US2197009A - Conversion of higher boiling hydrocarbons - Google Patents

Conversion of higher boiling hydrocarbons Download PDF

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US2197009A
US2197009A US125687A US12568737A US2197009A US 2197009 A US2197009 A US 2197009A US 125687 A US125687 A US 125687A US 12568737 A US12568737 A US 12568737A US 2197009 A US2197009 A US 2197009A
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hydrocarbons
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pyrolytic
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Jr Arthur E Pew
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Houdry Process Corp
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G9/00—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G9/14—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils in pipes or coils with or without auxiliary means, e.g. digesters, soaking drums, expansion means

Definitions

  • the present invention relates to the treatment Aof composite hydrocarbon materials, such as those occurring in or derived from petroleum, coal, shale or other source, natural or artificial, to produce therefrom valuable hydrocarbons suitable for useas fuel in internal combustion engines, including lower boiling hydrocarbons of the type of benzines, naphthas, gasolines, kerosenes andthe like. More particularly, it is conm cerned with the production of such lower boiling hydrocarbons from higher boiling hydrocarbons containing both clean, easily vaporizable material or distillate stock and diiiicultly vaporizable material of the type of heavy distillation residues.
  • a number of pyrolytic or thermal processes for converting higher boiling hydrocarbons into lower boiling hydrocarbons are well known to the art and various systems differing from one another only in minor respects are in common use.
  • a 20 more recent development involves the catalytic transformation of hydrocarbons by a continuous process utilizing twoor more converters containing absorbent catalytic materlal which is periodically regenerated or reactivated, preferably in situ, so that each converter may be alternately on stream and in regeneration, as indicated, for example, in the copending application of Eugene J. Houdry, Serial No. 610,567, filed May 11, 1932, and issued as Patent No. 2,078,247 on April 27, 1937.
  • 'I'he pyrolytic systems produce usually, from fresh feed, a lower yield of high anti-knock motor fuel than does the catalytic system but appear to handle partially converted or transformed material with reasonable facility. Because of this facility, many pyrolytic systems involve internal recycling of distillate stocks having clean distillate or gas oil characteristics, obtained, usually, from fractionation of the con,- verted material or synthetic crude leaving the re ⁇ action zone. 'I'he pyrolytic systems perform at greater efficiency on distillates of the gas oil type than on residual materials of the general type of those remaining from the distillation of crude petroleum.
  • the pyrolytic systems can produce motor fuels of good anti-knock rating only under severe operating conditions and at the cost of relatively low yields of desired product with attendant high yields ofgas and unconverted residua.
  • the motor fuel so produced sometimes contains relatively large amounts of sulphurous compounds, because of the tendency of sulphurhydrocarbon'compounds to concentrate in residual stocks, and is therefore often quite difficult to rene.
  • the high production of coke reduces (Cl. ISG-49) the time eiliciency of the system by requiring frequent shut-downs for removing the accumulated coky deposits.
  • 'Ihe catalytic system is best adapted to operations where successive residues from transformed material produced in separate, distinct and successive catalyst cracking operations or passes are segregated to provide charging stocks for the separate and successive passes, usually effected at progressively Aincreasing severity of reaction conditions.
  • this system makes its best product in the first pass or when transforming virgin or fresh feed. In the rst pass, it produces high yields of high anti-knock motor fuels from residual stocks, as well as from distillates.
  • the motor fuel is easily refined, regardless of the source and characteristics of the charge, and, in addition, the residue remaining after separation of the motor fuel from the transformed products or synthetic crude made in the catalytic system is clean, has charactertstics and uses of a gas oil or distillate fuel oil and is suitable for use as a' charging stock to a pyrolytic system,
  • One object of the present invention is to provide a unitary system containing catalytic'and pyrolytic reaction zones disposed and arranged so that the advantages of each type of zone are secured and the disadvantages of each minimized or even avoided. Another object is to provide for exibility of operation. Another object is to realize economies of heat and of equipment. Other objects will be apparent from the detailed discussion which follows.
  • the invention involves a pyrolytic or thermal reaction zone A, shown enclosed by a light full line, and a catalytic reaction zone, enclosed by a broken line, and indicated generally by reference character B, and a single fractionating zone containing fractionator I.
  • the latter is connected to a source of fresh feed and to both reaction zones A and B and functions coincidently and cooperatively with both reactions so as:
  • the selected charges comprising (a) One or more streams of clean higher boiling hydrocarbon distillates which are fed to ref action zone A and (b) A still higher boiling fraction containing substantiallyall the diflicultly vaporizable or residual hydrocarbons present in the fresh charge, which fraction is admitted to reaction zone B;
  • the selected or segregated distillate or distillates charged to zone A may contain partially converted distillates of restricted and controlled boiling range as well as fresh or virgin stock, and
  • the higher boiling material separated from the reaction products may be charged to reaction zone A along with or as an adjunct to the feed to that zone, or, the unitary system may be operated to provide, in addition to the desired end point motor fuel, higher boiling materials of controlled amount and character and having the uses and properties of domestic and Diesel distillatefuels.
  • fresh charge which may be, for example, a whole crude petroleum oil or a derivative thereof, such as a topped crude, or any blend or composite mixture of hydrocarbons containing both easily vaporizable and diillcultly vaporizable materials which may be made or may occur in refinery practice, is continuously admitted to the unitary system by line 2 and conducted through the latter to heater 3 wherein it is heated to distillation temperature and is then sent through line l to fractionating column I. Any desired portion of the charge may be preheated in heat exchanger 5, located in line 2 and provided with a valved by-pass therearound.
  • fractlonator I From fractlonator I there is withdrawn one or more higher boiling side stream distillate fractions, as for example, a heavy naphtha by line 6, a relatively light gas oil by line 1 and a relatively heavy gas oil by line 8, the heavy unvaporized residuum is withdrawn from fractlonator through line 9.
  • the distillate fraction or fractions are conducted into reaction zone A by suitable branch connections, such as those shown, while the distillation residue withdrawn from fractionator I by line 9 is fed to reaction zone B, in which zones the desired conversion takes place.
  • reaction zone A may also be regulated so as to avoid recycling through reaction zone A of partially converted material boiling within the boiling range of the heavier portions of the charge to that zone.
  • the reaction products issuing from the reaction systems may have removed from them components boiling within the boiling range of a portion or even all of the gas oil issuing from fractlonator I by lines 1 and/or 8 for the purpose of improving the conversion in reaction zone A and/or to provide stock for fuels capable of meeting a wide range of volatility specifications.
  • All lower boiling hydrocarbons of the desired end boiling point made in the unitary system as hereinafter described and any of such hydrocarbons introduced thereinto with the fresh charge are withdrawn from fractlonator I as a single stream or blend by overhead vapor line 23.
  • This blend may be subjected to any desired treatment either before or after condensation.
  • the vapor in line 23 may be condensed in condenser 24 and have fixed or incondensable gases removed therefrom in separator 25 provided with gas outlet 26, hydrocarbon condensate withdrawal line 21 and a connection 28 for removing condensed steam. Any desired amount of condensate may be returned to fractlonator I by line 29 to be used as reflux, while the remainder may be withdrawn from the system by line 30.
  • Pyrolytic reaction zone A may contain one or any desired number of systems of any known or desired type for effecting pyrolytic or thermal conversion of higher boiling hydrocarbons in the vapor phase, liquid phase or mixed phase, as for example, utilizing equipment and operating conditions used in the pyrolytic conversion systems commonly known as Cross, Dubbs, tube and tank, De Florez, true vapor phase, gyro, Holmes-Manley, etc.
  • Three such pyrolytic systems are indicated in the accompanying drawing, each comprising a cracking furnace 32a connected by valved transfer line 33a to flash chamber or tower 34a which is provided with a valved residue or tar Withdrawal line 35a and a valved vapor outlet 36a.
  • Each of the pyrolytic systems is selectively connected to each of the lines 6, I and 8 by suitable manifolds and valved branched lines, shown, and to products vapor line I0 by valved vapor outlet 36a.
  • the charge to pyrolytic zone A may be a single stream of distillate, in the interest of high yield of good quality product it is preferable to separately convert a plurality of streams of distillates having restricted or relatively narrow boiling ranges under separate and distinct operating conditions. It is particularly advantageous to separately convert naphtha fractions and gas oil cuts for naphthas generally require more severe reaction conditions (high temperature and/or pressure) than do the higher boiling gas oil cuts.
  • partially converted distiliates in line 20 may be mixed with one or more of the gas oil cuts issuing from fractlonator I, it is preferable to separately convert the partially converted distillate.
  • the hydrocarbons charged to any oi the conversion units or systems in zone A may be subjected to the action of temperatures within the range of 750 to 1200 F. and pressures of from substantially atmospheric or slightly below to 3000 iba/sq. in. gauge. or more, the
  • Pyrolytic systems usually provide suitable apparatus for effecting separation of heavy unconvertible residues from the remaining and clean distillate portions of the reaction products made in the system.
  • Such equipment often takes the i'orm of flash vaporizers which may effect reduction of such residues to coke or which may permit withdrawal of the residues as liquid having con-1 trolled characteristics, which liquid may be used as a residual fuel or for the starting material for road oils or asphalts.
  • Flash chambers 34a in reaction zone A are used for this purpose. Each may be operated so that a heavy viscous tarry residue is removed therefrom by valved line 35a, or, in order to meet refinery demands for more fluid residual oils, condensation of the heaviest portions of the vaporous reaction products in transfer line 33a may be effected withthe aid,
  • a suitable coolingv iiuid which may, for example, be admitted to lines 33a by valved inlets 33e.
  • the resulting condensate is withdrawn as part of the residue.
  • the remaining vapors often have an end boiling point within the boiling range of the charge to zone A and can be conducted directly to vapor line I4 by means of manifold 31, shown selectively connected to vapor lines 30a.
  • each pyrolytic system is selectively connected to fractionator ⁇ I and separator I3 by manifolds I0 and 31 respectively.
  • the distillates leaving zone A sometimes have boiling ranges which also permits by-passing of separator I 3 by manifold 37.
  • catalytic zone B conforms in general to that disclosed in the aforesaid Patent No. 2,078,247, issued to Eugene J. Houdry on April 27,V 1937, and that disclosed in United States Patent No. 2,031,600 issued to J. W. Harrison et al.
  • Converters' 42h may be of any suitable type which provide reaction chambers containing a regenerative adsorptive or catalytic contact mass of any desired type capable of promoting the desired transformation.
  • the mass is of a slicious nature and is in comminuted or molded form, comprising, for example, molded pieces composed essentially of a blend of silica and another metal oxide, such as alumina.
  • the blend may be of natural or artificial origin, including colloidal and precipitated gels and activated hydrosilicates of alumina of a clayey nature. 'Good results are ob tained with a catalyst having a weight ratio4 of silica to alumina in the mass of 395:1, or more, and other characteristics as disclosed in the copending application of Eugene J. Houdry, Se-
  • the contact mass may contain one or more suitable ingredients, such as metals or metallic oxides, for aiding the transforming reactions and/or the regeneration of the mass by combustion of contaminants deposited thereon during the transformation period, as set forth, for example, in the copending application of Eugene J. Houdry, Serial No, 35,101, led August 7, 1985, which issued as Patent-No. 2,078,951 on May 4, 1937.
  • suitable ingredients such as metals or metallic oxides
  • Converters 42a are preferably conducted and arranged for use alternately on-stream and in regeneration in situ of said catalyst in a manner to permit feeding of a continuous stream of réellectant material to the battery of converters, fresh regenerating medium, such as air or other oxygen bearing material being admitted to the converter orv converters undergoing regeneration by line 3Ib and valved branch or branches 45h, while spent regenerating medium is vented from valved branch or branches 46h and line 4'Ib, respectively.
  • fresh regenerating medium such as air or other oxygen bearing material
  • a suitable heater such as tubular heater 38h wherein it is raised to reaction ternperature and a substantial portion of it vapor-- ized.
  • a suitable inert diluent fluid such as steam, is admitted to heater 38h, as by line 48h, in amounts which usually lie within the range of 5 to 25% by weight of the heated charge.
  • the heatedstream after rejection therefrom of unvaporized material in separator 39h, at substantially atmospheric or low superatmospheric pressure, preferably, not in excess of lbs/sq. in. gauge, is passed through the contact mass in converters 42b for an operating or run periodv during which the contact mass is maintained at a temperature within the range of 750 to 925 F.
  • reaction products made in either or both of the reaction zones have removed from them any and substantially all material which is within the boiling range of thecharge to zone B.
  • One method of effecting such removal is by controlled partial condensation while utilizing a heat exchange medium.
  • vaporous reaction products leaving zone A preferably freed of any tar made in that zone, may be conducted by line I0 to line II, containing vaporous reaction products made in zone B, and passed, with the latter, through heat exchanger 5 into line I2, in heat exchange relation with controlled amounts of cold fresh charge to effect the desired partial condensation.
  • 'I'he resulting mixture of liquid and vapors is conducted through line I2 to separator I3.
  • the vapors, containing the desired lower boiling hydrocarbons produced in both reaction zones leave separator I3 by vapor line I4 vand are conducted to fractionator I to be fractionated with the charge. These vapors may be led by line I4 to line 4 wherein they mix with the heated fresh charge and together with it be admitted to fractionator I and/or, all or any desired portion of the vapors in line I4 may be condensed and the III) condensate admitted to fractionator I, preferably at a point above the point of admission of the charge thereto, to serve as a temperature controlling medium after the manner of a refluxing agent to assist in maintaining balanced and controlled operation of fractionator I.
  • the condensatefproduced in heat exchanger 5 is withdrawn from separator I3 by line I5.
  • This condensate is clean and possesses other characteristics which render it suitable for use as a distillate, domestic or Diesel fuel oil or as a distillate or gas oil cracking stock. If desired, it may have entrained lower boiling hydrocarbons removed therefrom in steam stripper I6 provided with steam inlet line I1 and vapor outlet line I8 which discharges into vapor line I4.
  • the stripped condensate leaving the stripper I G by line I9 may be conducted by valved line 20 to reaction zone A to be further converted therein along with or as an adjunct to the one or more distillate streams entering that zone, or all or any desired portion of it may be withdrawn from the system by valved line 2
  • valved line 22 interconnecting lines I5" and I9. It is usually desirable to add additional amounts of inert diluent fluid to the vapors leaving separator 39h. to insure maintenance of vapor phase condition in lines 43h, b and in converters 2b. Such adition may be up to 10% by weight of steam, as by line 49h.
  • a whole petroleum crude as for example, an East Texas crude may be continuously charged to fractionator I and divided therein into straight run gasoline, a heavy naphtha cut having a boiling range of the order of 400 to 500 F. issuing therefrom by line 6, one or more gas oil ⁇ cuts issuing therefrom by lines 1 and/or 8 and having an end point of about 650 to r100 F., and a residue, leaving the co1- umn by line 9, containing substantially all portions of the crude boiling above the end boiling point of the gas oil.
  • the heavy naphtha may be subjected to the action of a temperature of the order of 900 to 930 F.
  • the residue in line 9 may be admitted to heater 38h and heated to about 890 F., about 15% by weight of superheated steam being addedto the residue during the passage through the heater, as by line 48h.
  • the heated residue may then traverse separator 39h and be separated therein into a vapor fraction and a heavy tar having an A. P. I. gravity of the order of The vapor fraction under a pressure of the order of 15 lbs./sq. in.
  • gauge may then be admitted to one of the converters 42h and passed through a catalyst contained therein and comprising molded pieces of activated hydrosilicate of alumina in which the silica to alumina weight ratio is of the order of 3/2:1, having incorporated therewith about 1% by weight of an oxide of manganese as a regeneration promoter and maintained at a temperature Stripper I6 of the order of 860 F. 'I'he rate of feed of the vapors to the contact mass may be oi' the order of 3:4 (3 volumes of condensed vapors per hour to 4 volumes of contact mass).
  • the catalytic synthetic crude is conducted from reaction zone B by line Il, and, along with the vapors in line I0, is subjected to controlled partial condensation by passing the combined vapors in heat exchange relation with fresh charge in heat exchanger 5 so as to produce a liquid fraction containing substantially all portions of the synthetic crude from both reaction zones which boil above the end boiling point of the gas oil cut. 'I'he resulting mixture of liquid and vapor may then be passed through line I2 to separator I3, from which the vapors containing all lower boiling hydrocarbons present in both synthetic crudes may be conducted by line I4 to line 4 and thence into fractionator I, along with heated fresh charge, to be fractionated with the latter.
  • the high boiling condensate in line I5 may be freed of entrained and lower boiling hydrocarbons, as in steam stripper I6, and withdrawn from the system, or, if substantially complete consumption of fresh charge is desired, such condensate may be conducted through line to the lower unit in pyrolytic zone A to be therein subjected to the action of a temperature of the order of 880 F. and a pressure of the order of 1750#/sq. in. gauge for about three minutes.
  • 'I'he synthetic crude produced from such condensate after being freed of heavy residue in vessel 34a may be discharged into line I0 along with the other pyrolytic synthetic crudes.
  • two of the streams of distillate being fed to zone A may be combined and converted together in a single system, thus leaving the one system free for the necessary shutdown without interrupting the operation of the unitary system. For example: if one of two pyrolytic units operating on gas oil cuts requires cleaning, the charge to these two units may be temporarily combined and fed to the unit not requiring cleaning, while making any desired adjustment of the reaction conditions of the unit left in service; When it becomes necessary to clean a unit acting on the naphtha cut the charges to two other two units operating on heavier distillates may be combined as above described and the naphtha stream shifted to the unit thus left off Stream.
  • pyrolytic and catalytic zones A and B operate interdependently and simultaneously, with maximum utilization of fresh feed, to produce, from the latter, in desired proportions, high quality valuable hydrocarbons of the motor fuel or gasoline type, along with valuable higher boiling fuels of distillate and/or residual types.
  • pyrolytic Zone A handles only materials which it is capable of acting upon to best advantage, i. e., clean and easily vaporizable stocks.
  • catalytic zone B transforms only virgin or unconverted material.
  • pyrolytic and catalytic reaction zones for producing high quality lower boiling hydrocarbons from higher boiling hydrocarbons have been combined in a manner that permits each system to operate at high efflciency and to best advantage.
  • the unitary system which permits substantial economies of heat and of equipment. also provides for flexibility of operation that allows for yields of lower and higher boiling fuels in proportions suitable for meeting current and local refinery and market conditions of supply and demand. 'I'his flexibility is realized with maximum utilization of fresh feed to the system.
  • the unitary system provides for production of lower boiling hydrocarbons of high quality, including the ease with which they can be refined, regardless of the characteristics of the original charge.
  • Vaporizer 38h and separator 39h may be replaced by a contact vaporizer, such for example, as that disclosed in U. S. Patent No. 1,989,927, issued to Eugene J. Houdry on February 5, 1935, or as disclosed in the copending Houdry application, Serial No. 32,170, led July 19, 1935.
  • the process comprising feeding to a fractionating zone a charging stock comprising easily vaporizable and diilcultly vaporizable higher boiling hydrocarbons, removing from said zone a distillate cut and a residual fraction, said residual fraction containing diflicultly vaporizable higher boiling hydrocarbons, subjecting said distillate cut to conditions of'pyrolytic conversion to produce therefrom desired lower boiling hydrocarbons of the motor fuel type, subjecting said residual fraction to catalytic cracking conditions including the use of a solid adsorptive contact mass ',capable of promoting cracking reactions to produce from said fraction desired lower boiling hydrocarbons of the motor fuel type.' separating from products of the pyrolytic 'and catalytic reactions hydro--l carbons boiling within the boiling range of said residual fraction, feeding reaction products remaining after said separation to said fractionating zonevto be fractionated Itherein along with said charging stock, removing a motor fuel fraction of controlled end point from said fractionating zone,
  • a heater for fresh charge a fractionating column connected to said heater and adapted to eiect separation of lower boiling hydrocarbons from higher boiling hydrocarbons and to divide the latter into at least one distillate fraction and a residual fraction', a catalytic transformation system connected to said column so'as to re,
  • said catalytic system comprising heating means for producing hydrocarbon vapors from said residue, a plurality of converters selectively connected to said heating means and containing a bed of regenerative, adsorbent silicious contact mass, said converters being adapted and arranged for use alternately in the transformation of hydrocarbons and in regeneration of said mass in place, a pyrolytic conversion system adapted to receive said distillate fraction from the aforesaid column and providing heating and converting means therefor, means for conducting reaction products from each of said systems to said fractionating column, and means associated with said last named means for separating and removing the highest boiling components of said reactionA products from the latter.
  • a heater for fresh charge a fractionating column connected to said heater and adapted to eiect separation of lower boiling hydrocarbons from higher boiling hydrocarbons and to divide the latter into at least one distillate fraction and a residual fraction
  • a catalytic transformation system connected to said column so as to receive said residual fraction
  • said catalytic system comprising heating means for producing hydrocarbon vapors from said residue, a plurality of converters selectively connected to said heating means and containing a body of regenerative, adsorbent contact mass in the form of small pieces of regular sizes and shapes, said converters being adapted and arranged for use alternately in the transformation of hydrocarbons and in regeneration of said mass in place, a pyrolytic conversion system adapted to receive said distillate fraction and providing heating and converting means therefor, means associated with said pyrolytic system for separating and removing from the
  • a heater for heating fresh charge to distillation temperature a fractionating column' provided with an inlet connection, an overhead vapor outlet connection for lower boiling hydrocarbons, at least two side stream distillate connections for higher boiling hydrocarbon fractions of relatively higher and relatively lower boiling ranges and an outlet for distillation residue, a connection from said heater to said inlet connection, at least two pyrolytic conversion systems, a connection between said side stream connection for relatively lower boiling range distillate and one of said systems, a connection between the other of said side stream connections and another pyrolytic system, a catalytic transformation system comprising a heater for effecting vaporization of a substantial portion of said distillation residue, a separator connected to said last named heater for removing unvaporized material from vapors leaving said heater and providing an overhead vapor connection, and a plurality of converters selectively connected to said separator through said last named vapor
  • a' heater for fresh charge a fractionating column connected to said heater and adapted to eiect separation of lower boiling hydrocarbons from higher boiling hydrocarbons and to divide the latter into a plurality of distillate fractions and a residual fraction
  • a catalytic transformation system connected to said column so as to receive said residual fraction
  • said catalytic systemV comprising heating means for producing hydrocarbon vapors from said residue, a plurality of converters selectively connected to said heating means and containing regenerative, adsorbent silicious contact mass, said converters being adapted and arranged for use alternately in the transformation of hydrocarbons and in regeneration of said mass in place, a plurality of pyrolytic conversion systems, each one of said pyrolytic systems being connected to said fractionating column so as selectively to receive any one or any desired combination of said distillate fractions, means

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Description

April 16, 1940. A. E. PEW, JR
coNvERsIoN OF'HIGHER BOILING HYpRocARBoNs Filed Feb. l5. 1957 Patented lApr. 16, 1940 UNITED STATES CONVERSION F HIGHER BOILING HYDROCARBONS Arthur E. Pew,
Jr., Bryn Mawr, Pa., assignor, by
mesne assignments, to Houdry Process Corporation, Wilmington, Del., a corporation of Dela- Application February 15, 1937, Serial No. 125,687
11 Claims.
The present invention relates to the treatment Aof composite hydrocarbon materials, such as those occurring in or derived from petroleum, coal, shale or other source, natural or artificial, to produce therefrom valuable hydrocarbons suitable for useas fuel in internal combustion engines, including lower boiling hydrocarbons of the type of benzines, naphthas, gasolines, kerosenes andthe like. More particularly, it is conm cerned with the production of such lower boiling hydrocarbons from higher boiling hydrocarbons containing both clean, easily vaporizable material or distillate stock and diiiicultly vaporizable material of the type of heavy distillation residues.
A number of pyrolytic or thermal processes for converting higher boiling hydrocarbons into lower boiling hydrocarbons are well known to the art and various systems differing from one another only in minor respects are in common use. A 20 more recent development involves the catalytic transformation of hydrocarbons by a continuous process utilizing twoor more converters containing absorbent catalytic materlal which is periodically regenerated or reactivated, preferably in situ, so that each converter may be alternately on stream and in regeneration, as indicated, for example, in the copending application of Eugene J. Houdry, Serial No. 610,567, filed May 11, 1932, and issued as Patent No. 2,078,247 on April 27, 1937. 'I'he pyrolytic systems produce usually, from fresh feed, a lower yield of high anti-knock motor fuel than does the catalytic system but appear to handle partially converted or transformed material with reasonable facility. Because of this facility, many pyrolytic systems involve internal recycling of distillate stocks having clean distillate or gas oil characteristics, obtained, usually, from fractionation of the con,- verted material or synthetic crude leaving the re` action zone. 'I'he pyrolytic systems perform at greater efficiency on distillates of the gas oil type than on residual materials of the general type of those remaining from the distillation of crude petroleum. When working on such residues it is often true that the pyrolytic systems can produce motor fuels of good anti-knock rating only under severe operating conditions and at the cost of relatively low yields of desired product with attendant high yields ofgas and unconverted residua. The motor fuel so produced sometimes contains relatively large amounts of sulphurous compounds, because of the tendency of sulphurhydrocarbon'compounds to concentrate in residual stocks, and is therefore often quite difficult to rene. The high production of coke reduces (Cl. ISG-49) the time eiliciency of the system by requiring frequent shut-downs for removing the accumulated coky deposits. 'Ihe catalytic system, on the other hand, is best adapted to operations where successive residues from transformed material produced in separate, distinct and successive catalyst cracking operations or passes are segregated to provide charging stocks for the separate and successive passes, usually effected at progressively Aincreasing severity of reaction conditions. In general, this system makes its best product in the first pass or when transforming virgin or fresh feed. In the rst pass, it produces high yields of high anti-knock motor fuels from residual stocks, as well as from distillates. The motor fuel is easily refined, regardless of the source and characteristics of the charge, and, in addition, the residue remaining after separation of the motor fuel from the transformed products or synthetic crude made in the catalytic system is clean, has charactertstics and uses of a gas oil or distillate fuel oil and is suitable for use as a' charging stock to a pyrolytic system,
One object of the present invention is to provide a unitary system containing catalytic'and pyrolytic reaction zones disposed and arranged so that the advantages of each type of zone are secured and the disadvantages of each minimized or even avoided. Another object is to provide for exibility of operation. Another object is to realize economies of heat and of equipment. Other objects will be apparent from the detailed discussion which follows.
A concrete embodiment of the invention is set forth diagrammatically in the accompanying drawing or flow chart.
The invention involves a pyrolytic or thermal reaction zone A, shown enclosed by a light full line, and a catalytic reaction zone, enclosed by a broken line, and indicated generally by reference character B, and a single fractionating zone containing fractionator I. The latter is connected to a source of fresh feed and to both reaction zones A and B and functions coincidently and cooperatively with both reactions so as:
(1) To provide selected or segregated charging stock for each of said zones, the selected charges comprising (a) One or more streams of clean higher boiling hydrocarbon distillates which are fed to ref action zone A and (b) A still higher boiling fraction containing substantiallyall the diflicultly vaporizable or residual hydrocarbons present in the fresh charge, which fraction is admitted to reaction zone B;
(2) 'Io receive and fractionate the reaction products or synthetic crudes from both reaction zones, after such products have had removed from them substantially all material higher boiling then the charge to zone A or within the boiling range of the charge to zone B, and. optionally, a portion of the material within the boiling range of the charge to zone A, so that,
(a) The selected or segregated distillate or distillates charged to zone A may contain partially converted distillates of restricted and controlled boiling range as well as fresh or virgin stock, and
(b) The charge to reaction zone B is substantially free of partially converted material; and
(3) To provide a stream of desired end point lower boiling hydrocarbons which comprises a blend of substantially all of such material which is present in (a) The fresh charge and (b) In the products from both reaction zones A and B.
When it is desired to effect complete or substantially complete consumption of fresh feed, the higher boiling material separated from the reaction products may be charged to reaction zone A along with or as an adjunct to the feed to that zone, or, the unitary system may be operated to provide, in addition to the desired end point motor fuel, higher boiling materials of controlled amount and character and having the uses and properties of domestic and Diesel distillatefuels.
Referring more particularly to the drawing, fresh charge, which may be, for example, a whole crude petroleum oil or a derivative thereof, such as a topped crude, or any blend or composite mixture of hydrocarbons containing both easily vaporizable and diillcultly vaporizable materials which may be made or may occur in refinery practice, is continuously admitted to the unitary system by line 2 and conducted through the latter to heater 3 wherein it is heated to distillation temperature and is then sent through line l to fractionating column I. Any desired portion of the charge may be preheated in heat exchanger 5, located in line 2 and provided with a valved by-pass therearound. From fractlonator I there is withdrawn one or more higher boiling side stream distillate fractions, as for example, a heavy naphtha by line 6, a relatively light gas oil by line 1 and a relatively heavy gas oil by line 8, the heavy unvaporized residuum is withdrawn from fractlonator through line 9. The distillate fraction or fractions are conducted into reaction zone A by suitable branch connections, such as those shown, while the distillation residue withdrawn from fractionator I by line 9 is fed to reaction zone B, in which zones the desired conversion takes place.
In some instances, as for example, when the fresh charge bears relatively large amounts of organic sulphur compounds and/or when it contains unusually large amounts of diflicultly vaporizable or tarry nature, it is desirable to withdraw a long residuum from fractlonator i by line 9 containing substantial amounts of the higher boiling distillate portions of the charge. Such practice facilitates handling of the residuum in reaction zone B and provides for reduction in the sulphur content of the desired reaction products. In such cases, heat exchangers or any other suitable equipment for effecting separation from the reaction products of material boiling within aiaaooa the boiling range of the charge to zone B is operated to condense larger quantities of the synth'etic crudes. Such partial condensation may also be regulated so as to avoid recycling through reaction zone A of partially converted material boiling within the boiling range of the heavier portions of the charge to that zone. To this end. the reaction products issuing from the reaction systems may have removed from them components boiling within the boiling range of a portion or even all of the gas oil issuing from fractlonator I by lines 1 and/or 8 for the purpose of improving the conversion in reaction zone A and/or to provide stock for fuels capable of meeting a wide range of volatility specifications.
All lower boiling hydrocarbons of the desired end boiling point made in the unitary system as hereinafter described and any of such hydrocarbons introduced thereinto with the fresh charge are withdrawn from fractlonator I as a single stream or blend by overhead vapor line 23. This blend may be subjected to any desired treatment either before or after condensation. When it is desired to effect direct condensation of the lower boiling hydrocarbons the vapor in line 23 may be condensed in condenser 24 and have fixed or incondensable gases removed therefrom in separator 25 provided with gas outlet 26, hydrocarbon condensate withdrawal line 21 and a connection 28 for removing condensed steam. Any desired amount of condensate may be returned to fractlonator I by line 29 to be used as reflux, while the remainder may be withdrawn from the system by line 30.
Pyrolytic reaction zone A may contain one or any desired number of systems of any known or desired type for effecting pyrolytic or thermal conversion of higher boiling hydrocarbons in the vapor phase, liquid phase or mixed phase, as for example, utilizing equipment and operating conditions used in the pyrolytic conversion systems commonly known as Cross, Dubbs, tube and tank, De Florez, true vapor phase, gyro, Holmes-Manley, etc. Three such pyrolytic systems are indicated in the accompanying drawing, each comprising a cracking furnace 32a connected by valved transfer line 33a to flash chamber or tower 34a which is provided with a valved residue or tar Withdrawal line 35a and a valved vapor outlet 36a. Each of the pyrolytic systems is selectively connected to each of the lines 6, I and 8 by suitable manifolds and valved branched lines, shown, and to products vapor line I0 by valved vapor outlet 36a.
Although the charge to pyrolytic zone A may be a single stream of distillate, in the interest of high yield of good quality product it is preferable to separately convert a plurality of streams of distillates having restricted or relatively narrow boiling ranges under separate and distinct operating conditions. It is particularly advantageous to separately convert naphtha fractions and gas oil cuts for naphthas generally require more severe reaction conditions (high temperature and/or pressure) than do the higher boiling gas oil cuts. Although partially converted distiliates in line 20 may be mixed with one or more of the gas oil cuts issuing from fractlonator I, it is preferable to separately convert the partially converted distillate. The hydrocarbons charged to any oi the conversion units or systems in zone A may be subjected to the action of temperatures within the range of 750 to 1200 F. and pressures of from substantially atmospheric or slightly below to 3000 iba/sq. in. gauge. or more, the
pressures and temperatures used in any given system being dependent upon the type of system, and, to some extent, upon the source and characteristics of the charge thereto. 'I'he general tendencies are toward: (1) slightly less severe operating conditions with higher boiling range characteristics and/or lower A. P. I. gravities of the charging stocks; and (2) somewhat more severe operating conditions when the charge is comprised to substantial extent of partially converted material.
Pyrolytic systems usually provide suitable apparatus for effecting separation of heavy unconvertible residues from the remaining and clean distillate portions of the reaction products made in the system. Such equipment often takes the i'orm of flash vaporizers which may effect reduction of such residues to coke or which may permit withdrawal of the residues as liquid having con-1 trolled characteristics, which liquid may be used as a residual fuel or for the starting material for road oils or asphalts. Flash chambers 34a in reaction zone A are used for this purpose. Each may be operated so that a heavy viscous tarry residue is removed therefrom by valved line 35a, or, in order to meet refinery demands for more fluid residual oils, condensation of the heaviest portions of the vaporous reaction products in transfer line 33a may be effected withthe aid,
if necessary or desirable, of a suitable coolingv iiuid which may, for example, be admitted to lines 33a by valved inlets 33e. The resulting condensate is withdrawn as part of the residue. In such instances, the remaining vapors often have an end boiling point within the boiling range of the charge to zone A and can be conducted directly to vapor line I4 by means of manifold 31, shown selectively connected to vapor lines 30a.
Thus, each pyrolytic system is selectively connected to fractionator` I and separator I3 by manifolds I0 and 31 respectively. When a coking operation is conducted in chambers 34a the distillates leaving zone A sometimes have boiling ranges which also permits by-passing of separator I 3 by manifold 37.
In a preferred form of the invention, catalytic zone B conforms in general to that disclosed in the aforesaid Patent No. 2,078,247, issued to Eugene J. Houdry on April 27,V 1937, and that disclosed in United States Patent No. 2,031,600 issued to J. W. Harrison et al. on February 25, 1936, and comprises: (1) a heater 38h of any desired type for receiving and vaporizing a substantial part of the charge to zone A (2) one or more vessels or separators 39h connected to heater 38h for removing any unvaporized material from the vapors produced in the latter, these separators 39h being provided with vapor and tar outlet lines 40h and 4Ib, respectively; and (3) two or more converters 42h arranged in parallel and selectively connected to vapor line 40h by line 43h and valved branches 44D. They are also connected to products line II by valved branches h. Converters' 42h may be of any suitable type which provide reaction chambers containing a regenerative adsorptive or catalytic contact mass of any desired type capable of promoting the desired transformation. Preferably, the mass is of a slicious nature and is in comminuted or molded form, comprising, for example, molded pieces composed essentially of a blend of silica and another metal oxide, such as alumina. The blend may be of natural or artificial origin, including colloidal and precipitated gels and activated hydrosilicates of alumina of a clayey nature. 'Good results are ob tained with a catalyst having a weight ratio4 of silica to alumina in the mass of 395:1, or more, and other characteristics as disclosed in the copending application of Eugene J. Houdry, Se-
rial No. 600,581, filed March 23, 1932 and renewed July 3, 1936 which issued on May 4, 1937, as Patent No. 2,078,945. If desired, the contact mass may contain one or more suitable ingredients, such as metals or metallic oxides, for aiding the transforming reactions and/or the regeneration of the mass by combustion of contaminants deposited thereon during the transformation period, as set forth, for example, in the copending application of Eugene J. Houdry, Serial No, 35,101, led August 7, 1985, which issued as Patent-No. 2,078,951 on May 4, 1937. Converters 42a are preferably conducted and arranged for use alternately on-stream and in regeneration in situ of said catalyst in a manner to permit feeding of a continuous stream of vreactant material to the battery of converters, fresh regenerating medium, such as air or other oxygen bearing material being admitted to the converter orv converters undergoing regeneration by line 3Ib and valved branch or branches 45h, while spent regenerating medium is vented from valved branch or branches 46h and line 4'Ib, respectively.
'I'he residue in line 9, preferably while still hot,
is admitted to a suitable heater such as tubular heater 38h wherein it is raised to reaction ternperature and a substantial portion of it vapor-- ized. In order to assist in such vaporization and to minimize thermal cracking of the residue, as well as to assist in the subsequent catalytic trans` formation, a suitable inert diluent fluid, such as steam, is admitted to heater 38h, as by line 48h, in amounts which usually lie within the range of 5 to 25% by weight of the heated charge.
The heatedstream, after rejection therefrom of unvaporized material in separator 39h, at substantially atmospheric or low superatmospheric pressure, preferably, not in excess of lbs/sq. in. gauge, is passed through the contact mass in converters 42b for an operating or run periodv during which the contact mass is maintained at a temperature within the range of 750 to 925 F.
The reaction products made in either or both of the reaction zones have removed from them any and substantially all material which is within the boiling range of thecharge to zone B. One method of effecting such removal is by controlled partial condensation while utilizing a heat exchange medium. According to the drawing, vaporous reaction products leaving zone A, preferably freed of any tar made in that zone, may be conducted by line I0 to line II, containing vaporous reaction products made in zone B, and passed, with the latter, through heat exchanger 5 into line I2, in heat exchange relation with controlled amounts of cold fresh charge to effect the desired partial condensation. 'I'he resulting mixture of liquid and vapors is conducted through line I2 to separator I3. The vapors, containing the desired lower boiling hydrocarbons produced in both reaction zones leave separator I3 by vapor line I4 vand are conducted to fractionator I to be fractionated with the charge. These vapors may be led by line I4 to line 4 wherein they mix with the heated fresh charge and together with it be admitted to fractionator I and/or, all or any desired portion of the vapors in line I4 may be condensed and the III) condensate admitted to fractionator I, preferably at a point above the point of admission of the charge thereto, to serve as a temperature controlling medium after the manner of a refluxing agent to assist in maintaining balanced and controlled operation of fractionator I. The condensatefproduced in heat exchanger 5 is withdrawn from separator I3 by line I5. This condensate is clean and possesses other characteristics which render it suitable for use as a distillate, domestic or Diesel fuel oil or as a distillate or gas oil cracking stock. If desired, it may have entrained lower boiling hydrocarbons removed therefrom in steam stripper I6 provided with steam inlet line I1 and vapor outlet line I8 which discharges into vapor line I4. The stripped condensate leaving the stripper I G by line I9 may be conducted by valved line 20 to reaction zone A to be further converted therein along with or as an adjunct to the one or more distillate streams entering that zone, or all or any desired portion of it may be withdrawn from the system by valved line 2| to be used for fuel oil or any other desired purpose. may be by-passed by valved line 22 interconnecting lines I5" and I9. It is usually desirable to add additional amounts of inert diluent fluid to the vapors leaving separator 39h. to insure maintenance of vapor phase condition in lines 43h, b and in converters 2b. Such adition may be up to 10% by weight of steam, as by line 49h.
In a typical operation of the unitary system wherein a 400 F. end point gasoline is the desired product, a whole petroleum crude, as for example, an East Texas crude may be continuously charged to fractionator I and divided therein into straight run gasoline, a heavy naphtha cut having a boiling range of the order of 400 to 500 F. issuing therefrom by line 6, one or more gas oil` cuts issuing therefrom by lines 1 and/or 8 and having an end point of about 650 to r100 F., and a residue, leaving the co1- umn by line 9, containing substantially all portions of the crude boiling above the end boiling point of the gas oil. The heavy naphtha may be subjected to the action of a temperature of the order of 900 to 930 F. and a pressure of about 1375 lbs./sq. in. gauge for about 90 seconds in the upper pyrolytic system in reaction zone A and the gas oil subjected to the action of a temperature of about 890 F. and a pressure of about 1750 lbs/sq. in. for about three minutes, namely, in the second of the pyrolytc units to eiect the desired conversion of these fractions. After removal of the heavy tar therefrom as in flash vaporizer 34a, the synthetic crude vapors produced in the pyrolytic units are vented from zone A into vapor line I0. Meanwhile the residue in line 9 may be admitted to heater 38h and heated to about 890 F., about 15% by weight of superheated steam being addedto the residue during the passage through the heater, as by line 48h. The heated residue may then traverse separator 39h and be separated therein into a vapor fraction and a heavy tar having an A. P. I. gravity of the order of The vapor fraction under a pressure of the order of 15 lbs./sq. in. gauge may then be admitted to one of the converters 42h and passed through a catalyst contained therein and comprising molded pieces of activated hydrosilicate of alumina in which the silica to alumina weight ratio is of the order of 3/2:1, having incorporated therewith about 1% by weight of an oxide of manganese as a regeneration promoter and maintained at a temperature Stripper I6 of the order of 860 F. 'I'he rate of feed of the vapors to the contact mass may be oi' the order of 3:4 (3 volumes of condensed vapors per hour to 4 volumes of contact mass). The catalytic synthetic crude is conducted from reaction zone B by line Il, and, along with the vapors in line I0, is subjected to controlled partial condensation by passing the combined vapors in heat exchange relation with fresh charge in heat exchanger 5 so as to produce a liquid fraction containing substantially all portions of the synthetic crude from both reaction zones which boil above the end boiling point of the gas oil cut. 'I'he resulting mixture of liquid and vapor may then be passed through line I2 to separator I3, from which the vapors containing all lower boiling hydrocarbons present in both synthetic crudes may be conducted by line I4 to line 4 and thence into fractionator I, along with heated fresh charge, to be fractionated with the latter. The high boiling condensate in line I5 may be freed of entrained and lower boiling hydrocarbons, as in steam stripper I6, and withdrawn from the system, or, if substantially complete consumption of fresh charge is desired, such condensate may be conducted through line to the lower unit in pyrolytic zone A to be therein subjected to the action of a temperature of the order of 880 F. and a pressure of the order of 1750#/sq. in. gauge for about three minutes. 'I'he synthetic crude produced from such condensate after being freed of heavy residue in vessel 34a may be discharged into line I0 along with the other pyrolytic synthetic crudes.
When one of the pyrolytic systems requires cleaning two of the streams of distillate being fed to zone A may be combined and converted together in a single system, thus leaving the one system free for the necessary shutdown without interrupting the operation of the unitary system. For example: if one of two pyrolytic units operating on gas oil cuts requires cleaning, the charge to these two units may be temporarily combined and fed to the unit not requiring cleaning, while making any desired adjustment of the reaction conditions of the unit left in service; When it becomes necessary to clean a unit acting on the naphtha cut the charges to two other two units operating on heavier distillates may be combined as above described and the naphtha stream shifted to the unit thus left off Stream.
By the above indicated methods of operation and/or by other methods which are slight variations therefrom, it will be apparent to those skilled in the art that pyrolytic and catalytic zones A and B, respectively, operate interdependently and simultaneously, with maximum utilization of fresh feed, to produce, from the latter, in desired proportions, high quality valuable hydrocarbons of the motor fuel or gasoline type, along with valuable higher boiling fuels of distillate and/or residual types. In all instances, pyrolytic Zone A handles only materials which it is capable of acting upon to best advantage, i. e., clean and easily vaporizable stocks. while catalytic zone B transforms only virgin or unconverted material.
By the present invention pyrolytic and catalytic reaction zones for producing high quality lower boiling hydrocarbons from higher boiling hydrocarbons have been combined in a manner that permits each system to operate at high efflciency and to best advantage. The unitary system, which permits substantial economies of heat and of equipment. also provides for flexibility of operation that allows for yields of lower and higher boiling fuels in proportions suitable for meeting current and local refinery and market conditions of supply and demand. 'I'his flexibility is realized with maximum utilization of fresh feed to the system. Furthermore, while maintaining the above advantages, the unitary system provides for production of lower boiling hydrocarbons of high quality, including the ease with which they can be refined, regardless of the characteristics of the original charge.
It is to be understood that the drawing and explanation thereof are only exemplary of the invention. Many minor variations in the equipment and the operation will be apparent to one skilled in the art. Such variations are embraced within the scope of the invention and -include among other considerations, various known or desired methods of controlling the temperatures of one or more of the various streams of fluid in the system for purposes of realizing heat and other economies. For example, fresh charge may be utilized to control the temperature of the pyrolytic synthetic crude entering the iiash chambers of the pyrolytic zone and/or for controlling the temperature of either or both of the fractions leaving such flash chambers. 'Ihe invention is applicable; also when a suitable viscosity breaking unit or process is used as an adjunct to the vaporizer 38h for the bottoms cut of fresh charging stock. Vaporizer 38h and separator 39h may be replaced by a contact vaporizer, such for example, as that disclosed in U. S. Patent No. 1,989,927, issued to Eugene J. Houdry on February 5, 1935, or as disclosed in the copending Houdry application, Serial No. 32,170, led July 19, 1935.
'I'he present invention is, in some respects, generally related to my copending applications Serial Nos. 111,780 and 116,699, filed November 20, 1936 and December 19, 1936, respectively. It is directed, however, to specific features of process and apparatus not involved or claimed in these copending applications, including features for controlling the characteristics of charging material fed to and reaction products obtained from separate pyrolytic and catalytic conversion zones. One of the salient features of the present invention, which distinguishes it from the inventions set forth and claimed in the aforesaid copending applications, relates to interdependent conversion systems and process for operating such systems involving the use of a single fractionating zone for handling both charging material and regulated portions of the reaction products. Further distinctions will be apparent upon reference to the claims in this and the said copending applications.
I claim as my invention:
1. In the production of lower boiling hydrocarbons of the motor fuel type, the process comprising feeding to a fractionating zone a charging stock comprising easily vaporizable and diilcultly vaporizable higher boiling hydrocarbons, removing from said zone a distillate cut and a residual fraction, said residual fraction containing diflicultly vaporizable higher boiling hydrocarbons, subjecting said distillate cut to conditions of'pyrolytic conversion to produce therefrom desired lower boiling hydrocarbons of the motor fuel type, subjecting said residual fraction to catalytic cracking conditions including the use of a solid adsorptive contact mass ',capable of promoting cracking reactions to produce from said fraction desired lower boiling hydrocarbons of the motor fuel type.' separating from products of the pyrolytic 'and catalytic reactions hydro--l carbons boiling within the boiling range of said residual fraction, feeding reaction products remaining after said separation to said fractionating zonevto be fractionated Itherein along with said charging stock, removing a motor fuel fraction of controlled end point from said fractionating zone, subjecting the separated fraction of said products to separate pyrolytic cracking to produce lower boiling hydrocarbons of the motor fuel type, and fractionating products of the last named cracking step in said fractionating zone along with said charging stock and'said remaining catalytic and pyrolytic products.
2. In the production of lower boiling hydrocarbons of the motor fuel type from a wide boiling range composite hydrocarbon starting material containing botheasily vaporizable and diillcultly vaporizable hydrocarbons which are above the gasoline boiling range, the steps of process which comprise introducing said starting material into a fractionating zone, thereinA separating said material into at least two fractions of different boiling range characteristics, a lower boiling or distillate fraction and a higher boiling or residual fraction, said lower boiling fraction being composed primarily of hydrocarbons higher boiling than gasoline, including components within the gas oil boiling range, and said higher boiling or residual fraction containing substantially all of the diflicultly vaporizable portions of said starting material, heating and feeding at least a substantial portion of said residual fraction, primarily in vapor phase, to a confined reaction zone containing a solid adsorptive, substantially incombustible cracking catalyst and maintained under conditions so as to eiiect a conversion or cracking of said higher boiling or residual fraction to substantial extent into lower boiling hydrocarbons of the 'motor fuel type, passing the aforesaid lower boiling or distillate fraction through a second confined reaction zone while maintaining the same under conditions 'capable of effecting a pyrolytic conversion thereof to substantial extent into lower boiling hydrocarbons ofthe motor fuel type, passing a portion only of the reaction products issuing from said reaction zones into 'the aforesaid fractionating zone, therein to be fractionated in admixture with the aforesaid hydrocarbon starting material, said portion of said products beingof controlled boiling range and comprising substantially only hydrocarbons boiling below the boiling range of the aforesaid higher boiling or residual fraction, and withdrawing from said fractionating zone a blend of 'lower boiling hydrocarbons within the motor fuel range produced in both said pyrolytic and catalytic reaction zones.
3. In the production oflower boiling hydrocarbons of the motor'fuel type from a high boiling composite hydrocarbon starting materialof wide boiling or residual fraction containing substantially all of the diiilcultly vaporizable portions of said starting material, heating and feeding at least a substantial portion of said residual fraction, primarily in vapor phase, to a confined reaction zone containing a solid, adsorptive, substantially incombustible catalytic material and maintained under conditions so as to effect a catalytic conversion or cracking of said higher boiling or residual fraction to substantial extent into lowerl boiling hydrocarbons of the motor fuel type, passing the aforesaid lower boiling or distillate fraction through a second confined reaction zone maintained under conditions capable of effecting a pyrolytic conversion of the same to substantial extent into lower boiling hydrocarbons of the motor fuel type, separating higher boiling hydrocarbons within the range of the aforesaid residual fraction from remaining cornponents of the products of reaction issuing from said pyrolytic and catalytic reaction zones, blending lower boiling reaction products remaining after said separation with said starting material, and separating from the resulting blend a lower boiling motor fuel of controlled end point While simultaneously producing the aforesaid distillate and residual fractions.
4. In the production of lower boiling hydrocarbons of the motor fuel type, the process of establishing in simultaneous, cooperative and interdependent operating relation a pyrolytic reaction zone and a catalytic reaction zone, each of said zones being capable of and adapted to effect conversion of higher boiling hydrocarbons into lower boiling hydrocarbons, and a single fractionating zone, in the latter continuously dividing a composite hydrocarbon material containing both easily vaporizable and difficulty vaporizable higher boiling hydrocarbons into at least one clean higher boiling distillate fraction and a residual fraction containing substantially all the difficulty vaporizable portions of the charge, feeding said distillate fraction to said pyrolytic zone while maintaining the latter under suitable conditions to effect thermal conversion of said distillate into lower boiling hydrocarbons, vaporizing a substantial proportion of said residual fraction and charging the resulting vapors, substantially free of unvaporized liquids and of extraneous reactant gases, to said catalytic zone maintained under conditions favorable to the production from said residue of high antiknock lower boiling hydrocarbons, and adsorptive silicious catalytic material being maintained within said catalytic zone, removing the reaction products from each of said zones, separating from said reaction products substantially al1 hydrocarbons within the boiling range of said residual fraction, feeding the remainder of said reaction products to said fractionating zone to be fractionated along with said charge, removing from said fractionating zone a blend of the aforementioned lower boiling hydrocarbons of the motor fuel type, and feeding the higher boiling hydrocarbons separated from said reaction products to said pyrolytic zone to be therein converted into lower boiling hydrocarbons.
5. In the production of lower boiling hydrocarbons of the motor fuel type from a high boiling composite hydrocarbon starting material containing both easily vaporizable and dlilicultly vaporizable hydrocarbons which are above the gasoline boiling range, the steps of process which comprise introducing said starting material into a fractionating zone, therein separating said starting material into at least two fractions of different boiling range characteristics, a lower boiling or distillate fraction and a higher boiling or residual fraction, said lower boiling fraction being composed predominantly of hydrocarbons higher boiling than gasoline, including components within the gas oil boiling range. and said higher boiling or residual fraction containing substantially all of the diiculty vaporizable portions of said starting material, heating said residual hydrocarbon fraction and separating tarry components having a gravity of the order of 15 A. P. I. from the remaining portions thereof, feeding the last-mentioned or remaining portions, primarily in vapor phase, to a confined reaction zone containing a solid adsorptive silicious cracking catalyst and maintained under conditions to effect a catalytic cracking or transformation of the said remaining portions of said residual fraction to substantial extent into lower boiling hydrocarbons including a substantial prol portion of components within the gasoline boiling range, passing the aforesaid lower boiling or distillate fraction through a second confined reaction zone while maintaining the same under conditions capable of effecting a pyrolytic conversion thereof to substantial extent into lower boiling hydrocarbons of the motor fuel type, passing products of reaction issuing from each of said confined zones having a boiling range below that of the aforesaid higher boiling or residual fraction into the aforesaid fractionating zone, thereby to be fractionated in admixture with the aforesaid hydrocarbon starting material, and withdrawing from said fractionating zone a blend of lower boiling hydrocarbons composed largely of components within the gasoline boiling range produced in both said pyrolytic and catalytic conversion zones.
6. In the production of lower boiling hydrocarbons of the motor fuel type, the process of establishing in continuous cooperative and interdependent operating relation pyrolytic reaction zones, a single fractionating zone, and at least one catalytic reaction zone containing regenerative silicious contact material capable of promoting transformation of higher boiling hydrocarbons into lower boiling hydrocarbons, heating to distillation temperature a composite hydrocarbon charging material having substantially the boiling range characteristics of a whole crude petroleum oil, feeding said heated charge to said fractionating zone, withdrawing from the latter a heavy naphtha fraction, at least one gas oil fraction and a liquid distillation residual fraction, separately converting said naphtha and gas oil fractions into lower boiling hydrocarbons in individual ones of said pyrolytic zones, effecting vaporization of a substantial portion of said residual fraction, passing the resulting vapors through said silicious contact material within said catalytic reaction zone while maintaining the latter at a temperature within the range of '750 F. to 925 F. to convert such vapors to substantial extent into lower boiling hydrocarbons, withdrawing reaction products from said pyrolytic and catalytic reaction zones, combining said pyrolytic and catalytic reaction products, removing from the combined products substantially all hydrocarbons boiling within the range of said residual fraction, admitting the remainder of said combined products to said fractionating zone to be therein fractionated along with said charge, and withdrawing as product from said fractionating zone a blend of substantially all the desired end point lower boiling hydrocarbons produced in said catalytic and pyrolytic reaction zones.
7. In the production of valuable lower boiling hydrocarbons of the motor fuel type, the process of heating to distillation temperature a composite hydrocarbon starting material containing a mixture of both easily vaporizable hydrocarbons of the distillate fuel type and more diflicultly vaporizable hydrocarbons of the residual fuel type, feeding the heated mixture to a fractionating zone, withdrawing from said zone a plurality of distillate fractionns of differing boiling ranges and higher boiling than the aforementioned motor fuel, and a bottoms fraction containing approximately all of the hydrocarbons in said st'arting material which boil above 750 F. including said difilcultly vaporizable hydrocarbons, heating and vaporizing a substantial proportion of said bottoms fraction land feeding the resulting heated vapors to a reaction zone containing a solid, adsorptive catalytic material, comprising essentially a blend of silica and alumina, to effect transformation of said vapors into high antiknock lower boiling hydrocarbons, withdrawing reaction products from said catalytic zone and introducing a substantial proportion of said products boiling below the boiling range of said bottoms fraction into said fractionating zone to be therein fractionated along with said starting material, feeding said distillate fractions from said fractionating zone to separate respective reaction zones, each maintained under conditions so as to eiect pyrolytic conversion of said distillate fractions into lower boiling hydrocarbons, withdrawing reaction products from the aforementioned pyrolytic reaction zones, removing from the last-mentioned reaction products substantially all hydrocarbons higher boiling than the highest boiling of said distillate fractions, ad-
mitting the remainder of said last-mentioned reaction products to said fractionating zone to be therein fractionated along with said hydrocarbon starting material and products from said catalytic reaction zone, and withdrawing from said fractionating zone lower boiling hydrocarbons of the motor fuel type comprising a blend of hydrocarbons produced in both the catalytic and pyrolytic reaction zones.
8. In apparatus for producing lower boiling hydrocarbons from charging material containing both easily vaporizable and diflicultly vaporizable higher boiling hydrocarbons, in combination, a heater for fresh charge, a fractionating column connected to said heater and adapted to eiect separation of lower boiling hydrocarbons from higher boiling hydrocarbons and to divide the latter into at least one distillate fraction and a residual fraction', a catalytic transformation system connected to said column so'as to re,
ceive said residual fraction, said catalytic system comprising heating means for producing hydrocarbon vapors from said residue, a plurality of converters selectively connected to said heating means and containing a bed of regenerative, adsorbent silicious contact mass, said converters being adapted and arranged for use alternately in the transformation of hydrocarbons and in regeneration of said mass in place, a pyrolytic conversion system adapted to receive said distillate fraction from the aforesaid column and providing heating and converting means therefor, means for conducting reaction products from each of said systems to said fractionating column, and means associated with said last named means for separating and removing the highest boiling components of said reactionA products from the latter.
9. In apparatus for producing lower boiling hydrocarbons from charging material containing both easily vaporizable and diilicultly vaporizable higher boiling hydrocarbons, in combination, a heater for fresh charge, a fractionating column connected to said heater and adapted to eiect separation of lower boiling hydrocarbons from higher boiling hydrocarbons and to divide the latter into at least one distillate fraction and a residual fraction, a catalytic transformation system connected to said column so as to receive said residual fraction, said catalytic system comprising heating means for producing hydrocarbon vapors from said residue, a plurality of converters selectively connected to said heating means and containing a body of regenerative, adsorbent contact mass in the form of small pieces of regular sizes and shapes, said converters being adapted and arranged for use alternately in the transformation of hydrocarbons and in regeneration of said mass in place, a pyrolytic conversion system adapted to receive said distillate fraction and providing heating and converting means therefor, means associated with said pyrolytic system for separating and removing from the pyrolytic reaction products substantially all hydrocarbons higher boiling than said distillate fraction to leave a vapor fraction comprising essentially hydrocarbons lower boiling than said residual fraction, means for conducting said vapor fraction to said fractionating column, means for conducting catalytic reaction products from said catalytic system, means for separating and removing as liquid from said catalytic reaction products substantially all hydrocarbons higher boiling than said distillate fraction to leave a vapor fraction comprising essentially hydrocarbons lower boiling than said residual fraction, means for conducting said last named vapor fraction to said fractionating column, and means for conducting said last named liquid fraction to said pyrolytic system.
10. In apparatus for producing lower boiling hydrocarbons from charging material containing easily vaporizable and diillcultly vaporizable higher boiling hydrocarbons, in combination, a heater for heating fresh charge to distillation temperature, a fractionating column' provided with an inlet connection, an overhead vapor outlet connection for lower boiling hydrocarbons, at least two side stream distillate connections for higher boiling hydrocarbon fractions of relatively higher and relatively lower boiling ranges and an outlet for distillation residue, a connection from said heater to said inlet connection, at least two pyrolytic conversion systems, a connection between said side stream connection for relatively lower boiling range distillate and one of said systems, a connection between the other of said side stream connections and another pyrolytic system, a catalytic transformation system comprising a heater for effecting vaporization of a substantial portion of said distillation residue, a separator connected to said last named heater for removing unvaporized material from vapors leaving said heater and providing an overhead vapor connection, and a plurality of converters selectively connected to said separator through said last named vapor connection, said converters containing a regenerative contact mass comprising essentially a blend of silica and alumina in molded form and being adapted for use alten' nately in transformation of hydrocarbons and in regeneration in place, a connection between said residue outlet connection and said last named heater, lines for conducting reaction products from said catalytic system, lines for withdrawing pyrolytic reaction products i'rom each pyrolytic system, means including separating means associated with said pyrolytic systems and with said catalytic system for receiving reaction products therefrom and separating from said reaction products as liquid substantially all hydrocarbons issuing from said systems which are as high boiling as said highest boiling distillate fraction, and vapor connections between said separating means and said fractionating column for conducting the remainder of the reaction products into said column.
l1. In apparatus for producing lower boiling hydrocarbons from charging material containing both easily vaporizable and diiilcultly vaporizable higher boiling hydrocarbons, in combination, a' heater for fresh charge, a fractionating column connected to said heater and adapted to eiect separation of lower boiling hydrocarbons from higher boiling hydrocarbons and to divide the latter into a plurality of distillate fractions and a residual fraction, a catalytic transformation system connected to said column so as to receive said residual fraction, said catalytic systemV comprising heating means for producing hydrocarbon vapors from said residue, a plurality of converters selectively connected to said heating means and containing regenerative, adsorbent silicious contact mass, said converters being adapted and arranged for use alternately in the transformation of hydrocarbons and in regeneration of said mass in place, a plurality of pyrolytic conversion systems, each one of said pyrolytic systems being connected to said fractionating column so as selectively to receive any one or any desired combination of said distillate fractions, means for removing from the reaction products made in any of said systems hydrocarbons boiling within the boiling range of said residue, and means for conducting the remainder of said products from the last-mentioned means to said fractionating column.
ARTHUR E. PEW, Ja.
CERTIFICATE OF CORRECTION. l Patent No. 2,197,009. `April 16, 191m.
- ARTHUR E. PEw, JR.
It is hereby certified that 4error' appears in the printed specification of the above numbered patent requiring correction as follows: Page l, second column, line 2l, for "charactertstics" read characteristicsug page 2, first column, line T5, for the word "exchangers" read exchanger; page Il, first column, line 5C, for "adition" read --addition; page 6, first column, lines 58 and )42, claim )4, and second column, line 9, claim 5, for "difficulty" read -difficultly-'; page Y, first column, line l5 claim Y, for "fractionns" read --fractions; and that -the said Letters Patent should be read with this correction therein that the same may conform to the record of the case in the Patent Office.-
Signed and sealed this 18th day of June, A. D. 19140 Henry Van Arsdale (Seal) Acting Commissioner of Patents.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2819203A (en) * 1950-04-15 1958-01-07 Sinclair Refining Co Process for the thermal cracking of catalytic cycle gas oil stocks

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2819203A (en) * 1950-04-15 1958-01-07 Sinclair Refining Co Process for the thermal cracking of catalytic cycle gas oil stocks

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