US2884368A

US2884368A - Process for the pyrolysis and gasification of hydrocarbonaceous materials

Info

Publication number: US2884368A
Application number: US566205A
Authority: US
Inventors: Sweeney Maxwell Patrick
Original assignee: United Engineers and Constructors Inc
Current assignee: United Engineers and Constructors Inc
Priority date: 1956-02-17
Filing date: 1956-02-17
Publication date: 1959-04-28
Anticipated expiration: 1976-04-28

Description

Apnl 28, 1959 M. P. SWEENEY ,8

PROCESS FOR THE PYROLYSIS AND GASIFICATION OF HYDROCARBONACEOUS MATERIALS Z'Sheets-Sheet 1 Filed Feb. 17, 1956' Elm l EPARAT/ON F/ G' I 27 VESSEL v V V 26 v /5 4 Z 7 25 v 9 /0 47 ie BURNER v HEAT 5 E EXCHANGE}? 3 l8 2 aw IIVM/Q 2 V PREHEATER sum 5 I 9 30 34 I, I I V22 v 20 1 L \V/ 2/ HYDROGARBON FEED CYCLONE SEPARATOR l4 3 2/8 zzr 220a i 25 BURNER 220 FRACUOIVATOR INVENTOR.

Maxwell Pafn'c/r Sweeney BYh/s al/orneys AMMM April 28, 1959 M P. SWEENEY 2,884,368

PROCESS FOR THE PYROLYSIS AND GASIFICATION OF HYDROCARBONACEOUS MATERIALS Filed Feb. 17, 1956 2 Sheets-Sheet 2 QAS/F/ER PRODUCT CO-K GAS and GASQQENE /3// 303 3 5 645 0/1. I -334 6A5! F/ER 0 5 5 IN V EN TOR.

Maxwell Parr/"ck Sweeney Y his affarn eys MAM.

RECYCLE Recycle 60 United States Patent PROCESS FOR THE PYRGLYSIS AND GASIFICA- TION OF HYDROCARBONACEOUS MATERIALS Maxwell Patrick Sweeney, Philadelphia, Pa., assiguor to United Engineers & Constructors Inc., Philadelphia, Pa., a corporation of Delaware Application February 17, 1956, Serial No. 566,205

17 Claims. (Cl. 208-53) This invention pertains to a method for the production of valuable gaseous, liquid, and solid products from lower value hydrocarbonaceous materials, and particularly to a method for the pyrolysis of hydrocarbonaceous substances, in the presence of finely divided solid material, without the disadvantages normally associated with the use of such material.

The invention is of use in many diflFerent applications; for example in the production of valuable gaseous and liquid products and coke from petroleum residues and low value gaseous hydrocarbons, in the gasification and carbonization of coal, lignite and peat and in petroleum refining.

Prior to the present invention a number of processes have been suggested for converting lower value hydrocarbonaceous materials, such as lower paraffins, residual fuel oils and coal, to more valuable gaseous and liquid products, and coke.

In general, these processes have been run at three different temperature ranges, below about 1100" F., above 1800" F. and in the intermediate range between about 1100 F. and about 1800 F.

Below about 1100 F., the products are primarily lower molecular weight normally liquid paraflinic hydrocarbons.

Above about 1800 F. the products are largely carbon and normally gaseous materials having a high acetylenic content.

In the range between about 1100 F. and about 1800 F. the proportion of aromatic substances is large, increasing with increasing temperature, above about 1100" F. and reaching a maximum around 1500 F. These aromatic materials have a high sale value and in most cases are the most desirable product. However, many of the aromatics so produced tend to polymerize in the presence of other pyrolysis products and at the temperatures in question, i.e. 1100 F. to 1800 F., to produce high molecular weight liquid pitch.

The question how best to control the several reactions involved and to collect the large variety of difierent products formed has given rise to a number of different techniques for conducting pyrolysis processes in this temperature range and for furnishing the heat necessary for the pyrolysis.

It has been proposed, for example, to charge the low cost hydrocarbonaceous feed to a fluidized bed of finely divided solids maintained at pyrolysis temperature and to conduct all of the cracking in the bed. The difficulty with this technique is that it is inherently inflexible. Reaction time, temperature, and other conditions vary with diflerent feed materials and products, and it is desirable to have an apparatus capable of handling a variety of different feeds to make a variety of different products. Vessels suitable for holding a fluidized bed must, however, be designed for a limited range of operating conditions, and are not easily altered to diflferent conditions. Moreover, in many instances it is desirable to quench the ice intermediate products and prevent the pyrolysis feaction from going to completion. This cannot conveniently be done with a single fluidized bed. I

It has also been proposed to conduct the pyrolysis reaction in a hot moving streamof gases and entrained solids and then deliver the reacted stream into a suitable separation device, such as a cyclone separator, where the va-porou-s pyrolysis products would be separated from the solids. Processes of this type have the drawback that they are difficult to control to give products of uniform composition. Moreover, where the pyrolysis products are quenched, as by spraying oil into the sep aration device, high molecular Weight pitch molecules deposit on the walls of the separator, or pass out of the separator and deposit in downstream apparatus. In either case, removal of the high molecular material is an expensive operation.

In a large number of prior techniques the heat necessary for pyrolysis has been furnished by burning the solid coke or char produced. The most usual technique is to withdraw solid pyrolysis product from the reaction zone where it is formed, and burn part of it in a heater, and often in a fluidized bed, to heat the unburned remainder which is then reburned to the reaction zone.

This technique is open to several objections. The ash produced contains oxides of vanadium, nickel and iron. Since the unburned solids are continuously recirculated, this ash and the oxides contained therein build up in the system and cause serious problems of corrosion, particularly at temperatures of say 1400 F. and above.

In addition to problems of corrosion, concentration of metallic oxides in the fluidized solids causes very serious difficulties of temperature control. Thus at a reactor temperature of say 1400" F., and under the reducing conditions maintained in the reactor, the metal oxides give up a substantial portion of their oxygen. They are later reoxidized in the heater. The oxidation reaction in the heater is highly exothermic and the reduction reaction in the reactor is endothermic, causing the heater to overheat excessively and the reactor to cool off excessively, and making it difiicult to maintain a proper temperature in the reactor without having the heater operate at an excessively high temperature.

It has also been found that the reduced oxide containing particles formed in the reactor tend to stick to each other and to the reactor surfaces, causing difiiculties in fluidization.

It may further be pointed out that while prior pyrolysis systems of the types described have been utilized to treat petroleum residues, to present knowledge no attempt has been made to replace basic refinery equipment, such as atmospheric and vacuum distillation equipment or thermal and catalytic cracking equipment with such systems. This is so despite the fact that such conventional basic equipment presents a very large cost element, particularly in smaller plants of say 5000 to 50,000 bbL/day capacity.

It is an object of the present invention to provide a more economic method and apparatus for the production of high value solid, liquid, and gaseous products from low value hydrocarbonaceous materials, than has hitherto been available.

It is a further object of the invention to provide a method and apparatus of the class described in which a maximum amount of liquid aromatic products can be obtained.

It is another object of the invention to provide an economic method and apparatus of the class described using a mass of finely divided solid carbonaceous materials.

It is a further object of the invention to provide a process and apparatus of the class described in which the necessary heat can be drawn from the combustion oti eqlge f or rr ecl during the process, under conditions which are more easily controlled than has hitherto been possible.

Itwis. a furthernobject. of. theinvention to provide a method and. apparatus .of' the class described in which 'It is a furtherrobject offthednvention to provide a method and apparatus of the class. described in which either hydrocarbon oil, or coal, or both, can be used siehdstwk;

lt is' a further object of the invention to provide a method and apparatus of the class described in which sueeessiv ,eXpOS1 re of ashrcontaining material to oxidizset! educi a o d ti s isrminimized- It'is a further object of the invention to provide a' pgocess and. apparatus of the class described in which corrosive oxides are easily removed from the system.

I is. t l n tha bj ct f e nv nt t Provide msthc s nd. pparatus. .-v h finin ipe simpler-arm s pe i an. hos P ently av lable...

.Aeeor ng to the inyention, theseand other objects trE'IbeEyQeen abouullOQ" F, and about 1800 and, prsi rahly qabetw en bo .0 nd b t stpar ally p rol se a d f e re m, y charge,

"25 anc iienu ained finely divided solids, delivering the combi'ne ream of hot gases, solids andfeed to a fluidized Pals. iv de sqlids removing p u p ymlrsi f omsa d Tl auslacf l fluid zed eds-r t y o s emrsramrecin t e manne nd ca e Pr v s a nd of temperature for-a relatively extendedtime without undue enlargement of'equipment, until their pyrolysis: is uniormly postula d If on the other ha nd,' the products are quenched either by n aintaining the bed at a low temperature, or by using a quenching spray as described more fully below, the fliiidize'd bed'providesa large surface area for incompIeteIY pyrQIysedliquids to deposit upon, I preventing their-depositing on andfouling I downstream apparatus.

'The solid 'particles in the hot stream and in thefluidized' bed; are preferably, but not necessarily, the COkQf'OF'ChHl' produced by the pyrolysis. If desired, this; coke may be augmented or replaced by other solid carbonaceous material such as coal, lignite, oil shale or the like,-or char or coke from some external source.

It-is also within the scope of the invention to use av more inert material, for example, sand. Entrained in the moving stream, the solid particles serve to bring the stream gasesto the desired temperature, either by heating or by cooling them. The particles also provide a u f ce-upon hichccke me y-pyro y f the flagran -d posit.

'I'he ,hydrocarbonaceous=materials which can be used.

as feed in the novel process include such materials. as,

for example,,- coal, oil,sha,le, lignite, peat, residualfuel oil ;such; as Bunker C fuel oil, coke oven lay-product: Fs-l 934d? e asl dltqedncmde ;oil-, virgin distillate z-gass ned by heating a hydrocarbonaceous feed stream i d t sa but. moving s r m fj s p rolysis may be kept at a high easily controlled '45 ofthermalflywheel'which permits a.rnore. stable and easily controlledpyrolysis; Thus, heavy liquid; products oils, catalytic recycle gas oils, kerosenes, naphthene, and lower parafiins having two or more carbon atoms in the molecule, such as propane, butanes, and ethane.

The gaseous stream containing entrained solids into which the hydrocarbon feed is introduced, may be derived from several sources. Where the primary purpose is to produce a high heating value utility gas, the entraining gas.is.preferably one which may easily be separated" from the gaseousproducts of pyrolysis, or else which will not detract from the value of the product. Such. gases may for example be steam or recycled product gas.

Where, on the other hand, a diluted product gas is acceptable, 7 the entraining gases may be products of combustion, e.g. CO and/ or nitrogen.

The temperature-,at'which vthe pyrolysis is conducted will vary to some extent with the materials being reacted and with the products desired. Generally, however, as indicated above, it will. be between about 1100 F. and aboutlfiOO" FL, preferablyrbetween about 1100 F. and aboutlYOOf F. Pressure is not considered critical andmaybe atmospheric or as high as, for example, 2050 p.s,i,g. Reaction time mayvary from say about 0.1 .to about 5 "seconds.

Preferably, the heat necessary forpyrolysis is furnished" by burningfinely divided coke or char produced in the pyrolysis reaction. In;a preferred form of-the invention, the coke is burned in a slagging type combustion; device. By this is meanta combustiondevice so designed that theash is,converted to a liquid slag which may be drained-away, rather than passing off overhead to gatherin downstream products and apparatus. Such combustion, devices include those having'cyclonic combustion chambers in,,which the finely divided fuel is burned'in a,vortically moving body of hot gases. Furnaces of this i type are well known in the artandare-described, for example in Patents Nos. 836,145, 836,219; and2,357,30l. Th'ey;-are cornmonly referred toas cyclone furnaces. Where the solid material entrained-in the gases priorto feedintroductionis not carbonaceous, it will of course not be possible to use a slagging type burner.

Itiisalso within the, scope of the invention to obtain the heat necessary for pyrolysis in-whole orin part from sources other than the coke produced. Thus, where the coke has a-sale value higher than available external fuels, it may be recovered and in its place-the cheap external" fueLmay be burned in any type of a conventional burner. Injcertain cases, the value, of the coke may be-higher than the fuel gas produced -by pyrolysis and there the fuel-gas may beburned in place of or in partial replace-- ment of the coke. 1

The way in which the heat of pyrolysis is transferred from'its-source to the ,hydrocarbonaceous feed varies." Preferably, however, where the solid products of pyrolysis areburned to producethe necessary heat, no portion of *the solids introduced intoa zonewhere substantial oxidation takes place .is reintroduced into the reaction zone; In thispway, building up of'metal oxidesv in.the. system is; avoidedr In one embodiment, hot gaseous products of combustion drawn from a burner are made to entrain finely divided solids having a lower temperature than -the hot gases, and it is to this stream that the hydrocarbonaceous feed is added This embodiment is simple anddirectand requires-a minirnum of equipment.

In' asecond-embodiment, hot gaseous products of' combustion drawn froma burner are used to heat up a-:mass-of-finelydivided solids, which is then separated from the products of combustion and entrained in another stream ofgases to which is charged the hydrocar-;

bonaceousnfeed;v This :other gas stream maybe, for ex-' ample-steamer recycled'productrgas. Thesecond em, bodiinent: has the ,-advantage: of r avoiding contamination;- of-;the gaseousproducts of pyrolysis by-inert components suchrasyCQ Such;co-ntamination ;would, result werev hezhocprn ucts iofi-combustionzbroughtdirectly into corn; tact: withathe feeds;

ph nd a final xotherm c p ase. the endothermic p ,the hydrocarhonaceous feed eenv'ertedintqsub ces -l: '|'e lieyecl to consist of free radicals and un'sa'tu d gpmpdnnus", which have higher enthalpies than the nail pioduct's'. In "the second stage, these'interrnediate high enthalpy, substances rfeconibinetofoiin the final pion ers" and in" sodoiiig' r ease heat. V In the p'resent" r cess, ne i al endothermic phase or the" cracking reaction ma be carried out before the mixture of the gases and solid particles reaches the fluidized e an the exothe hfi portion may then be 651; ed out in the iiuidrzed b eidj this arrangement, the heat of reaction aid's in maintaining thefbed, with its relatively large cross-sectional "area and volume, at reabfiofi tem e at e I. j i f i A er t e y b t por i ns f, e; v ti i.my be carried to completion before the reactants reach the fluidized bed and the may be maintained at a rela-' tively temperature to quench the reaction products andvprevent the formation of undesirable materials; By ehqh i i n i man er, 'i el l b iten' s Q high ba l ai r sa ase t 9n the =P t l 9 PQk'e andxarqt n remq di mm th W a team W e e they, w uld tandfiq dsaa i i r fer. l e and. 15 15 usnt .d s ill i men -v, f n w rys h some? ai f he,b d .m y1bem in a a s trby w h: drawing solid materialfrom the bed heating or cooling it, as in a heat exchanger, and retu rningit to the bed. It is; f. soi eda so qs n l to ha ei h r, the 951 thermic or the exothermic parts split between the reaction stream and the fluidizedbed, H 1 V I 2 In; another aspect of the invention, especially useful where a relatively heavy hydrocarbonacequs feed, such as Bunker C fuel oil or coke oven tar is charged to a hot moving stream of gases and entrained solids, materials having a molarH/ C (hydrogen/carbon) ratio, rela; tive to the hydrocarbonaceousfeed, rnay "be added to the hot stream before the ,feed itself is introduced. Such materials may include, for example, hydrogen, or hydrocarbons such .as methane, ethane, ethylene, propane. propylene, and butane ;By ,using such additions, the proportion of lower boiling materials in ,the. Pyro lysis pro dnot is increased and, the proportion of pitchis decreased. In particular where butaneis used, the proportionof valuablebutadiene is increased. In addition, sulphur which would normally remain ,in the coke or char resi due is'carried overhead as H28, increasing the value of the char or coke.

The materialsadded may be obtained from sources outside the pyrolysis system. However, the fixed gases produced by pyrolysis contain materials having a high H/C ratio and preferably these gases, or a portion of th'enji, are recycled and added' to the hot stream.,.

' Except in the case wherejthe material added consists principally of hydrogen, it is generally desirable to inject the added material at a point on the hot gaseous e11 trained soli'dslstream where the temperature, of thehot stream is suffi cient to at least" partially crack the added substance; for exam le at between about 1500? F. and about 170051 In this way, additional valuable prodnets are formed and a high partial pressure of hydrogen is orea'ted 'in the zone Where pyrolysis of the main feed material is to' be carried out. A high partial pressure of hydrogen enhances the efiEects noted above, namely a doc e in the production of pitch, an increase inthe' trjty of lower boiling materials, and a more valuable res1 It is also within the scope of the invention, where the sagas b d, h ijs" medium may be" water; as is iffejably'a liquid hydro ar bon, suchfor example ss as" The amount of oil is preferably re ulated" so' that will remain at a temperature suflicient to crack the:

sprayed oil' itself, this adding" to the qiialntify of desirable. vapors removedfroriithesp 'r'a one, t i The pyrolysis methods hich' have been air ines re applicable to many industries ln particular, manta: comprises a metho of refining permit ing in which crude oil is topped wr meve asoliriej-a'ii d thensubjiicted' to the pyrolysisni'ethods de's i eaabov; The invention further inc des an apparatus forlthe pyrolysis oraymtxarsonaemn materials whichQcomprises in :combina'tfion, an enlar ed ves el adsptedtdflsup;

. taiiiin'g entrained sends, and means r r iaeadhein port afiuidizedbed of finely divided solids, a leading to said enlarged sepai'atory vessel, "has c"oni-' prising a slagging type combustion device connecting with said conduitfor generatin'ga hot stream of gasesrconta hyqmc'arbbmons reeaingintesaid c n uit. er specifically, n one em oqiment, the invention provides apparatuscomprising, in'combinatioihl icond it, aslaggi'ng type burner having a hot gasouuei coiinc 3b; to one and of t'he conduit, an enlargedvessd adapted? to support a fluidize be-('1 of finely, divided solids can: i eoted to the other and of said conduit, nah-s: rd; an is: (hiding finely divideds'oli era" point aloiig'thell r t if said manna ape means for mmaneing afiy' star;

; bonaceous material to" said condiiit at aipointf b tween' the point of introduction of solids thereto aiid the end of the conduit joined to said vessel. e a v In another embodiment, apparatus according toth'eirfl yentionscornprises a' first s'eparatoiy' vessel, atse cond sep aratorjy vessel adapted to support a fluidized beater finely divided solids, first conduit mean f f transferring solids from; said first to said second vessel, meansfor' intro ducing a hydrocarbonaceous feed into said coiid a slagging type combustion device, second conduit mess? joining said combustion devicewith' said first separat yessel, 1 means for introducings'olids from said second? separatory vessel to said'se'condconduit means and me ns for ,conveying solids'from said' first s'e'paratory vessel" to" saidburner. H e In both embodiments, theconduits may haveyerit c nstrictions or threats at the point where the hy rdcar bon feed is introduced, N g, f j By choice of proper conditions of operatio nland (feed stock, a great variety of valuable products canbe pro;

diene, cy clopenta'di'ene, gasolene, benzene, toluene, Xylene, naphthalene, resin-formers, creosote oil, electrodegral de pitch, and coke, and synthesis gas for the product of arm monia, methanol, synthetic fuels, and the likei 3 L V Inthe detailed description which follows, memes will be made to the accompanying 'drawings'in which:

Fig. 1 is a schematic flow diagram arose type'of pyrol ysis system according to the invention Wherein lijotgase ous products of combustion are brought into direct contacttwiflh the hydrocarbonaceous feed, 7 g j Fig. 2 is asche ma tic fiowdia'grarri of a second type Oli pyrolysis system according to the invention' in,ubhicli'heat is transferred to the hydrocarbon feed' by mea nsof finely dividedsolids, v i h Fig, 3 is a schematic flow diagram showing elements, of a preferred type os etrde'nm' refining system usingj the prolysis system of Fig. 2, and I H i Fig. 4 is aschematic flow diagram showing eleme s, of another type ofpetzroleum refining system also using Referring first to Fig. 1, a

assgses 7 to one embodiment of the invention, may comprise a U-, shaped conduit 3 extending between a cyclone burner 4 an enlarged separation vessel, or gasifier 5, suitable for containing a fluidized bed of finely divided solids 6.

i A line 7, having a valve 27, is provided for feeding solids from the bed 6 to the burner 4. A line 8 is provided for introducing oxygen, air, or other oxygen-containing gas to the burner 4. The burner has a draw-off 28 for liquid slag.

' A line 9 is provided for introducing finely divided solids from the bed 6 to the conduit 3 at a point 10 downstream from the connection between the conduit 3 and the burner 4.

The conduit 3 has a Venturi throat 2 and at the throat a line 1 is connected to the conduit for the introduction of a hydrocarbonaceous feed. A preheater 11 is furnished for preheating the feed.

"The gasifier 5 has an internal solids separator such as a cyclone separator 12 lfor further separating entrained solids from the gaseous products emanating from the bed 6. A line 13 is provided for removing such products from the vessel.

To provide a means for controlling the temperature in bed 6, a heat exchanger 16 is provided, together with a line 14 leading from the bed 6 to the heat exchanger 16. A valve 15 controls the fiow through. line 14. Cooled solids are returned from the heat exchanger 16 to conduit 3 by means of a line 17 and a valve 18. A line 19, having a valve 20, is provided for withdrawing solids from line 17. A line 21, having a valve 22, is arranged for the introduction of fiuidizing gas into line 17.

' In the preferred mode of operation, a fluidized bed 6 of finely divided solids is established in separation vessel 5. These solids are preferably coke, of the general type to be produced, but they may be other solid material, such for example as coal, lignite, or oil shale. The temperature in the vessel 5 is maintained between about 600 F. and about 1800 F., preferably between about 800 F. and about 1700 F., and the pressure between about p.s.i.g. and about 2000 p.s.i.g., preferably between about p.s.i.g. and about 300 p.s.i.g. A certain amount of the finely divided solid material is continuously with- [drawn from the bed 6 through line 7 and is fed to the cyclone burner 4, where it is burned with air or oxygen introduced through line 8. The hot gaseous products of combustion from burner 4, at a temperature between about 1400 F. and about 5000 F., preferably between about 2000" F. and about 3200 F., enter conduit 3 and are mixed with additional carbonaceous solids withdrawn from the bed 6 through line 9. These solids enter the conduit 3 at point 10, and are entrained in the hot gases and serve to cool the gases, preferably to between about 1200 F. and about 2000" F. The pressure of the gases at this point is between about 0 p.s.i.g. and about 2050 p.s.i.g., preferably between about 6 p.s.i.g. and about 305 p.s.i.g.

The mixture of hot products of combustion from burner 4 and solid particles pass through the Venturi throat 2 where they pick up the hydrocarbonaceous feed, introduced from the line 1, after having been preheated in heater 11. Upon introduction of the feed into the conduit 3, pyrolysis is initiated.

The temperature of the materials in the reaction zone downstream of the Venturi throat is between about 1100 F. and about 1800 R, preferably between about 1100 F. and about 1700 F. The pressure is maintained between about 0 p.s.i.g. and about 2050 p.s.i.g., preferably between about 6 p.s.i.g. and about 305 p.s.i.g.

As indicated generally above, in one embodiment of the invention, the endothermic part of the pyrolysis reaction is preferably completed in the conduit 3. The exothermic part, on the other hand, may be carried out in the conduit 3 or in the gasifier 5. Where the exothermic part is carried out in the gasifier, the gasifier is operated at a temperature between about 1100" F. and about 8 1800 F., preferably between about 1100 F. and about 1700 F., and at a pressure between about 9 p.s.i.g. and about 2050 p.s.i.g.

Where the gasifier bed is used to quench the products of reaction, the gasifier, is operated at a temperature between about 600 F. and about 1100 F., preferably between about 800 F. and about 1100 F., and at a pressure between about 0 p.s.i.g. and about 2000 p.s.i.g., preferably between about 0 p.s.i.g. and about 300 p.s.i.g. Under these conditions, further reaction of the cracked products is suppressed and the heavy pitch materials produced by the cracking reaction are condensed onto the solid particles, leaving the cracked products to pass out overhead through cyclone separator 12 and line 13. The products emerging through line 13 may be condensed and further treated, as for example by distillation steps not shown.

To maintain the bed of fluidized particles 6 at proper temperature, a stream of such particles may be withdrawn through line 14 and valve 15 and passed through a heat exchanger 16 where it is cooled. The cooled material is then returned to the bed 6 through line 17, valve 18, and conduit 3. If desired, a certain amount of this carbonaceous material may be withdrawn as product through line 19 and valve 20. To maintain the proper fiow of material in line 17, a suitable fiuidizing gas, such as steam, may be introduced through line 21 and valve 22.

The combustion carried out in burner 4 produces, in addition to the hot gases delivered to the conduit 3, a liquid slag which is withdrawn through off-take 28. This slag contains a large part of the corrosive oxides originally present in the coke. The use of a combustion device, producing a liquid slag, thus furnishes a convenient way to prevent such oxides from building up in the system and minimizes corrosion problems.

As noted above, the combustion-supporting gas introduced through line 8 may be either air or oxygen. With air, a fuel gas can be produced having a heating value in the neighborhood of 200 to 600 B.t.u. per cubic foot, depending on the type of material charged. Using air, the production of materials such as 'a'cetylene and butadiene is favored because the diluting effect of the nitrogen results in a lowered partial pressure of hydrocarbon. Such lower partial pressure favors net formation of unsaturated compounds because of the reduced chance for polymerization due to the lowered concentration.

If it is desired, on the other hand, to have the product gas high in B.t.u. content, e.g. 600-1S00 B.t.u. per cubic foot, or have it most suitable for the recovery of ethylene, oxygen should be used instead of air at point 8. The use of oxygen to support combustion in the cyclone burner 4 obviates compressing a product diluted with nitrogen to the 500 to 700 pounds per square 'inch necessary to separate the ethylene from other gases present.

In bringing the apparatus shown in the drawing on stream, steam may be introduced through line 8 and finely divided coke having a particle size between about 10 microns and about 0.1 inch introduced through line 23 and valve 24. When the bed 6 has been filled to a sufiicient depth, air or oxygen is introduced through line 8 and additional coke is introduced to the conduit 3, through line 24 and valve 25. Only sufiicient oxygen or air is introduced to supply the proper amount of heating. Excess oxygen or air is avoided. Hydrocarbon feed is then slowly introduced through line 1. The hydrocarbon is converted into coke in the conduit 3 and bed 6 builds up in the gasifier 5. The carbon introduced through

valves

24 and 25 is then gradually reduced and valves 26 and 27 are opened to permit carbon particles from the bed 6 to How through lines 7 and 9 and thence into the cyclone burner 4 and conduit 3 respectively.

As indicated above, the system described has great flexibility of operation. Thus for example, solid materials may be charged through line 30 and admixed with a gas or liquid introduced through line 1 to the preheater 11. sfiefi gaiias may inelude ayamcs'r sgsac eais 'iiiate'f rial such as coal, ligni te, peat; bilsli'ale', or eves aninert u'raterial such assand. arerm 's'dc as, new, introdiloe'd iiithis inann'ei', may be carb in the duct 3 and Se haration vessel 5 to give gaseoiis iroducts and, a coke o'r char. Depending or the" quantity b f oxyg'en' present in the separation yessfel a certain amount "of gasifi tion to carbon monxide may also occur,

" e1 .-e tlie solid is nori-calrbohac'eous, it forms L for the: coke produced from theliqiiid or gaseous ma t al'tofdebosit on. Iii this instance, it is desirable to lconibustion device other than the slagging type shown in the drawing.

1 is possible to dispense entirely vyithjreheater i1; Closing ofi Valve 3 4 and charging fluid feed through line ai1d solid material through line 31 v r desired, the hydrocarbonaceous material charged to the system may beentirely' solid material l ngtliis' eYeht, yalye 34 is closed and the coal or simila solid y rq a n q fee ma r a i h r e .s 't 3 bmi h. line 1 m ndiot e' v n r a b l ,i dueedjthrough line 33. to move the finely divided solid to the duct 3;

" Aiurtherernbodirnent of the amended shown N Fig. 2. As shown in that figure, a system according the invention may comprise a g asifier 1'00 haying an upper enlarged separating section 121 of r nore o'r less cylindrieal sha 'ie and an elongated, ta' iere'd leg 101. The up- 156% edition 121 is adapted to support and contain afiu'idizedbed of finely divided solids 106; Adjacent the gasifier are a burner, such as a sla'gging-typeeyclone 102 and a cyclone separator 103. A duct 104 leads from the exhaust end 105 of the burner 102k the cyclone separator 103'. Theburner has air inlet 107 and an outlet 108 for liquid'slag. A'trans'fer line 109 for flui diied solids leads frointhe bed 106 in gas'ifier 100 to the duct 104. A line 110 is provided supply fluidiz'ilig' 'gasg su ch as steam, to the line 109 to maintain the solids being transferred through that line in fluidized condition and toaid in conveying the solids.

- Alinell l extends from the bottom of cyclone sepf arator 103 to the bottom of the leg 101 of the g'asifier 100 to enable solids to be transferred from the cyclone to the gas'ifier. Inert fluidizin: gas, e.'g. steam; may be furnished for this transterg through

lines

112 and 113; located on line 111 and aillie b0tt0lfi of leg 101, re spectively. Aline 122 is provided just down tream froni line 112 for theintroduction' of material having a high I I/C ratio; such as recycled product gas. A feed line 114 for hydiocarbonacebus ndaterial is located at the bottom of leg 101 downstream from line 122 Sprays 124, fed throu'gh a line 123 are furnished at the bottoifi o'f'theen1arged section 121 of gasifier 100 for supplying oil to quenchthe'r'naterials being 121 through 1e 101,

A line 115 extends between the cyclone separator 103 ahd the burner 102 for furnishing solidstdthe cyclone burner; The inlet 119 for the line 115 is preferably arranged on the Wall of the cyclone: 10$,s'6n11e distance u fro'in' its yerte'x, so that the solidsjfurhis'h'ed to the burner 102 are preferably larger than those drawn 011 the VertX of the cyclone for delivery tothe ga-sifier '100'.

' A d aw-be um; 116 is provided for ren'io'ving some' iir; the solids moving through line 115 Where it is desired to w I In a preferred method of operating the system illiisirecover coke as a product.

trated in Fig. 2, a bed 106 of earbonaceous' solids, such as coke or char having a particlesize between'iabout 10 microns and about 0.1 inch is established in" the upper section 121 of the gasifier Itis maintained at be t v ven about 600 F. and about 1800 F; preferably betjv yeen about 800 F and about 1700 F., the precise temperaturedepending on the reactantsQthe products 'de sired, and whether the bed is being used tIo quench or to complete the pyrolysis. The pressure is reprieve delivered to the section A certa n One stream, havmg o ime-ice;

.. g i er r A v qly jis le i n r as t e n f fli substan es; t t fix l jsfibf m me sulphur @9 2: tent of the solidpyrolysrs' residue. Such materials may e int dqcs th pu hl d te the bottom of leg 10]. f 4; 1 1? 1 10 2,1: thi ad is usua ly d p ie a fi at h the gas introduced thin air or oxygen. V Hydrocarbonaceous grater-gal, liquid, gas or solid, is

fed'iht'o iii v hot" entrained solids th'rough'lirie'114 m or 101. Thi'simaterialf 5%? as 11's; a hdicok or whlch in Pa t de o the enim? Hel s ts ms ini g throiigh" use 118 may .2 1 shew; t e q i L- The solids" are withdrawn 101 the fluidized bed 106;" In such ar ang m'e'nt, the heat re lafsedidgififig the eirothernii'c pug he ps us maintain the tem erature offi'u'idiz d swat rea 'iQ'n' revs:

Altrnat ely; 56th pblfti ns 6f the pyrolysis can be ear: 4 5 bed" 106 can be used to ced' below, as explained is degrees part of (l1 q 7 my be ao; 'inplislidby' iiians of oil; 7E oily" snfinnd mraugu 12411111 1136123? Spraying oil at this point not only q lmches the products or pyrolysis, but also permits crackingbf 'materials such as gas oil, which may themselvies have been producedby the pyrolysis. The amount of. oil used is preferably limited to not more than that which will bring the temperature of the gases down to th'bracking temperature of the oil being sprayed, e.g. to not less than 800 F. and preferably to 800-1200 R, where the sprayed oil is 'gas' The composition of the hydrocarbon feed charged through line 114 is subject to the same wide variation, which has been described in connection with Fig. 1.

As indicated above, the pyrolysis method and apparatus which have been described may'bensed with great advantage in the refining of petroleum."' Two refining systems employing the novel methodand apparatus are shown schematically in Figs. Band 4.

Referring to Fig. 3, akrefihing' system according to the invention may comprise a pyrolysis unit indicated generally as 200, and a fractionator 201. The pyrolysis unit 200 is of the general type discussed above'in connection with Fig. 2 and comprises 'a gasifier 202 having an enlarged upper section 203 "suitable for supporting a bed of fluidized solids,"and an elongated tapered lower leg 204, a cyclone burner 205, a cyclone separator 206, and a duct 207 connecting the burner 205 and the sepa rator 206 with the bottom of thele'g 204'. A solids drawofl chamber 209 is provided'on' a wall of the upper portion 203 of gasifier'202 anda line 210 connects this draw-'oif'chambe'r with the duct 207." An air inlet line 211 is provided for burner 205. Asolids draw-01f chamber 212 is provided'on a wall of cyclone separator 206 and a line 213 connects this draw-offchamber with the air inlet line 211 to theburner 205." A line 214 is provided for removing gases from separator 206.

' An internal cyclone 215 having a dip leg 216 is mounted in the upper section 203 of gasifier 202 and a line 217 is provided to receive the gases discharged from gasifier 202 through this cyclone 21 5.

Fractionator 201 has an upper section 218 and a lower section 219, separated by an a'ccumulatorpan 220 having a chimney 220a. Each section contains a number of trays 221. Thenumber and design of these trays depends on various factors, such as the composition of the feed, and are readily calculated by those skilled in the art. 0 i i A heat exchanger 222 is set up adjacent the fractionator 201 and a line 223 is provided for furnishing 'fluid from a tray in the bottom section 219 of the fractionator to the heat exchanger. A line 224 is arranged to return at least a portion of this fluid to the fractionator and a line 225, connecting with this line 224, permits a portion of the fluid to be withdrawn after passing through the heat exchanger 222.

A line 226 for crude oil feed passes through heat exchanger 222 and discharges to the upper section 218 of the fractionator. Aline 227 is provided for delivering liquid from the accumulator pan to the bottom of the leg 204 of gasifier 202. A line provided for withdrawing residue from the bottom of the lower sec tion 219 of the fractionator. This line 228 has a branch 229 which joins the line 227, permitting at least a portion of the residue from the bottom of fractionator 201 to be charged to the leg of the carbonizer. Another brarich 230 of line leads back to the lower portion 219 of the fractionator, quenching the gaseous products of gasifier 202 discharging through line 217.

In operation, a fluidized bed or finely divided carbonaceous material, such as the coke produced in the process, is maintained in the upper section 203 of carbonizcr 202. This bed is maintained at a temperature between about 600 and 1800 E, preferably between about 800 and about 1800, F. by withdrawing colge p odu d therein hr u line 19. ep n i om entt nins ases n separa or- 296mg" burni gs Par 9 the separated coke in burner 205, all as described above in connection with Fig. 2.

Crude oil is introduced through line 226. It is preheated in heat exchanger 222 and charged to the upper section 218 of fractionator 201. There, gasolene and lower boiling components are removed overhead through line 231. The residual liquid collects on accumulator pan 220 and is charged through line 227 to the leg 204 of gasifier 202. Here it meets a stream of inert gas, such as steam, introduced through lines 232 and 233, and hot entrained solid coke particles, and is pyrolysed in the leg 204, or in the leg 204 and in the fluidized bed 234 to give coke and a mixture of gas oil, gasolene containing some aromatics, and fixed gases containing a high proportion of ethylene and other olefins. These products are removed through cyclone 215 and line 217 and meet the residuum from fractionator 202 flowing through line 230 which serves to quench the high temperature gases. The combined stream of gases and residue is returned to the lower section 219 of fractionator 201 where further separation is carried out.

A side stream comprising naphthalene oil can be withdrawn from the lower section 219 of the fractionator through line 223 and used to heat the crude in heat exchanger 222. A part of this naphthalene oil can then be withdrawn through line 225 and the balance returned to the fractionator through line 224.

A part of the fuel oil residue from the lower section 219 of fractionator 201 can be charged to the gasifier through branch 229 of line 228. Another part may be withdrawn as product through line 235.

Another system for refining petroleum according to the invention is shown in Fig. 4. Again the system comprises a pyrolysis unit 300 and a fractionator 301. The pyrolysis unit is similar in construction to that shown in Fig. 3. It comprises a gasifier 302 having an enlarged upper section 303 and an elongated lower leg 304, a separator 306 and a burner 305. A duct 307 is provided for delivering hot gases from burner 305 to separator 306, and a line 313a is arranged to deliver solids from separator 306 to burner 305 for use as fuel. Air or oxygen may be fed to burner 305 through line 311a. A line 308 carries hot solids from the separator 306 to the gasifier 302 and a line 310 carries solids from the gasifier to duct 307. A line 337 is provided for supplying a gas having a high H/C ratio, such as recycled product gas, to'the gasifier 302.

The fractionator 301 comprises a number of bubble trays 311 of conventional design. A line 312 connects the top of gasifier 302 to a point near the bottom of fractionator 301. A line 313 is provided for introducing crude oil into line 312. Another line 314 connects the bottom of fractionator 301 with the bottom of gasifier leg 304. A gas oil side stream may be drawn off fractionator 301 through line 315. A part of the gas oil may be sprayed through sprays 335 to quench the hot products of pyrolysis and crack the gas oil. The overhead from the fractionator is removed through line 316.

'In operation, a fluidized bed 334 is established in the upper section 303 of gasifier 302 as described above in connection with Figs. 2 and 3. Crude oil is charged through line 313 and serves to quench the hot gases emanating from the carbonizer. The combined stream is delivered to fractionator 301 where a gaseous stream, comprising fixed gases and gasolene, is removed overhead. Gas oil is removed as a side stream through line 315. A portion of this material is delivered to sprays 335 where it serves to partially quench the hot products of pyrolysis to say 800- 12O0 F. and is itself cracked to gasolene. The bottoms from the fractionator, comprising all components of the crude oil boiling above about 350 F. are sent through line 314 to the bottom of car bonizer leg 304 and into the fluidized bed 334. Recycled product gas may. be added to the charge to bed 334 rou line 3 Using the apparatus of Fig. 1, 750 barrels per hour of a Bunker C fuel oil are introduced into preheater 11 and heated to about 600 F. About 20,000 pounds per hour of coke are burned with air in the burner 4 to give a tem perature at the outlet of the burner of about 3000" F. About 600,000 pounds per hours of coke are introduced at point into conduit 3 to cool the hot gases from the hea'terto a temperature of about 1600 F. The tempera ture in the gasifier 5 is maintained at about 1200 F.

About 85,000 standard cubic feet per minute of volatile products are withdrawn through line 13, having the following approximate analysis Weight percent Oil gas Aromatic liquids 20 Gombustion products 55 200 pounds per hours of coke are withdrawnthrou'gh valve 20. h i Example II JIhe procedure described in Example I is carried out ex cept that oxygeniiistead of air is introduced through line 8. The temperature at the outlet of the burner is about 4000F'. The temperature just upstream from the .Venturi throat 2 is about 1700 F. and the temperature in the g'asifier is about 1150 F. The product removed through line 13 analyzes approximately as follows:

H Weight percent Qlillsa'sj Aromatic liquids Combustion products V 30 5000 pounds of coke per hour are withdrawn through valve 20. i

' I Example 111 The' p'r' ee's'e described in Example I is carried out, but ab 17,000 standard cubic feet per minute of propane ea as the hydrocarbon feed. Approximately 3000 standardcubic feet per minute of fuel gas are introduced to, cyclone burner, with suflicient air for combustion. The te'rj nperatu re atv the outlet of the burner is about 3 200fjF; About 400,000 pounds per hour of coke are removed from the gasifier through line 9 and introduced into the conduit at 10. The temperature just upstream tim t e Venturi throat 2 is about 1s0o F. The temp'ratur e in the bed 6 is about 1400 F. A small amount of coke is interm'ittently removed through line 20. About 05,000 standard cubic feet per minute of gaesous produt are removed through line 13, analyzing approximately as follows Weight percent Oi s Afromatie liquids 5 Combustion products Example V l00barrels per hour of a heavy Bunker C fuel are introducedinto heater 11 in the syst en t of Fig. 1, and heated to about 600 F. 100 tons per hour of drogen.

coal are added through valve 31 and the mixture is duced into the system at point 2; About Buttons per hour of coke are gasified in burner 4 using about 50,000 standard cubic feet per'minut of a mixture of oxygen and steam in about equal proportions, giving a temp ra: hire at the outlet or about 2500 F- About 300,000 pounds per hour of coke are introduced at point 10 i ntd conduit 3 to cool the hot gases from the heater to a te'r'n' perature of about 1600 F. The temperature in the gasifier 5 is maintained at about 700 F. in order to quench the gaeous products, to remove unstable compounds by reaction and to remove heavy pitches by conden'sation onto the coke.

About 100,000 standard cubic feet per minute of volatile products are withdrawn through line 13, having the following approximate analysis:

Weight percent Oil gas 12.5, Aromatic liquids 7.5 Partial combustion products 80.0 100.6

The partial combustion product contains over 30% hy Example V 1000 barrels per hour of a Bunker C fuel oil are introduced into the system of Fig. 2. About 3,510,000 pounds per hour of coke are withdrawnfrom the gasifier and charged to duct 104. 55,100 pounds pet: hour of this coke are charged to burner 102 where they are burned with air to give a' liquid slag and hot combus tion products, and 3,440,000 pounds per hour are re cycled through line 111. 27,000 gallons per hour of gas oil are sprayed through sprays 124 into bed 106. The temperature in the g'asifier' bed is about 1300 F. About 66,000 standard cubic feet per minute of water-free volatile products are withdrawn through line 118, having th following approximate analysis:

Weight percent Oil s t .7 Aromatic distillates 21 Pitch 32 Example VI The conditions of Example V are repeated, except additional fuel oil is burned in burner 102 to supplement the heat obtained from burning product coke, and about 37,000 standard cubic feet per minute of recycled prod uct gas having the following composition:

Percent CH 65 Heavier gases 5 are charged through line 1 22. The resulting volatile products withdrawn through line 118 have the following composition (on a recycle-gas free basis):

Example VII v 100,000 pounds per hour of bituminous coal, having the following approximate analysis:

Weight percent Carbon 76 A h Volatile combustible matter 26 are introduced through line 114 into the system of Fig. 2. Steam used as the fluidizing and conveying medium in line 113. The temperature of the gasifier bed is kept at 1300 F. 76,000 pounds per hour of char are drawn from cyclone 103 and returned via line 111 to the gasifier. The water-free gaseous product removed through line 118 amounts to around 520,000 standard cubic feet per hour and has the following approximate analysis:

Weight percent Coal gas 7 Aromatic liquids 27 Example VIII 1000 bbls. per hour of a 38 API mid-continent crude oil containing about 32% reduced crude after atmospheric distillation, is fed through line 226 into fractionator 201 in the apparatus of Fig. 3. 600 bbls. per hour of topped crude is removed from accumulator pan 220 and charged to pyrolysis unit 200 along with 50 bbls. per hour of the fuel oil bottoms removed from the lower section 219 of fractionator 201. A fluidized bed of petroleum coke at a temperature of about l 100 F. and pressure of about p.s.i.g. is maintained in carbonizer 202. Total products obtained are (wt. percent of the crude):

- Weight percent Gas (ethylene about 24%; propylene and heavier,

18% by volume) 3,6 Gasolene Naphthalene oil 1 Fuel oil (viscosity equivalent to ASTM #6) l6 Coke 7 100 Example IX 1000 bbls. per hour of the same crude used in Example VIII are charged through line 313 in the system of Fig. 4. 400 bbls. per hour of bottoms from the fractionator 301 are fed to gasifier 302. A fluidized bed of coke is maintained in the gasifier at a temperature of about 1100 F. and a pressure of about 25 p.s.i.g. 250 bbls. per hour of gas oil are recycled through line 336 and sprays 335. Total products obtained are (approx. wt. percent of the crude) Weight percent Gas 08-25% ethylene and up to total olefins) 15 Gasolene 45 Gas oil 28 Coke -Q 12 Example X Example IX is repeated except that 14,800 standard cubic feet per minute of recycled product gas having the following composition:

Percent H 30 CH; Heavier gases 5 From a consideration of the foregoing description, it will be seen that the invention provides a simple, direct, versatile and economical method and apparatus for the production of gaseous, liquid, and solid products by pyrolysis of hydrocarbonaceous materials. Only one fluidized bed is required so that the initial cost is lower and maintenance is reduced as compared with prior sys: terns. The necessary heat can be furnished by combustion of the coke produced, and this combustion is carried out under conditions which are flexible and easy to control, and which permit corrosive oxides present in the fuel to be removed from the system. Pyrolysis of the hydrocarbonaceous feed is done under conditions where deposition of coke on heat transfer surfaces is not aproblem.

The process described is inherently flexible in that the time and temperatures of reaction can be readily and independently adjusted by varying the length of the conduit, and the temperatures both in the conduit and in the separation zone. This ability is valuable especially. where it is desired to produce in optimum amounts the most valuable products by feeding stocks of varying character at different points along the conduit, and where it is desired to produce certain relatively unstable cornpounds such as butadiene, which require that the mate rial be very quickly brought up to temperature, cracked for a relatively short time, and then quenched below the temperature at which these compounds will react with other material present, or polymerize.

The novel process is valuable in many industries. In particular, as in the forms illustrated above, it can be used with great economy in petroleum refineries of modcrate size.

What is claimed is:

1. A process for the pyrolysis of hydrocarbonaceous material which comprises charging a feed stream of hydrocarbonaceous material into a hot moving reaction stream of gases and entrained finely divided carbonaceous solids to heat said stream to between about 1100 F. and

about 1800 F. and to at least partially pyrolyse said. feed stream, delivering the combined feed and reaction streams to a fluidized bed of said finely divided solids, removing vaporous products of pyrolysis from said bed, removing carbonaceous solids from said bed, burning a first portion of the solids removed from said bed in a combustion zone apart from a second portion of said solids removed from the bed to give hot gases and an ash"v residue, removing at least a portion of said residue from the process, contacting the second portion of the solids with the hot gases produced in said combustion zone to reheat said second portion, and using the solids so reheated in forming said reaction stream.

2. The method claimed in claim 1 and in which the overall pyrolysis reaction has an endothermic part and an exothermic part, and comprising conducting the endothermic part of the pyrolysis reaction in the reaction stream and the exothermic part in the fluidized bed.

3. The method claimed in claim 1 and comprising adding to the reaction stream a material selected from the group consisting of hydrogen and hydrocarbonaceous materials having a higher H/ C ratio than the hydrocarbona-. ceous feed.

4. The method claimed in claim 1 and comprising contacting the reaction stream with a quenching medium immediately prior to delivery to the fluidized bed. i

5. The method claimed in claim 4 wherein the quenching medium is a hydrocarbonaceous material and is itself at least partially cracked during the quenching process.

6. The method claimed in claim 1 wherein the reaction stream is moved upwardly into the fluidized bed.

7. The process claimed in claim 1 in which the solids are burned under conditions such that a liquid slag is solids and thereby heating said feed stream to between about 1100 F. and about 1800 F., and at least partially pyrolysing said feed stream, delivering the combined feed and reaction streams to a fluidized bed of finely divided solids, removing vaporous products of pyrolysis from said bed, removing a first stream of solids from said bed, burning said first stream of solids in a combustion zone to form a high temperature stream of gaseous products of combustion and an ash residue, removing at least a portion of said residue from the process, removing a second stream of solids from said bed and entraining solids from said second stream in said high temperature stream of gaseous products of combustion to form said reaction stream.

9. A process for the pyrolysis of hydrocarbonaceous material which comprises charging a hydrocarbonaceous feed material into a first moving reaction stream of gases and entrained, hot, finely divided carbonaceous solids and thereby heating said feed to between about 1100 F. and about 1800 F. and causing at least partial pyrolysis of said hydrocarbonaceous material, delivering the combined feed and reaction stream to a fluidized bed of finely divided solids, removing vaporous products of pyrolysis from said bed, removing a stream of solids from said bed and entraining said solids in a second moving stream of hot gases, to heat said solids, delivering said second moving stream of hot gases with the heated solids entrained therein to a separating zone, removing hot solids from said separating zone and burning said solids in a combustion zone to produce said second moving stream of hot gases and an ash residue, removing at least a portion of said residue from the process, removing additional hot solids from said separating zone and entraining said additional solids in a stream of gases to form said reaction stream.

10. The method claimed in claim 9 in which the finely divided solids are solid products of pyrolysis.

11. The method claimed in claim 9 wherein the solids are burned under conditions such that a liquid slag is formed.

12. A process for the distillation of petroleum which comprises feeding crude petroleum into a first moving stream of hot hydrocarbonaceous gases, fractionating the combined stream of crude petroleum and hot gases to give a product boiling above about 350 F., charging said product to a hot moving stream of gases and entrained finely divided carbonaceous solids to heat said product to between about 1100 F. and about 1800 F. and thereby at least partially pyrolyse said product, delivering the combined stream resulting from the step last referred to, to a fluidized bed of said finely divided solids, removing vaporized products of pyrolysis from said bed, to form said first moving stream of hot gases, removing solids from said bed, burning a first portion of the solids removed from said bed in a combustion zone apart from a second portion of said solids removed from said bed to give hot gases and an ash residue, removing at least a portion of said residue from the process, contacting the second portion of the solids with the hot gases produced in the combustion zone to reheat the second portion and using the solids so reheated to form the hot moving stream of gases and entrained solids referred to.

13. A process for the refining of petroleum which comprises topping crude petroleum to remove a fraction comprising gasoline and lower boiling materials, heating said topped crude to between about 1100 F. and about 1800 F. to at least partially pyrolyse said topped crude, by charging said topped crude to a .hot moving reaction stream of gases and entrained carbonaceous solid particles, delivering the resulting combined stream to a fluidized bed of said finely divided solid carbonaceous particles, removing vaporous products of pyrolysis from said bed, removing solids from said bed, burning a first portion of the solids removed from said bed apart from a second portion of the solids removed from said bed to generate hot gases and to produce an ash residue, removing at least a part of said ash residue from the process, contacting the hot gases so generated with said portion of the solids removed from said bed and thereby reheating said second portion of solids, and using the solids so reheated to form the first mentioned reaction stream.

14. The method claimed in claim 13 in which the solids are carbonaceous and are burned under conditions such that a liquid slag is formed.

15. The process claimed in claim 13 wherein the crude petroleum is topped by co-fractionation with the vaporized products of pyrolysis.

16. Apparatus for the pyrolysis of hydrocarbonaceous material comprising, in combination, a conduit having an inlet and an outlet, a slagging type combustion device having a hot gas outlet connected to the inlet of said conduit, a vessel adapted to support a fluidized bed of finely divided solids connected to the outlet of said conduit, means for conveying solids from said bed to said combustion device means for conveying finely divided solids from said vessel and introducing them into said conduit at a point along its length and means for introducing a hydrocarbonaceous feed into said conduit at a point nearer to the outlet of said conduit than the point of introduction of said finely divided solids.

17. Apparatus for the pyrolysis of hydrocarbonaceous materials comprising, in combination, a first separatory vessel, a second vessel adapted to support a fluidized bed of finely divided solids, first conduit means for transferring solids from said first to said second vessel, means for introducing a hydrocarbonaceous feed into said first conduit means, a slagging type combustion device having a hot gas outlet, second conduit means joining said hot gas outlet with said first separatory vessel, means for introducing solids from said second vessel directly into said second conduit means and means for conveying solids from said first separatory vessel to said combustion device for burning therein.

References Cited in the file of this patent UNlTED STATES PATENTS 1,646,760 Miller Oct. 25, 1927 2,357,301 Bailey et al Sept. 5, 1944 2,485,315 Rex et al. Oct. 18, 1949 2,557,680 Odell June 19, 1951 2,700,017 Brown Jan. 18, 1955 2,700,642 Mattox Jan. 25, 1955 2,710,827 Gornowski a- June 14, 1955 2,719,114 Lefler Sept. 27, 1955 2,734,020 Brown Feb. 7, 1956 2,737,479 Nicholson Mar. 6, 1956 UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 2,88-,,368 April 28, 1959 Maxwell Patrick Sweeney It is hereby certified that error appears in the printed specification of the above numbered patent requiring correction and that the said Letters Patent should read as corrected below.

Column 10, line 1, for "2B0 p.,s.i.g, reed w 2000 p s,i.g., line '75, for "sparys" reed sprays column 11, line 18, for "Referring to Fig. 3" read m Referring first to Fig. 3 column 13, line '72, for

"Example V" read Example IV e Signed and sealed this 6th of October 1959.

Attest:

KARL H. AXLINE ROBERT C. WATSON Commissioner of Patents Attesting Oificer

Claims

1. A PROCESS FOR THE PYROLSIS OF HYDROCARBONACEOUS MATERIAL WHICH COMPRISES CHARGING A FEED STREAM OF HYDROCARBONACEOUS MATERIAL INTO A HOT MOVING REACTION STREAM OF GASES AND ENTRAINED FINELY DIVIDED CARBONACEOUS SOLIDS TO HEAT SAID STREAM TO BETWEEN ABOUT 1100*F. AND ABOUT 1800*F. AND TO AT LEAST PARTIALLY PYROLYSE SAID FEED STREAM, DELIVERING THE COMBINED FEED AND REACTION STREAMS TO A FLUIDIZED BED OF SAID FINELY DIVIDED SOLIDS, REMOVING VAPOROUS PRODUCTS OF PYROLYSIS FROM SAID BED, REMOVING CARBONACEOUS SOLIDS FROM SAID BED, BURNING A FIRST PORTION OF THE SOLIDS REMOVED FROM SAID BED IN A COMBUSTION ZONE APART FROM A SECOND PORTION OF SAID SOLIDS REMOVED FROM THE BED TO GIVE HOT GASES AND AN ASH RESIDUE, REMOVING AT LEAST A PORTION OF SAID RESIDUE FROM THE PROCESS, CONTACTING THE SECOND PORTION OF THE SOLIDS WITH THE HOT GASES PRODUCED IN SAID COMBUSTION ZONE TO REHEAT SAID SECOND PORTION, AND USING THE SOLIDS SO REHEATED IN FORMING SAID REACTION STREAM.