued to Evans et al. December 3, 1946. A purge gas inlet'25 is provided immediately below partition ZI. Inverted gas distributing troughs 26 of angular shape are positioned above the partition 2| and these are supplied with a cooling gas or liquid from external header 39 to which are connected tubes 21 which extend under the troughs and have outlet orifices 38 thereon. A vertical tube 23 extends down into the upper section of chamber I0 and terminates below the solids feed conduit I4 at a point located centrally with respect the chamber walls. An air inlet pipe 3U connects into the upper end of tube 28. A smaller tube 3l extends centrally downwardly with tube 28 and terminates above the lower end of tube 28. Fuel is supplied to the upper end of tube 3I through pipe 32. A reactant inlet tube 33 extends into the chamber Hl and terminates on itsupwardly facing end a short vertical distance below and directly in line with the tube 28. A perforated distributing cap 35 is provided on the end of tube 33. A ring type manifold 36 provided with spaced openings along its lower face is positioned within chamber I0 between the levels of the facing ends of tubes 28 and 33 and an inlet pipe 31 connects into the ring manifold. An external elevator Il which may be of conventional design is provided for transfer of solids from outlet I9 to a point above hopper I3 from which the solids ilow to the supply hopper via duct 4I.
The application of this invention to a process for converting propane to acetylenecontaining products may be taken as typical. An inert refractory contact material such as granular carborundum, existing at about 700 F., enters the chamber IS from hopper i3. Fuel gas such as reiinery gas or in some cases fuel oil introduced from pipe 32 into tube 3| and air is introduced from pipe 30 into tube 28, so as to provide a combustible gas mixture issuing from the lower end of tube 28. Combustion of the fuel occurs in the substantially compact bed in a narrow zone close to the lower end of tube 28. This burning zone usually does not extend more than about 3 4 inches away from the outlet of tube 28. Thus, there is provided a hot nucleus of combustion in said column in which the solid material is heated to temperatures of the order of 2300 F. and higher. The solids flowing down in the portion of the chamber laterally surrounding the nucleus of combustion are at a much lower temperature so that the temperature along the vessel walls is of the order of 'ZOO-800 F. Flue gas formed by the combustion is caused to reverse its direction of flow so that it passes up through the annular bed around tube 2B into receiving space I6 from which it is withdrawn 5, 'via pipe il. Propane which may` or may not contain some preheat is introduced via tube 33 upwardly into the bed at a location above its lower end and directly below the location of introduction of the air and fuel mixture so that the propane is contacted with heated solids flowing down from the combustion nucleus into what may be called a reaction nucleus. The reaction nucleus, existing at or above 2300" F., is surrounded laterally by solids existing at substantially lower temperature of the order of 'ZOO-800 F. The reaction. products which are unstable under the conditions in the reaction nucleus are caused to reverse in ilow direction and to--pass downwardly through the adjacent cooler contact material in the bed between the tube 33 and the vessel walls whereby the products are quenched to a level at which they are stable and do not undergo further reaction. The gasiform products pass on down through the bed of mixed solids in the portion of the bed below the reaction nucleus and are with drawn from gas receiving space il via outlet pipe l2. The hot solids from the reaction nucleus gradually become mixed with cooler surrounding solids at levels inthe bed below the reaction nucleus so that the mixed solids reaching the cooling section 50 may exist at a temperature of the order of 80G-900 F. or lower, depending upon the relative amounts of solid flow in the hot nucleus and in the surrounding portion of the bed. The solids are then cooled by introduction of a suitable cooling fluid such as steam or water or flue gas supplied via header 39. The cooled solids are transferred by elevator 50 to hopper I3 from which they again flow to chamber Ill. Usually very little if any coke is deposited upon the solid material. If any such coke is deposited, it may be removed by diverting a portion of the solids from chamber lil through a suitable kiln. Alternatively, the burning may be accomplished byv introduction of limited amounts of air into the section l] with the cooling fluid or accomplishing the combustion in hopper i3. Gas inlet 43 and outlet 44 are provided on hopper I3 for this purpose. Usually where the contact material is not a catalyst, coke removal therefrom is unnecessary.
It is desirable to substantially prevent interiiow of gaseous reactants and combustion gases between the nucleus or" combustion and the nucleus of reaction. One method of accomplishing this is to introduce a seal gas such as steam or ue gas into the bed via manifold Se. The steam pressure is maintained sufficiently above that in the combustion and reaction nucleuses to cause steam to flow both upwardly and downwardly through the bed from its location of introduction. Further control is efected by maintaining balance between the amount of oxygen introduced via pipe 30 and withdrawn in one form or another via pipe Il. When this is done, only gases from the combustion nucleus plus a very small amount of seal gas will be withdrawn via pipe il while only hydrocarbon conversion products plus a small amount of seal gas will pass down through the bed to outlet I2. This operation may be effected by providing a flow measuring orice 5| on air inlet SEE to actuate a flow control instrument 52 which controls diaphragm valve 53. The valve is controlled so as to maintain a nxed amount of air feed. The fuel feed may be similarly controlled in the proper flow measuring orifice 56 on the ue gas outlet pipe l1. Alternatively, the valve 54 may be located on pipe l1.
It will be noted that while the reaction temperature in the above operation is of the order of 2300o F. and upwards, thewalls of chamber IU are subjected only to the much lower temperature of they flowing bed surrounding the combustion and reaction nucleuses. The only structural surfaces exposed to the extreme temperatures are portions of the gas inlet tube 28, reactant inlet tube 33 and the steam manifold 3e. These members may be constructed of refractory material suitable for ywithstanding high temperatures. The remainder of the apparatus may be constructed of material presently used in conventional catalytic cracking' reactors and the like which operate at temperatures below l000 F.v Moreover, the solids enter and leave the reaction chamber at temperatures far below the reaction temperature so that they can be practicably conveyed by means of mechanical conveyor equipment. Also, it will be noted that theV actual combustion and reaction Zones are very small in size and are positioned close together within the same chamber whereby a' great saving in material and in unit height is effected as compared with continuous conversion systems known heretofore. Further simplification of design and improvement of operation is effected due to the lateral placement of the quench Zone with respect the reaction zone Within the same chamber. This effects a reduction in unit height, eliminates a separate quench chamber and permits more accurate control of the period during which the reactant is maintained at the very high reaction temperatures. Many of the reactions of the type to which this method and apparatus may be applied require only a fraction of a second, after which the products should be quenched to slow or preferably to substantially stop further reaction or at least to prevent decomposition of the reaction products. The method and apparatus of this invention by providing a Very small reaction nucleus surrounded by a much larger mass of cooler solids is well adapted for accurate control of reactions of the type discussed above.
Because of the closeness of the combustion and reaction zones and their small size relative to the entire bed of solids in the chamber l@ and because of the uniform downward solid iiow maintained across the entire bed,v very little mixing occurs between cool solids from the surround bed and the hot solids passing down from the combustion core or nucleus to the reaction core or nucleus. If desired, however, suitable baling may be provided to discourage any tendency for Such mixing which mightoccur in this section of the bed. An arrangement for accomplishing this is shown in Figure 2 in which there is shown that section of the Vessel id of Figure l in which the fuel combustion and hydrocarbon conversion takes place. Corresponding members in Figures l and 2 bear like numerals. It will be noted that a cylindrical tube 'l is supported by rods 69 concentrically around the upwardly extending portion of the reactant inlet 33. This tube may be constructed of a suitable refractory material such as fused alumina, carborundum, etc. The tube Hi extends upwardly a vertical distance above the level of the upper end of the pipe 33 and downwardly a somewhat greater distancev beyond the same level. The tube lll is narrowed in cross-section along a portion of its length at II below the outlet of pipe 33 so as to inhibit downward gas ow from the outlet of pipe 33 while permitting downward flow of solids. Thus, in this arrangement the reaction Zone may be considered to be concentrated in that portion of the tube IIJ above the outlet from pipe 33 and in the bed a short distance directly above and in line with the tube 'ill where the gas fans out and reverses in its direction of flow. A second refractory tube I2 having substantially the same diameter as tube l is supported from rods 'i3 below and adjacent the lower end of the combustion gas inlet tube 28. The seal gas inlet arrangement is modified somewhat from that shown in Figure 1 and comprises a refractory cone T5 placed centrally in the chamber I and about midway between the lower end of tube 28 and the upper end of tube 33, an inlet pipe 74, insulated along part of its length, delivering uid under the cone 'I5 and a refractory tube 'I5 surrounding the cone l5. Vertical spaces are provided between tubes 'I2 and 'I6 and between tubes 'I5 and lo where the combustion gases and reactant gases respectively may fan out and reverse in flow direction. An annular shaped, perforated manifold IEB may be provided in the space between the vessel wall and tube 'I6 for seal gas supply to the portion of the vessel outside tube 16. An inlet pipe liconnects into the manifold It for seal gas supply.
In operation, a portion of the relatively cooled inert refractory solid material introduced into the upper end of the vessel I0 ows into the upper end of tube 'I2 and becomes heated by the fuel combustion occurring within the tube. The heated solid material ows down through tube 'I5 and into the upper end of tube 'I0 where it meets the reactant uid and supplies the heat for effective pyrolytic conversion thereof. The solid material, cooled somewhat due to release of heat for the hydrocarbon reaction passes on through tube 'I0 and mixes with cooler material in the bed therebelow. Meantime, cooler solid material ows down through the annular passage i8 formed between the walls of the chamber IIJ and the tubes 12, 'I6 and l0 and nally joins the stream of material flowing from the lower end of tube 10. Since the rate of downward now of solid material in the portion of the bed below tube 'Ill is maintained constant entirely across the horizontal cross-section of the bed by virtue of the flow control partitions 2l and 22 of Figure 1, the relative amounts of solid i'low by way of the tubes 12, 'I6 and 'I0 and by way of the annular passage Iiimay be accurately controlled by proper control of the relative areas of the annular passage I8 and of the tube 'It at the level of the lower end of tube 10. If desired, a suitable arrangement adjustable from outside the chamber I0 may be provided for varying the effective area for solid flow at the lower end of tube l0. The mixed fuel and air stream issuing from tube 28 flows for the most part down through the moving bed of solids within the confines of tube l2 while the fuel combustion occurs. The flue gas formed flows out from under tube l2, fans out into annular passage 18 and then passes upwardly to the receiving space I6 shown in Figure 1. A small part of the gas may by-pass the tube 'I2 and flow up through the bed around tube 28. The combustion of this gas will occur before it reaches the portion of the bed over the annular passage 'i8 so that the solids heated by combustion of this gas are principally solids which Would enter tube I2 anyway.
Lif
If desired, the tube 'I2 may be extended upwardly beyond the tube 28 and restricted in cross-section along a portion of its length similarly to tube 'I0 so as to further insure concentration of combustion heat supply to solids flowing down through tube l2. The ue gases will, of course, give up some sensible heat content to the cooler solids in the upper portion of the bed above the combustion zone but this constitutes only a minor portion of the total heat capacity of the mixed gas entering from tube 28. Hydrocarbon reactants supplied into tube IIJ either as a liquid or gas or as a powder suspended in gas soon become converted to gasiform products which ow out from the upper end of tube I0 and over into the cooler stream of solids in passage '18. I-Iere the reactant is quenched to a temperature which may be controlled by controlling the inlet temperature of solids to chamber I0 and the amount of solid now in passage 'I8 relative to the amount of reactant introduction to chamber I0. It is pointed out at this point that the terms gasiformj gaseous and the like as used herein in describing and in claiming this invention 4are used in a broad sense to cover materials existing in the gaseous phase under the particular conditions of temperature and pressure involved regardless of what may be the normal phase of such materials under atmospheric conditions.
Since the tubes l0, 'I2 and 'I6 shown in Figure 3 are provided simply as bailles to aid in guiding the flow when needed and not as insulators, they need not be of any greater thickness than dictated by structural strength requirements. In some operations these tubes may be constructed of alloys adapted to withstand high temperatures.
It will be understood that the invention is not contemplated as being limited to the particular shape and form of the chamber shown in Figures l and 2 or to the particular details shown for the mixed combustion gas and reactant gas introduction and Withdrawal or to the described means for controlling uniformity of solid material now or for effecting its transfer outside the chamber I0. It is contemplated that in some forms of the invention the initial direction of the reactant introduction may be other than upward and that it may be withdrawn from the chamber at loca-'f tions transversely across the bed from the point of reactant introduction and on the same level therewith.
It is further contemplated that the gasiform reaction products may be withdrawn directly from the reaction nucleus without passing through the surrounding insulating shield of cooler contact material. An arrangement of this type is shown in Figure 3 which shows a modied arrangement of the heating and reaction portion of the apparatus shown in Figure 1. Like elements in Figures 1, 2 and 3 bear corresponding numerals. In the arrangement of Figure 3, only a single cylindrica1 refractory tube I I0 is positioned within the vessel I0. This tube is so constructed as to provide gas collecting spaces II2 for reaction products. In operation the heating gases issue from tube 28 into the owing mass within tube I I0 and then pass upwardly through the passage between tubes I I0 and 28. The heated solids pass through the seal section in the vicinity of cone 'I5 and then into the reaction nucleus which is that portion of the mass within tube I I0 below the end of reactant inlet pipe I I5 and gas collecting space I I2. The reaction products are withdrawn from space I I2 via pipes I I6 and conduit I I8. It will be noted that in this arrangement the cool solid material 9 flowing in passage 18 is never contacted `bythe reactants.
It is further contemplated that more than one reaction nucleus may .be provided within a single chamber and an example `of an arrangement incorporating this embodiment is shown in Figure 4. In this figure there is shown a vessel comprised of a cylindrical upper section 8|, a cylindrical lower section 82 and an annular shaped intermediate section S3 in free solid flow communication at its ends with said upper and lower sections. A partition 84 forms the bottom of thefintermediate section and a ring of spaced tubes 85 depend from the partition to provide passageway for solid flow from the intermediate to the cylindrical lower section of the vessel. The vessel diameter is increased just above the partition 84 andthe lower shell of larger diameter is connected to the smaller diameter upper shell above its lower end so that an annular gas receiving space 85 is provided. A row of gas distributing troughs of which one can be seen at 86 is provided at an intermediate level in the lower section 82. Gas may be supplied to these troughs via conduit |25 and manifold 8l and individual feed pipes 88. A bell shaped member 89, open on its lower end, extends upwardly through a central portion of the top of section 8| from an intermediate level in said upper section. rThe member 89 is closed on its upper end except for a gas outlet se. A cylindrical baflle El extends downwardly for a short distance from the top of member 8e so as to provide a central solids receiving space and an annular gas space shielded from the central receiving space and communicating with outlet 88'. A conduit |3| extends down from the bottom of section 82 to a lift feed tank 82 positioned therebelow. An angular ring member S3 is attached around the inner wall of tanl; 92 to provide a gas inlet space 94 which communicates with a gas inlet pipe Q5 for secondary lift gas supply. Primary lift gas is supplied intov the tank through pipe t which extends vertically up through the bottom of the tank for a short distance. A vertical pipe 9'! extends upwardly from a point just above the end of pipe 36, through the conduit I3! and the reaction vessel into the separation chamber formed by member 89. rIhe pipe may be flared on-its upper end which terminates justshort of the space formed by baffle 9 In a lower portion of the annular section 83 there are provided a plurality of spaced refractory cylindrical tubes 99 arranged in a ring around the vessel. rThe tubes SQ are of smaller diameter thanthe width of the annular section and are positioned approximately midway between the walls forming the annular section so as to provide passage for fiow of solids through the tubes 93 and also passage for ow of solids between the tubes and adjacent vessel walls. Cylindrical baffle members llt are supported centrally within the tubes il@ to restrict the passage for solid flow along a portion of the lengths of tubes SS). The restriction so provided is insufficient to prevent the proper rate of solid flow through the tubes but provides a seal against reactant flow. Alternatively, seal gas inlets may be provided in place of members Il@ to provide a pressure seal against downward reactant flow in tubes 33. Outside the vessel there is provided a ring manifold its to which is connected reactant inlet conduit itl. Individual pipes |82 are connected to the manifold it@ at spaced intervals around the vessel and one of such pipes passes into each of the tubes S9 and terminates centrally within the tube inter- 10 mediate its ends. A second plurality of tubes IM which are equal .in diameter to tubes 99 are supported by suitable means (not shown) in the upper portion of section 83 so that each one of said tubes EM is positioned a spaced distance above and directly in line with one of the tubes $9. A ring manifold les for air supply is positioned above the vessel and is provided 'with an air feeder inlet conduit |06. A dropv tube lill depends from the manifold |2'5 to a point intermediate the ends of each one of the tubes HB4 which are of larger diameter than the drop tubes. A smaller drop tube |38 extends into and -terminates short of the end of each tube-|91. The tubes It connect on their upper ends to ring manifold |8 which is supplied with fuel from conduit Ulli. A gas outlet Uil connects into vthe top of ,section iii.4 A plurality of tubular sealj-gas distributors are positioned within sectiony83 between the tubes 99 and the tubes |94, soy that there is provided one distributor between -andjin line with each set of tubes 99 and |94. Each distributor i5 is formed of two concentrically arranged tubes of different diameter connected together by annular closure plates at opposite ends so as to provide an annular gas manifold.
`Perforations |46 in the wallsof the distributor permit gas to escape into the bed of lsolid material. Individual feed pipes |41 feeding from ring manifold |48 connect into the distributors |45. An inlet conduit |49 connects into the manifold |48.
The operation ofthe apparatus shown in Figure 4.- is similar to that discussed in connection with Figures 1 and 2 except that there are 'provided a plurality of combustion and reaction nucleuses rather than only one of each. Also, instead of employing a bucket elevator for transfer of solids, a gas lift is employed. Cooled granular material flows from section t2 as a compact stream through annular passage i2!) into the feed tank 92. The leg in passage |20 acts as .a seal against substantial escape of gas from the section 82 with the solid material. Solids are suspended in a suitable lift gas such as steam or flue gas in the lift pipe 9'! and are carried-upwardly into the separator 89. Here the lift gas is separated `from the solids and withdrawn through outlet 8B. The solid material then flows as a compact mass of particles into and through the section 8|. f g
If desired, the tubes 9Sfmay ybe replaced by two refractory rings of different diameter arranged concentrically in the annular section 83 so as to form between the rings a single annular shaped reaction nucleus to which reactant may be supplied at points spaced around the nucleus.
The tubes |04 and the seal gas distributors may be similarly modified.
It will be understood that the exact operating conditions and the exact apparatus dimensions employed in conducting this invention may Vary widely depending upon the particular application. In general, the reaction Zone which, in the modication shown in Figure 2 for example, can be considered as the portion of the bed within tube 18 beginning at the level of the reactant introduction and several inches of the bed above and in line with the tube l0 should be sized in consideration of the rate of reactant introduction to give the reactant residence time desired for the particular reaction involved. The rate of solid material flow into and through the tube 'Iii should be that which will supply the required heat for accomplishing the reaction. The diameter of the vessel I inrelation to the diameter of tube should be properly proportioned so that for a set temperature of solid material introduction to vessel l0, the solids flowing in the portion of the vessel between tube 'I0 and the vessel walls will be suillcient in amount to cool the reactant to the desired quench temperature. As an example of desirable operating conditions, in the conversion of methane to acetylene a reaction temperature within the range 2300 F.-3000 F., a pressure near atmospheric and a residence time of about 0.0001 to 1.0 seconds in the reaction nucleus are desirable. The products should be quenched to about 600 F. Ii desired, the products may be only partially quenched by the solid material to say about 900 F.1000 F. and then further quenched after withdrawal from the reaction vessel. When the methane charge is diluted with hydrogen or steam somewhat longer residence periods are permissible. In the case of conversion of ethane to acetylene the conversion temperature may be of the order of 1800 F.2300 F. In another example, the feed may be a mixture of sulfur vapor and n-butane in the ratio of about one-half to four parts of sulfur per part of n-butane. The reaction temperature may be of the order of 900 F.-l300 F. for a reactant residence time of about 0.5 to 2.0 seconds. The pressure may be nearly atmospheric. The resulting thiophene containing product should be quenched to about '750 F.- 800 F. and then withdrawn to a liquid quenching tower for further cooling. The ratio of solid material to reactant flow through the reaction nucleus will depend upon the specific heat of the solid material and of the reactant and the temperature and the heat of the reaction. In general, about 2-14 pounds o solid material per pound of reactant may pass through the reaction nucleus and the required amount of additional cooler solid material will flow between the reactor walls and the reaction nucleus to shield the walls from the high temperature and to quench the reaction products. In general, in order to permit handling of the solid material in mechanical conveying equipment or in order to permit use of inexpensive steels for both the transfer equipment of any type and for the reaction vessel and surge hoppers it is desirable to maintain the temperature of the solids introduced into the vessel l0 of Figures 1-3 at the vessel of Figure 4 below about 1200 F. and preferably below about 1000 F. The solids iiowing between the reaction nucleus and housing walls should also be maintained below these limits.
The solid heat carrying material employed in conducting the process of this invention should be adapted to withstand the high reaction temperatures involved without fusion, decomposition or serious cracking of the particles. The material should be hard and rugged so as to 4withstand attrition. Typical of inert materials which may be employed are pieces or lspheres formed of high alloy steels, pumice, mullite, fused alumina, silica, ores consisting principally of zirconium silicate complexes, etc. Typical of catalytic materials are treated clays, bauxites, inert carriers containing deposited metallic oxides such as deposits of the oxides of molybdenum, chromium, or tungsten and also certain synthetic associations of silica, alumina or silica and alumina to which small percentages of other materials such as metallic oxides may be added for special purposes. The solid material may be in the form of spheres, pellets, rods or pieces of irregular shape and the term granular as used herein is intended to broadly cover material in any of these forms as opposed to powdered material. The solid particles should fall within the range 0.006 to 1.0 inches in average diameter and preferably within the range about 0.2 to 0.5 inches average diameter.
It will be understood that the specific examples of apparatus design, operating conditions and application of this invention given hereinabove are exemplary in nature and are not intended as limiting the scope of this invention thereto.
I claim:
l. A process for rapidly heating reactants to a desired reaction temperature at which said reactants undergo reaction and then rapidly cooling the resulting products below reaction temperature which comprises: passing a granular contact material as a substantially compact column downwardly through a conined zone, directing a stream containing a mixture of an oxygen containing gas and a combustible fuel downwardly into an upper portion of said column below its surface to provide a hot nucleus of combustion within said column, the contact material in said nucleus'being heated to a temperature suitable for the desired reaction, tanning the resulting gaseous combustion products out into the cooler portion of the column surrounding said nucleus while reversing the direction of gas flow and withdrawing said gaseous products from the upper section of said column, injecting a stream of reactant iiuid upwardly into said column at a location below and in alignment with said nucleus of combustion to provide a nucleus of reaction to which the reaction heat is supplied by hot contact material flowing downwardly from said nucleus of combustion, whereby said uid reactant is converted to a gasiform reaction product in said nucleus of reaction, said nucleus of reaction being surrounded by cooler contact material flowing downwardly from the portion of said column surrounding said nucleus of combustion, fanning the gasiform reaction product out from said nucleus of reaction into the cooler portion of said column surrounding said nucleus of reaction while reversing the direction of gas now, whereby said gasiform product is quenched to a temperature below the reaction temperature, passing said gasiform reaction product downwardly through a lower portion of said column and then withdrawing it from said column.
2. A process for rapidly heating reactants to a desired reaction temperature at which said reactants undergo reaction and then rapidly cooling the resulting products below reaction temperature which comprises, maintaining a substantially compact column of downwardly flowing granular contact material in a conned zone, supplying contact material to the upper end of said column at an elevated temperature which is substantially below the desired reaction temperature, introducing a stream containing a combustible fuel and a combustion supporting gas into a core-like portion of said column below the surface thereof to effect combustion in said core-like portion and the heating of the contact material therein to the desired reaction temperature while leaving the portion of the column laterally surrounding said core-like portion at a temperature substantially below the reaction temperature, withdrawing the resulting gaseous combustion products from said column at a level above that of said stream introduction, introducing a stream of reactant feed existing below the reaction temperature into the heatedv core-like portion of said column below the level of said rst named stream introduction to eiect theheating ofsaid reactant fluid to the reaction temperature and to effect conversion of said reactant fluid to gasiform products, passing Vsaid gasiform products into a cooler portion of said column to eiect quenching to a temperature substantially below Ythe reaction temperature, withdrawing quenched gasiform products from said column at a level below that of reactant fluid introduction and withdrawing contact material from the lower section of said column at a temperature below the desired reaction temperature.
3. A process for rapidly heating reactants to a desired reaction temperature at which said reactants undergo reaction and then rapidly cooling the resulting products below reaction temperature which comprises: maintaining a substantially compact column of downwardly flowing granular contact material in a confined zone, supplying contact material to the upper end of said column at an elevated temperature'whicr. is substantially below the desired reaction temperature, withdrawing contact material from the lower section of said column, introducing a stream containing a combustible fuel and a combustion supporting gas into a core-like portion of said column below the surface thereof to effect combustion in said core-like portion and the heating of the contact material therein to the desired reaction temperature while leaving` the portion of the column laterally surrounding said core-like portion at a temperature Vsubstantially below the reaction temperature, `withdrawing the resulting gaseous combustion products from said column at a level above that of -said stream introduction, introducing a stream of reactant feed existing below the reaction temperature into the heated core-like portion of said column below the level of said first-named stream introduction to effect the heating of said reactant fluid to the reaction temperature and to eiect conversion of said reactant uid to gasifcrm products, passing said 'gasiform products into a cooler portion of said column t effect quenching to a temperature substantially below the reaction temperature, separating said quenched products from Contact material existing below the reaction temperature, cooling the contact material subsequent to separation from said products to a temperature suitable for its supply to the upper section of said column and returning the cooled contact `material to the upper section of said column.
4. A process for rapidly heating reactants to a desired reaction temperature at which said reactants undergo reaction and then rapidly cooling the resulting products below reaction temperature which comprises: maintaining a' .substantially compact column of downwardly flowing granular contact material in a conned zone, delivering the total solid Vmaterial supply to said column onto its upper end at a temperature substantially below the desired reaction temperature, withdrawing contact material from the lower section of said column at a temperature below said reaction temperature, establishing a heated core of contact material at a temperature at least as high as the desired reaction temperature within said column below the surface thereof and above the lower end thereof, said core being surrounded by contact material existing substantially below the reaction temperature, introducing the reactant into said heated core to eiect its conversion to gasiform products, flowing said products from said core into contact with cooler contact material 'in said column to effect its quenching to a temperature below the reaction temperature and withdrawing the quenched products from said column.
5. A- process for effecting high temperature conversions of a hydrocarbon charge to gasiforrn products which are unstable at the reaction temperature comprising: maintaining a substantially compact column of granular contact material in a coniined zone, replenishing said column solely by supplying granular contact inaterial to the upper end thereof at a temperature substantially below that reaction temperature required for eecting conversion ofthe hydrocarbon charge, withdrawing contact material eX- isting below said hydrocarbon-reaction temperature from the lower section of said column to eiect downward movement of the contact material in said column, establishing a heated nucleus of contact material heated to a temperature suitable for supporting said hydrocarbon conversion in a portion of said column located intermediate its ends, said nucleus being surrounded laterally and below by contact material existing substantiallyr below said reaction temperature, introducing a hydrocarbon charge directly into said heated nucleus to eiect its conversion to gasiform products, passing said products from said nucleusinto contact with adjacent cooler Contact material in said column to quench the products to a temperature at which further reaction is substantially prevented and withdrawing quenched products from the column at a level below said nucleus.
6. A method for rapidly heating fiuid hydrocarbon reactants to a desired reaction temperature at which they undergo endothermic conversion to form gasiform products and then rapidly cooling the reaction mixture which method comprises: maintaining a substantially compact column of downwardly flowing granular contact material in a confined Zone, supplying contact material to the upper end of said column at an elevated temperature which is substantially below the desired reaction temperature, withdrawing Contact material fromv the lower section of said column, introducing a stream containing a combustible fuel and a combustion supporting gas into a restricted section of said column lying intermediate its ends and lateral boundaries to effect combustion in a restricted nucleus within said column, whereby the contact material flowing downwardly through the heated nucleus is heated to a temperature suitable for supporting the endothermic hydrocarbon reaction while the contactmaterial in the surrounding portions of said column remains substantially Ybelow the reaction ternperature, introducing a uid hydrocarbon reactant into said heated nucleus at a level spaced k below the level of introduction of said stream of combustible fuel and oxygen containing gas to effect the endothermic conversion of said uid reactant to gasiform hydrocarbon products, passing the resulting gasiform reaction mixture from said nucleus into Contact with the contact material in a cooler portion of said column to quench the same below reaction temperature, withdrawving the Aquenched reaction mixture from said column and withdrawing contact material from the lower section of said colurnn.`
'7. A process for eiecting high temperature conversions of a hydrocarbon charge to gasiforrn products which `are unstableat the reaction temperature comprising: maintaining a substantially compact column of granular contact material 1n a confined zone, replenishing said column solely by supplying granular contact material to the upper end thereof at a temperature substantially below that reaction temperature required for eifecting conversion of the hydrocarbon charge, withdrawing contact material existing below said hydrocarbon reaction temperature from the lower section of said column to effect downward flow of contact material in said column, introducing a restricted stream of heating fluid containing a combustible fuel and an oxygen containing gas downwardly into said column at a location intermediate its lateral and longitudinal boundaries to provide a restricted nucleus of combustion within a portion of said column in which the moving contact material is heated to a reaction supporting temperature while the contact material laterally surrounding said nucleus remains substantially below the reaction temperature, causing the gas to reverse in its direction of flow in said column and withdrawing the gaseous combustion products from the upper section of said column above the level of said stream-introduction to said column, introducing a stream ofvhydrocarbon reactant fluid upwardly into a section of said column substantially above its lower end and directly below the location of introduction of said rst named gas stream so as to contact the heated contact material i'lowing down in said heated nucleus and to effect endothermic conversion of said hydrocarbon reactant to a gasiform product, causing the gasiform reaction mixture to reverse in its direction of flow and to pass downwardly through the adjacent cooler contact material in said column to effect quenching of the reaction mixture below the reaction temperature, with* drawing the quenched reaction mixture from said column at a level below that of the reactant introduction, and maintaining an inert gas seal in said column between the levels of introduction of said heating uid stream and said stream of hydrocarbon reactant.
8. A process for effecting high temperature conversions of a hydrocarbon charge to gasiform products which are unstable at the reaction temperature comprising: maintaining a substantially compact column of granular contact material in a conned Zone, replenishing said column solely by supplying granular contact material to the upper end thereof at a temperature substantially below that reaction temperature required for effecting conversion of the hydrocarbon charge, withdrawing contact material existing below said hydrocarbon reaction temperature from the lower section of said column to effect downward flow of contact material in said column, introducing a restricted stream of heating uid containing a combustible fuel and an oxygen containinggas downwardly into said column at a location intermediate its lateral and longitudinal boundaries to provide a restricted nucleus of combustion within a portion of said column in which the moving contact material is heated to a reaction supporting temperature while the contact material laterally surrounding said nucleus remains substantially below the reaction temperature, causing the gas to reverse in its direction of flow in said column and withdrawing the gaseous combustion products from the upper section of said column above the level of said stream introduction to said column, introducing a, stream of hydrocarbon reactant uid upwardly into a section of said column substantially above its lower end and directly below the location of introduction of said rst named gas stream so as to contact the heated contact material flowing down in said heated nucleus and to effect endothermic conversion of said hydrocarbon reactant to a gasiform product, causing the gasiform reaction mixture to reverse in its direction of iow and to pass downwardly through the adjacent cooler contact material in said column to eiect quenching of the reaction mixture below the reaction temperature, withdrawing the quenched reaction mixture from said column at a level below that of the reactant introduction, maintaining the pressure substantially the same at the locations oi introduction of said hydrocarbon reactant stream and said heating fluid stream and introducing an inert gas into said column at a level between said locations to prevent substantial mixing of the reactant and heating gas streams and recycling contact material withdrawn from the lower section of said column to the upper section thereof.
9. A process for eiecting high temperature conversions of a hydrocarbon charge to gasiform products which are unstable at the reaction temperature comprising: maintaining a substantially compact column of granular contact material in a confined zone, replenishing said column solely by supplying granular contact material to the upper end thereof at a temperature substantially below that reaction temperature required for effecting conversion of the hydrocarbon charge, withdrawing contact material existing below said hydrocarbon reaction temperature from the lower section of said column to effect downward movement of the contact material in said column, establishing a heated nucleus of contact material heated to a temperature suitable for supporting said hydrocarbon conversion in a portion of said column located intermediate its ends, said nucleus being surrounded laterally and below by contact material existing substantially below said reaction temperature, maintaining said heated nucleus laterally separated and insulated from the surrounding cooler contact material along atleast the major portion of its length but open to the rest of the column at its ends, introducing a hydrocarbon charge directly into said heated nucleus at a level where it is laterally separated and insulated and causing it to flow upwardly a short distance therein to effect its conversion to gasiform products, passing said products from said nucleus into contact with adjacent cooler contact material in said column to quench the products to a temperature at which further reaction is substantially prevented and withdrawing quenched products from the column at a level below said nucleus.
l0. A process for rapidly heating reactants to a desired reaction temperature at which said reactants undergo reaction and then rapidly cooling the resulting products below reaction temperature which comprises: maintaining a substantially compact column of downwardly flowing granular contact material in a coniined zone, supplying contact material to the upper end of said column at an elevated temperature which is substantially below the desired reaction temperature, withdrawing ccntact material from the lower section of said column to promote downward flow of contact material in said column, maintaining a plurality of horizontally spaced apart heated cores of contact material at a temperature suitable for supporting the desired reaction within said .column at a common level intermediate its ends, each of said cores being surrounded by contact material existing substantially below the reaction temperature, introducing a fluid reactant stream into each of said heated cores to effect conversion of said reactant to a gasiform product, flowing said gasiform product from said heated cores into contact with the cooler contact material in said column to elfect its quenching to a temperature below the reaction temperature and withdrawing the quenched product from said column.
l1. A process for cracking a hydrocarbon charge at elevated temperatures comprising: maintaining a substantially compact column of granular contact material in a confined zone, replenishing said column solely by .supplying granular contact material to ther upper end thereof at a temperature substantially below that reaction temperature required for effecting oo nverslon of the hydrocarbon charge, withdrawing contact material existing below said hydrocarbon reaction temperature from the lower section of said column to effect downward flow of Contact material in said column, introducing a restricted stream of heating fluid. containing a combustible fuel and an oxygen containing gas downwardly into said column at a location intermediate its lateral and longitudinal boundaries to provide a restricted nucleus of combustion within a portion of said column in which the moving contact material is heated to a reaction supporting temperature while the contact material laterally surrounding said nucleus remains substantially below the reaction temperature, causing `the gas to reverse in its direction of flow in said column and withdrawing the gaseous combustion products from the upper section of said column above the level of said stream introduction to said column, introducing a stream of hydrocarbon reactant fluid upwardly into a section of said column at a location spaced substantially above the lower end of said column and positioned a short distance Vbelow and laterally in line with said heated nucleus so as to effect the heating of said reactant to a suitable reaction temperature and the endothermic conversion of said Areactant to a gasiform product yin a reaction nucleus to which the heat is supplied by Yheated catalyst flowing down from said first named heated nucleus, causing the gasiform reactant mixture to ow into the cooler contact material in said column adjacent said reaction nucleus while changing its flow direction from upward to downward, whereby the reaction mixture .is cooled by the Contact material to a temperature below the reaction temperature at which the reaction is substantially inhibited, withdrawing the quenched reaction mixture from said column at a level below `that of the reaction nucleus but above the lower end of the column, extracting heat from said column at a still lower level to ready the contact material for recycling to the top of said column, passing the contact material 18 compact column of granular contact material in a conned zone, replenishing said column solely by supplying granular contact material to the upper end thereof at a temperature substantially below that reaction temperature required for effecting conversion of the hydrocarbon charge, withdrawing contact `material existing below said hydrocarbon reaction temperature from the lower section of said column to effect downward flow of contact material in said column, introducing a plurality of small streams of heating fluid comprising a mixture of a combustible fuel and an oxygen containing eas downwardly into Said Column at a yplurality of horizontally spaced locations on a common level within said column intermediate its ends .to provide a vplurality of laterally restricted cores of combustion in which the moving contact material is heated to a reaction supporting temperature while the contact material laterally surrounding each core remains substantially below the reaction temperature, reversing the direction of the `gas flow and withdrawing the gas resulting from the combustion upwardly through the column, introducing a separate stream of' vfluid hydrocarbon charg up,- wardly into said column at a location directly below each of said cores of combustion and udi'- rectly in the line o f hot contact material flow therefrom, .whereby the conversion of said hydrocarbon charge to lower boiling gasiform products is effected in a plurality of horizontally spaced apart reaction coros, each of which is surrounded laterally by contact material existing below the reaction temperaturacausing the rellltng gasiform reaction products to flow outwardly vfrom said cores into the vsurrounding cooler contact material and then downwardly within said .column to be withdrawn from a lower portion of said column whereby the gasiform products `are quenched below the reaction temperature kbefore being withdrawn from said column and maintaining an inert gaseous blanket between the cores of combustion and the cores of reaction so as to substantially prevent the mixing of heating and reactant charge fluids.
13. An apparatus for vconducting high temperature fluid reactions in the presenceiof a moying `granular material comprising in combination: an elongated upright Vessel adapted to conne a column of contact material, `means to supply contact material to the upper section of said Vessel and means to withdraw contact ma.- terial from the lower section thereof, inlet conduit for heating fluid introduction extending into an upper portion of said vessel and termi, nating on its downwardly facing, open lower end at a location substantialh7 spaced away ,from the confining walls of said Vessel and spfed ksubstantially below said means to supply contact material, an outlet for heating fluid connected near the upper end of said vessel above said 'inlet conduit, a reactant .inletextending into said ,vessel and terminating on its upwardly ,facing upper end at a location inlateral alignment with and spaced shortly below the .lower end yof said heating fluid inlet conduit, an outlet for reactant gasv connected into said Vvessel at a lower level than said reactantinlet, an .inlet for Vinert gas supply connected into said vessel at .a .level between said kheating fluid and reactant inlets.
14. The lapparatus Vof claim 13 further char.- acterized by .a refractory tube open -on its .ends mounted vertically in said vessel and `concentrically with the upwardly facing upper .end .of
said reactant inlet, `said tube being of largendi 19 ameter than said reactant inlet but of substantially less diameter than said vessel and extending upwardly and downwardly beyond the level of the upper end of said reactant inlet but terminating short of the level of the lower end of said heating fluid inlet.
15. An apparatus for conducting high temperature fluid reactions in the presence of a moving granular contact material comprising: a vertical vessel having contact material inlet means at its upper end and contact material outlet means at its lower end, a refractory tube positioned vertically within an intermediate portion of said vessel and spaced from the vessel walls, an inlet for fluid reactant extending into said refractory tube and terminating its upwardly facing delivery end centrally of the tube walls and a substantial distance from its upper and lower ends, a reactant outlet conduit connecting into said vessel below the reactant inlet, a heating fluid inlet conduit extending into said vessel and terminating on its downwardly facing delivery end along substantially the same vertical axis as the reactant inlet and a spaced distance above the upper end of said refractory tube, an outlet conduit for flue gas withdrawal connected into said Vessel substantially above the level of said last named inlet and an inlet for inert gas introduction connected into said vessel between the levels of said heating fluid and reactant inlets.
16. The apparatus of claim wherein said refractory tube is narrowed in its horizontal cross-section along a portion of its length above its lower end and below the level of the upper end of said fluid reactant inlet.
17. The apparatus of claim l5 with the further improvement of a second refractory tube positioned vertically within said vessel a short distance above said rst tube and adjacent the delivery end of said heating fluid inlet, said second tube being of larger diameter than said heating fluid inlet and being arranged in vertical alignment therewith.
18. An apparatus for conducting high temperature fluid reactions in the presence of a moving granular contact material which comprises: a vertical vessel having cylindrical-shaped upper and lower sections and an annular shaped intermediate section in communication at its upper and lower ends with said upper and lower sections; means defining a separation chamber said means comprising, a member of cylindrical cross section extending upwardly and centrally through the top of said vessel from an intermediate level within said upper section, closure means on the upper end of said member and a gas outlet near the upper end of said member; a gas outlet on said upper section of said vessel above said intermediate level; a closed chamber spaced centrally below said vessel; a vertical conduit extending downwardly from said vessel to said closed chamber; a vertical pipe open on its ends and substantially smaller in diameter than said conduit extending upwardly from an intermediate level within said closed chamber through said vessel to a location within said separation chamber intermediate the ends thereof; means to introduce a lift gas into said closed chamber below said pipe; a plurality of openended vertical, refractory tubes spaced in a ring around a lower part of said annular-shaped section of said vessel, said tubes being of diameter smaller than the width of said annular section and being spaced laterally away from the walls thereof; Ya second plurality of similar vertical refractory tubes, spaced in a ring around an upper part of said annular section, said second tubes being arranged in vertical alignment with said rst tubes so that the lower end of any one of said second tubes is located a short vertical distance above and directly in alignment with the upper end of one of said rst tubes; a separate inlet pipe for fluid reactant extending into each of said rst named refractory tubes and terminating on its upwardly facing delivery end centrally of the tube walls and intermediate the upper and lower ends thereof; means to withdraw reactant from the lower end of said annular section of said vessel; a separate inlet pipe for heating fluid extending into each of said second named refractory tubes and terminating on its downwardly facing delivery end centrally of the tube walls and intermediate the upper and lower ends thereof; and an inlet for inert gas connecting into said annular section at a level between said first and second named refractory tubes.
19. A process for effecting high temperature conversion of a hydrocarbon charge to gasiform products which are unstable at the reaction temperature comprising: maintaining a substantially compact column of granular solid material flowing through a confined housing, establishing a hot nucleus of solid material existing at a temperature suitable for the hydrocarbon conversion within a region of said column spaced substantially away from the housing walls, maintaining the flowing solid material between said hot nucleus and the walls of said housing at a temperature below that at which the hydrocarbon conversion will progress, introducing the hydrocarbon feed into said hot nucleus to effect its conversion to unstable gasiform products, passing the products from the hot nucleus over into the surrounding cooler solid material to effect the quenching of the products to a temperature at which further reaction of the formed products is substantially inhibited, and withdrawing quenched products from said housing.
20. A process for effecting high temperature conversion of reactant charges to gasiform products comprising: maintaining a substantially compact column of granular solid material flowing through a confined housing, establishing a hot nucleus of solid material in a region within said column spaced away from the walls of said housing, maintaining the solid material flowing in said column between said nucleus and the walls of said column at a temperature substantially below that in said nucleus so that the temperature near the walls throughout the housing are substantially below that in said nucleus, in-
troducing reactant charge directly into said hot nucleus to contact the hot solids and to become converted to gasiform products and withdrawing said gasiform products directly from said hot nucleus without flow through the surrounding cooler solids.
271. A process for effecting high temperature conversion of reactant charges to gasiform products comprising: maintaining a substantially compact column of granular solid material flowing through a confined housing, establishing a hot nucleus of solid material in a region Within said column spaced away from the walls of said housing, maintaining the solid material flowing in said column between said nucleus and the walls of said column at a temperature substantially below that in said nucleus so that the tem- 21 perature near the Walls throughout the housing are substantially below that in said nucleus, passing reactant charge into said hot nucleus to contact the hot solids and become converted to gasiform products and passing said gasiform products from said hot nucleus.
ERIC V. BERGSTROM.
REFERENCES CITED The following references are of record in the le of this patent:
Claims (1)
- 4. A PROCESS FOR RAPIDLY HEATING REACTANTS TO A DESIRED REACTION TEMPERATURE AT WHICH SAID REACTANTS UNDERGO REACTION AND THEN RAPIDLY COOLING THE RESULTING PRODUCTS BELOW REACTION TEMPERATURE WHICH COMPRISES: MAINTAINING A SUBSTANTIALLY COMPACT COLUMN OF DOWNWARDLY FLOWING GRANULAR CONTACT MATERIAL IN A CONFINED ZONE, DELIVERING THE TOTAL SOLID MATERIAL SUPPLY TO SAID COLUMN ONTO ITS UPPER END AT A TEMPERATURE SUBSTANTIALLY BELOW THE DESIRED REACTION TEMPERATURE, WITHDRAWING CONTACT MATERIAL FROM THE LOWER SECTION OF SAID COLUMN AT A TEMPERATURE BELOW SAID REACTION TEMPERATURE, ESTABLISHING A HEATED CORE OF CONTACT MATERIAL AT A TEMPERATURE AT LEAST AS HIGH AS THE DESIRED REACTION TEMPERATURE WITHIN COLUMN BELOW THE SURFACE THEREOF AND ABOVE THE LOWER END THEREOF, SAID CORE BEING SURROUNDED BY CONTACT MATERIAL EXISTING SUBSTANTIALLY BELOW THE REACTION TEMPERATURE, INTRODUCING THE RACTANT INTO SAID HEATED CORE TO EFFECT ITS CONVERSION TO GASIFORM PRODUCTS, FLOWING SAID PRODUCTS FROM SAID CORE INTO CONTACT WITH COOLER CONTACT MATERIAL IN SAID COLUMN TO EFFECT ITS QUENCHING TO A TEMPERATURE BELOW THE REACTION TEMPERATURE AND WITHDRAWING THE QUENCHED PRODUCTS FROM SAID COLUMN.
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US124463A US2548286A (en) | 1949-10-29 | 1949-10-29 | Method and apparatus for conducting hydrocarbon conversion reactions |
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Cited By (29)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2684390A (en) * | 1950-05-08 | 1954-07-20 | Union Oil Co | Conversion and quenching process and apparatus |
US2692903A (en) * | 1951-01-02 | 1954-10-26 | Phillips Petroleum Co | Method for converting hydrocarbons |
US2699986A (en) * | 1950-11-17 | 1955-01-18 | Phillips Petroleum Co | Manufacture of hydrogen |
US2726995A (en) * | 1950-09-13 | 1955-12-13 | Universal Oil Prod Co | Method for contacting and transporting subdivided contacting material |
US2739994A (en) * | 1952-04-21 | 1956-03-27 | Union Oil Co | Acetylene process |
US2741648A (en) * | 1953-05-25 | 1956-04-10 | Union Oil Co | Production of acetylene |
US2745723A (en) * | 1950-04-12 | 1956-05-15 | Houdry Process Corp | Apparatus for the conversion of liquid hydrocarbons |
US2748060A (en) * | 1952-05-09 | 1956-05-29 | Socony Mobil Oil Co Inc | Hydrocarbon conversion process and apparatus therefor |
US2767129A (en) * | 1950-07-27 | 1956-10-16 | Sinclair Refining Co | Process and apparatus for contacting hydrocarbons and catalysts particles in a moving bed |
US2767128A (en) * | 1951-05-02 | 1956-10-16 | Houdry Process Corp | Method and apparatus for contacting solids with fluids |
US2770582A (en) * | 1952-10-07 | 1956-11-13 | Socony Mobil Oil Co Inc | Method and apparatus for the conversion of high boiling liquid hydrocarbons |
US2770504A (en) * | 1951-02-14 | 1956-11-13 | Socony Mobil Oil Co Inc | Method for transfer of contact materials |
US2772315A (en) * | 1952-06-19 | 1956-11-27 | Socony Mobil Oil Co Inc | Dehydrogenation process |
US2772225A (en) * | 1952-05-24 | 1956-11-27 | Socony Mobil Oil Co Inc | Method and apparatus for effecting conversion of hydrocarbons |
US2783186A (en) * | 1951-07-07 | 1957-02-26 | Socony Mobil Oil Co Inc | Method and apparatus for hydrocarbon conversion |
US2816941A (en) * | 1953-11-27 | 1957-12-17 | Phillips Petroleum Co | Production of unsaturated hydrocarbons and apparatus therefor |
US2833837A (en) * | 1958-05-06 | Process and apparatus for high | ||
US2833838A (en) * | 1958-05-06 | Apparatus and process for high temperature conversions | ||
US2843532A (en) * | 1951-12-10 | 1958-07-15 | Phillips Petroleum Co | Method for converting hydrocarbons |
US2854405A (en) * | 1952-05-23 | 1958-09-30 | Socony Mobil Oil Co Inc | Continuous hydrocarbon conversion process employing a compact mass lift |
US2875146A (en) * | 1954-04-15 | 1959-02-24 | Phillips Petrolcum Company | Prevention of coke depositions in a hydrocarbon coking zone |
DE971805C (en) * | 1953-05-27 | 1959-04-02 | Exxon Research Engineering Co | Process and device for the conversion of hydrocarbon oils |
US2901421A (en) * | 1952-07-12 | 1959-08-25 | Socony Mobil Oil Co Inc | Method and apparatus for transfer of contact materials |
US2915459A (en) * | 1953-12-09 | 1959-12-01 | Houdry Process Corp | Art of circulating contact material |
US2923677A (en) * | 1958-09-18 | 1960-02-02 | Socony Mobil Oil Co Inc | Method and apparatus for the supply of hydrocarbon charge to conversion reactors |
US2935461A (en) * | 1956-01-20 | 1960-05-03 | Houdry Process Corp | Catalytic cracking of heavy charge stocks |
US2954415A (en) * | 1953-12-31 | 1960-09-27 | Topsoe Haldor Frederik Axel | Method of carrying out chemical reactions in the gaseous phase at high temperature by interaction with freely falling contact bodies present in the gaseous phase |
US3048476A (en) * | 1955-04-27 | 1962-08-07 | Kellogg M W Co | Conversion of hydrocarbons and carbonaceous materials |
US5648051A (en) * | 1989-07-19 | 1997-07-15 | Chevron U.S.A. Inc. | Apparatus and method for quenching in hydroprocessing of a hydrocarbon feed stream |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2378342A (en) * | 1941-12-31 | 1945-06-12 | Standard Oil Co | Catalytic conversion process and apparatus |
US2445328A (en) * | 1945-03-09 | 1948-07-20 | Hydrocarbon Research Inc | Conversion process for heavy hydrocarbons |
US2445327A (en) * | 1944-08-02 | 1948-07-20 | Hydrocarbon Research Inc | Fluidizing process for gasifying carbonaceous solids |
US2477502A (en) * | 1946-12-14 | 1949-07-26 | Socony Vacuum Oil Co Inc | Method for conducting gaseous reactions in the presence of a moving particle form solid |
-
1949
- 1949-10-29 US US124463A patent/US2548286A/en not_active Expired - Lifetime
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2378342A (en) * | 1941-12-31 | 1945-06-12 | Standard Oil Co | Catalytic conversion process and apparatus |
US2445327A (en) * | 1944-08-02 | 1948-07-20 | Hydrocarbon Research Inc | Fluidizing process for gasifying carbonaceous solids |
US2445328A (en) * | 1945-03-09 | 1948-07-20 | Hydrocarbon Research Inc | Conversion process for heavy hydrocarbons |
US2477502A (en) * | 1946-12-14 | 1949-07-26 | Socony Vacuum Oil Co Inc | Method for conducting gaseous reactions in the presence of a moving particle form solid |
Cited By (29)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2833837A (en) * | 1958-05-06 | Process and apparatus for high | ||
US2833838A (en) * | 1958-05-06 | Apparatus and process for high temperature conversions | ||
US2745723A (en) * | 1950-04-12 | 1956-05-15 | Houdry Process Corp | Apparatus for the conversion of liquid hydrocarbons |
US2684390A (en) * | 1950-05-08 | 1954-07-20 | Union Oil Co | Conversion and quenching process and apparatus |
US2767129A (en) * | 1950-07-27 | 1956-10-16 | Sinclair Refining Co | Process and apparatus for contacting hydrocarbons and catalysts particles in a moving bed |
US2726995A (en) * | 1950-09-13 | 1955-12-13 | Universal Oil Prod Co | Method for contacting and transporting subdivided contacting material |
US2699986A (en) * | 1950-11-17 | 1955-01-18 | Phillips Petroleum Co | Manufacture of hydrogen |
US2692903A (en) * | 1951-01-02 | 1954-10-26 | Phillips Petroleum Co | Method for converting hydrocarbons |
US2770504A (en) * | 1951-02-14 | 1956-11-13 | Socony Mobil Oil Co Inc | Method for transfer of contact materials |
US2767128A (en) * | 1951-05-02 | 1956-10-16 | Houdry Process Corp | Method and apparatus for contacting solids with fluids |
US2783186A (en) * | 1951-07-07 | 1957-02-26 | Socony Mobil Oil Co Inc | Method and apparatus for hydrocarbon conversion |
US2843532A (en) * | 1951-12-10 | 1958-07-15 | Phillips Petroleum Co | Method for converting hydrocarbons |
US2739994A (en) * | 1952-04-21 | 1956-03-27 | Union Oil Co | Acetylene process |
US2748060A (en) * | 1952-05-09 | 1956-05-29 | Socony Mobil Oil Co Inc | Hydrocarbon conversion process and apparatus therefor |
US2854405A (en) * | 1952-05-23 | 1958-09-30 | Socony Mobil Oil Co Inc | Continuous hydrocarbon conversion process employing a compact mass lift |
US2772225A (en) * | 1952-05-24 | 1956-11-27 | Socony Mobil Oil Co Inc | Method and apparatus for effecting conversion of hydrocarbons |
US2772315A (en) * | 1952-06-19 | 1956-11-27 | Socony Mobil Oil Co Inc | Dehydrogenation process |
US2901421A (en) * | 1952-07-12 | 1959-08-25 | Socony Mobil Oil Co Inc | Method and apparatus for transfer of contact materials |
US2770582A (en) * | 1952-10-07 | 1956-11-13 | Socony Mobil Oil Co Inc | Method and apparatus for the conversion of high boiling liquid hydrocarbons |
US2741648A (en) * | 1953-05-25 | 1956-04-10 | Union Oil Co | Production of acetylene |
DE971805C (en) * | 1953-05-27 | 1959-04-02 | Exxon Research Engineering Co | Process and device for the conversion of hydrocarbon oils |
US2816941A (en) * | 1953-11-27 | 1957-12-17 | Phillips Petroleum Co | Production of unsaturated hydrocarbons and apparatus therefor |
US2915459A (en) * | 1953-12-09 | 1959-12-01 | Houdry Process Corp | Art of circulating contact material |
US2954415A (en) * | 1953-12-31 | 1960-09-27 | Topsoe Haldor Frederik Axel | Method of carrying out chemical reactions in the gaseous phase at high temperature by interaction with freely falling contact bodies present in the gaseous phase |
US2875146A (en) * | 1954-04-15 | 1959-02-24 | Phillips Petrolcum Company | Prevention of coke depositions in a hydrocarbon coking zone |
US3048476A (en) * | 1955-04-27 | 1962-08-07 | Kellogg M W Co | Conversion of hydrocarbons and carbonaceous materials |
US2935461A (en) * | 1956-01-20 | 1960-05-03 | Houdry Process Corp | Catalytic cracking of heavy charge stocks |
US2923677A (en) * | 1958-09-18 | 1960-02-02 | Socony Mobil Oil Co Inc | Method and apparatus for the supply of hydrocarbon charge to conversion reactors |
US5648051A (en) * | 1989-07-19 | 1997-07-15 | Chevron U.S.A. Inc. | Apparatus and method for quenching in hydroprocessing of a hydrocarbon feed stream |
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