US3714023A - High octane gasoline production - Google Patents

High octane gasoline production Download PDF

Info

Publication number
US3714023A
US3714023A US00885859A US3714023DA US3714023A US 3714023 A US3714023 A US 3714023A US 00885859 A US00885859 A US 00885859A US 3714023D A US3714023D A US 3714023DA US 3714023 A US3714023 A US 3714023A
Authority
US
United States
Prior art keywords
zone
gasoline
reforming
cracking
saturate
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
US00885859A
Other languages
English (en)
Inventor
L Stine
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Honeywell UOP LLC
Universal Oil Products Co
Original Assignee
Universal Oil Products Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Universal Oil Products Co filed Critical Universal Oil Products Co
Application granted granted Critical
Publication of US3714023A publication Critical patent/US3714023A/en
Assigned to UOP, DES PLAINES, IL, A NY GENERAL PARTNERSHIP reassignment UOP, DES PLAINES, IL, A NY GENERAL PARTNERSHIP ASSIGNMENT OF ASSIGNORS INTEREST. Assignors: KATALISTIKS INTERNATIONAL, INC., A CORP. OF MD
Assigned to UOP, A GENERAL PARTNERSHIP OF NY reassignment UOP, A GENERAL PARTNERSHIP OF NY ASSIGNMENT OF ASSIGNORS INTEREST. Assignors: UOP INC.
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/04—Liquid carbonaceous fuels essentially based on blends of hydrocarbons
    • C10L1/06—Liquid carbonaceous fuels essentially based on blends of hydrocarbons for spark ignition
    • 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
    • C10G59/00—Treatment of naphtha by two or more reforming processes only or by at least one reforming process and at least one process which does not substantially change the boiling range of the naphtha
    • C10G59/02—Treatment of naphtha by two or more reforming processes only or by at least one reforming process and at least one process which does not substantially change the boiling range of the naphtha plural serial stages only
    • 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
    • C10G63/00—Treatment of naphtha by at least one reforming process and at least one other conversion process
    • C10G63/02—Treatment of naphtha by at least one reforming process and at least one other conversion process plural serial stages only
    • C10G63/04—Treatment of naphtha by at least one reforming process and at least one other conversion process plural serial stages only including at least one cracking step
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/02—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only
    • C10L1/023—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only for spark ignition

Definitions

  • this invention pertains to a combination of integrated reiinery processes including low severity reforming and cracking of hydrocarbons to provide a resulting high octane gasoline pool, requiring, in most cases, no lead addition for present-day gasoline octane requirements for internal combustion engines.
  • Aromatization of paraflins is achieved by the dehydroeyclization of straight chain p araflins having at least siX carbon atoms per molecule.
  • Dehydrocyclization is limited in the once-through reforming operations because as the aromatic concentrations increase through the reforming zone the rate of additional dehydrocyclization of paraffins is greatly reduced. This leaves unreacted parafns present in the reformate effluent which greatly reduces the octane ratin-g of the reformate.
  • the parains which at low reforming severity would pass through unreacted, are cracked, at high reforming severity, to yield partly gasoline material but largely light hydrocarbons. Because of the hydrogen present during the cracking step the light hydrocarbons are saturated forming primarily normal and non-normal para'fns in the C1 to C4 carbon number range.
  • the unreacted saturates which pass through the reforming zone typically are of low octane rating and in some cases require further processing to upgrade the gasoline pool. Further processing in order to improve the octane rating of the saturates leaving the reforming zone can be eliminated by in effect overwhelming the low octane components of the reformate by increasing the reformed severity of operations to produce an increased quantity of aromatic components. This type of operation has a twofold effect in increasing a reformate octane rating; first, additional high octane aromatic components are produced; and, secondly, the lower octane components are partially eliminated by being converted into aromatic components or into light products outside the gasoline boiling range.
  • light hydrocarbons generally refers to those hydrocarbons which have from one to four carbon atoms per molecule and is generally expressed in the art as C4-f
  • the light hydrocarbons having one and two carbon atoms per molecule are generally referred to as dry gases and are generally used as refinery fuel gas while the C3 and C4 portions of the light hydrocarbons are valuable; the C3 and C., oleiins can be used in the process of this invention for alkylate or polymer or isopropyl alcohol production.
  • the C3 and normal C4 parain portions of the light hydrocarbons are generally referred to as liquid petroleum gases and can be used as such.
  • Light naphtha streams generally refer to hydrocarbon streams containing hydrocarbons in the C5 and Cs carbon range.
  • the light naphthas generally are recovered directly, as virgin light naphthas, from a crude distillation unit.
  • the end boiling point of most light naphthas is generally from about 175 F. to about 200 F.
  • the heavy naphthas are generally referred to as those hydrocarbons streams having boiling points from about F. to about 400 F. which includes those hydrocarbons having carbon numbers of about 7 or greater and which boil below about 400 F.
  • the light cycle oils generally boil immediately above the heavy naphtha boiling range generally around 400 to 600 F. while atmospheric and vacuum gas oils are generally higher boiling materials having boiling ranges of about 600 to about 1200 F. with the atmospheric gas oils generally boiling at the lower end of the given temperature range.
  • the vacuum gas oils are generally distilled from the crude oil in a vacuum tower to prevent thermal cracking because of the relatively high boiling range of that material.
  • hydrocarbon boiling ranges there is a certain amount of overlap of the boiling range of the individual hydrocarbons of adjacent carbon numbers when referring to hydrocarbon boiling ranges in this specification.
  • the hydrocarbon stream identified by a boiling range shall be assumed to have about 10% of its volume boiling below the lower temperature and about 95% of its volume boiling below the upper temperature of its given boiling range.
  • a suitable hydrocarbon feed stock is contacted with a reforming catalyst to effect conversion of the reformer feed stock to a higher octane reformate product.
  • Hydrocarbon feed stocks which can be used in the reforming zone include hydrocarbon fractions containing naphthenes and parains. The preferred stocks are those consisting essentially of naphthenes and paraffins although in some cases aromatics or olefins or both aromatics and olefins may be present.
  • Preferred reformer feeds include straight-run gasoline, natural gasolines, and the like. It is frequently advantageous to charge thermally or catalytically cracked gasolines or higher boiling fractions thereof to the conversion process of the reforming zone.
  • the reformer charge stock may be a full boiling range gasoline charge stock having an initial boiling point of from about 50 F. to about 100 F. and an end boiling point within the range of from about 325 F. to about 425 F., or may be a selected fraction thereof.
  • the catalysts which can be used in the reforming zone include refractory inorganic oxide carriers containing a reactive metallic component thereon.
  • Inorganic refractory oxides which can be used as carriers for reforming catalysts include alumina, the crystalline aluminosilicates such as the faujasites or mordenite, or combinations of alumina and the crystalline aluminosilicates.
  • Metallic components which are generally recognized in the art as being favorable catalytic components for reforming operations generally include the Group VIII metals.
  • the Group VIII metals include iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium, and platinum.
  • Rhenium a Group VII-B metal
  • Reforming catalysts may also contain combined halogen as one of the catalytic components.
  • the halogens which can be used include uorine, chlorine, bromine, iodine or mixtures thereof.
  • Effective reforming operating conditions include temperatures within the range of about 800 F. to about 1100" F. and preferably between about 850 F. and about 1050 F., liquid hourly space velocities in the range of from about 0.5 to about 15.0 and preferably in the range of from about 1 to about 5 are normally used.
  • the quantity of hydrogen-rich recycle gas which is charged along with the hydrocarbon feed stock to the reforming zone. generally is present in amounts of from about 1/2 to about 20 moles of hydrogen per mole of hydrocarbon feed, and preferably from about 4 to about 12 moles of hydrogen per mole of hydrcserbon feed.:
  • the @farming 20H@ may be effected in any suitable process system familiar to those skilled in the art such as uidized type processes, moving bed-type process, etc.
  • Particularly suitable processes comprise the well-known fixed bed system in which the catalyst is disposed in the reaction zone, and the hydrocarbons to be converted are passed therethrough in either upward or downward flow.
  • the reforming zone reactor efuent, or reformate is generally passed through a separation zone where it can be fractionated to remove lighter weight components from heavier weight liquid components of the reformate and where the recycle gas, which is reused in the reforming zone can be easily separated. Since normal reforming operations produce excess amounts of gaseous hydrogen, a certain amount of the recycled gas is generally removed from the reforming system to maintain a given operating pressure. Reforming zone pressures generally used in normal reforming operations are generally within the range of from about l0 to about 1500 pounds per square inch.
  • the reforming zone used in this combination process is operated at low severity.
  • relatively high severity generally indicates high temperature or low space velocity or both high temperature and low space velocity operating conditions.
  • the direct results of high severity operations are generally noticed in the reformate octane being increased substantially. While the reforming zone used in this operation does not necessarily upgrade the octane of the reformer feed to that of the pool gasoline, the reforming zone feed stock is substantially improved in octane rating.
  • Low severity reforming operations as used in the specification and attached claims shall generally define a reforming process in which a large percentage of the naphthenes in the reformer feed are dehydrogenated to high octane aromatic compounds with the qualification that the dehydrocyclization of feed parains to aromatics is substantially reduced.
  • a more detailed definition of the term low severity reforming operations can include conversion of feed naphthenes to aromatics within the range of from about moles of aromatics produced per 100 moles of naphthenes charged to the reforming zone to about moles of aromatics produced per 100 moles of naphthenes charged to the reforming zone and less than about 40 moles of aromatics produced per 100 moles of alkanes charged to the reforming zone.
  • the function of the saturate cracking zone is to crack the saturated hydrocarbons fed to it by either thermal or catalytic means or both.
  • the feed stock to the staturate cracking zone can be the entire low severity reformer gasoline effluent or just the saturated portion thereof depending on whether there is an intermediate separation zone between the reforming zone and the saturate cracking zone,
  • the saturated cracking zone will primarily receive saturated feed stock comprising parains and cyclic paraffins.
  • aromatic hydrocarbons will also necessarily be present in the saturate cracking zone feed stock.
  • the saturate cracking zone must be able to selectively crack that zones feed stock saturates to lower ⁇ molecular weight hydrocarbons in a manner so as to minimize the production of dry gases such as methane, ethane, ethylene or acetylene, while maximizing the production of C3 and C4 saturates or unsaturates and cracked gasoline materials.
  • the saturate cracking zone produces cracked gasoline and valuable light hydrocarbons from most of the aromatic precursors which are not converted to aromatics in the reforming zone because of the requirement that the zone be operated at low severity conditions to gain an overall advantage in liquid yield of a high octane gasoline pool.
  • the materials produced in the saturate cracking zone generally comprise a relatively high octane cracked gasoline plus C3 through C5 light hydrocarbons comprising propane, propylene, normal and iso-butane, normal and isobutene, and pentanes and pentenes.
  • the products are eX- cellent feed stocks for other processes which form valuable gasoline components such as amines, esters, ethers, ketones, branched chain parafiins or alcohols.
  • the olefinic portion of the aforesaid light hydrocarbons is especially suited for conversion to the previously mentioned gasoline components while in general the parainic portion of the saturate cracking zone effluent which contains a relatively large amount of branched chain molecules is suited for production of alkylate gasoline.
  • a general but not all inclusive listing of individual valuable gasoline components which can be produced from the saturate cracking zone light hydrocarbons includes methyl alcohol, ethyl alcohol, isopropyl alcohol, isobutyl alcohol, tertiary butyl alcohol, isoamyl alcohol, tertiary amyl alcohol, hexanol, isopropylamine, n-butylamine, diethylamine, tirethylamine, methyl acetate, ethyl acetate, isopropyl acetate, isobutyl acetate, propylene oxide, n-propyl ether, isopropyl ether, m-butyl ether, isoamyl ether, acetone, methyl ethyl ketone, methyl n-propyl ketone, diethyl ketone, C3 alkylate or C4 alkylate.
  • reaction temperatures within the range of from about 850 F. to about 1200 F. and preferably temperatures within the range of from about 850 F. to about 1l501 F.
  • reaction temperatures within the range of from about 850 F. to about 1200 F. and preferably temperatures within the range of from about 850 F. to about 1l501 F.
  • olefinic light hydrocarbons propylene and butene
  • the contact time between the parainic cracking zone feed and the catalyst contained therein is the contact time between the parainic cracking zone feed and the catalyst contained therein.
  • the weight ratio of olens over saturates is almost directly related to the space velocity being used in the reaction zone. Increasing the space velocity of the saturate feed passing through the reaction zone increases the amount of olefinic hydrocarbons produced.
  • space velocity is generally measured in terms of weight hourly space velocity (WHSV) which is defined as the weight of charge oil per hour over the weight of the catalyst in the reaction zone.
  • WHSV weight hourly space velocity
  • the WHSV based on raw charge oil is most frequently used.
  • Weight hourly space velocities greater than about are preferred when effecting saturate cracking in the saturate cracking zone.
  • a portion of the eflluent material from this zone may be recycled back to the cracking zone to effect a further conversion to more valuable components.
  • the catalytic cracking zone requires a catalyst that specifically can produce the valuable saturated and unsaturated light hydrocarbons which can contribute to the process efficiency after further conversion to gasoline components. Additionally, the saturate cracking zone catalyst effects the production of a cracked gasoline product which contributes to the overall high octane gasoline pool which the combination process of this invention provides.
  • the catalyst used in this zone can be selected from a number of known materials including amorphous silica-alumina and zeolitic type aluminosilicates, both of which may contain composited thereon various catalytic components selected from the Periodic Table metals of combined or elemental character.
  • Cracking catalysts which may be used in the saturate cracking zone including certain types of silica-alumina, silica-magnesia, silica-zirconia and more preferably crystalline aluminosilicates characterized as having relatively high cracking activities.
  • the preferred crystalline aluminosilicate cracking catalysts can be mixed with less active amorphous type cracking catalysts or can be present in substantially pure form depending on the severities required of the process.
  • the crystalline aluminosilicate may be naturally occurring or synthetically prepared. In the latter case the crystalline aluminosilicate may be selected from the group of synthetically prepared zeolites A, Y, L, D, R, S, T, Z, E, F, U, Q, B, X, ZK-4, ZK-S, etc.
  • the naturally-occurring materials include faujasite, mordenite, montmorillonite, etc.
  • the catalyst comprises a crystalline aluminosilicate, or amorphous material
  • selected metals may be composited thereon by ion-exchange or impregnation methods.
  • the metals composited on the catalyst may include the rare earth metals, alkali metals, alkaline earth metals, Group VIII metals, etc., and various combinations thereof. Hydrogen may also be present within the catalyst to effect increased catalyst activity.
  • Thermal cracking conditions can vary from pressures ranging from about atmospheric to about 500 p.s.i.g. and a temperature of from about 900 F. to about l500 F.
  • FIG. l of the drawing represents the basic flow pattern of the invention where the saturate cracking zone contains a catalyst which selectively cracks the saturated portion of the reforming zone reformate while maintaining relative inertness towards the aromatic portions of the reformate.
  • a heavy naphtha feed from a source including a crude unit or other refinery processing equipment flows through line S together with recycle hydrogen from line 6 into reforming zone 1 wherein a portion of the feed stock is changed in structure to primarily aromatic structured molecules.
  • the reforming zone is operated at specific conditions to allow a maximum production of aromatic hydrocarbons with a minimum loss of liquid yield of gasoline.
  • the reaction conditions employed in reforming zone 1 are more specifically low severity conditions which are more specifically defined previously herein.
  • the efiiuent from the reforming zone 1 passes through line 7 to separation zone 2 wherein the gasoline portion of the reforming zone eiuent is separated from the lighter portions of the reforming zone efiiuent.
  • Off gas comprising primarily hydrogen is withdrawn from separation zone 2 via line 8.
  • a portion of this gas stream may be recycled via line 6 to the reforming zone.
  • a light hydrocarbon stream primarily comprising the C1 through C4 molecular weight hydrocarbons is withdrawn from separation zone 2 via line 9 while a C5/CG gasoline stream is withdrawn via line 10.
  • the material withdrawn via line may alternately be fed directly to the saturate cracking zone in admixture with the major gasoline portion of the reforming zone eluent which passes via line 11 to the saturate cracking zone 3.
  • Recycle material from the eiuent from the saturate cracking zone when used passes through line 32 in admixture with the feed to the saturate cracking zone.
  • the material fed to the saturate cracking zone is cracked to lower molecular weight light hydrocarbons which are removed via line 13 from separation zone 4 and to gasoline boiling range material which is removed via line 14 and collected for direct use as a valuable component of the overall refinery gasoline pool.
  • FIG. 2 there is located between the reforming zone 15 and the saturate cracking zone 18, extraction zone 17 which separates the aromatic constituents of the reforming zone gasoline from the saturated constituents present in the gasoline.
  • the saturated portion of the reforming zone reformate is passed into the saturate cracking zone in a relatively pure form.
  • the reforming zone 15 fresh feed flows through line and contacts a hydrogen rich gas stream flowing through line 21.
  • the resulting mixture continues through line 20 into the low severity reforming zone.
  • the reacted and unreacted material then passes into separation zone 16 where the reforming zone effluent is separated into a hydrogen-rich gas stream which Hows through line 23, a light hydrocarbon stream comprising C1 through C4 hydrocarbons which flows through line 24, a C5/C6 gasoline stream which ows through line and a CS-igasoline stream which ows through line 26 to extraction zone 17.
  • the C5/C6 gasoline stream may instead be diverted so as to ilow together with the C-lgasoline which flows through line 26.
  • extraction zone The following examples more specically illustrate the operation of the process of this invention and are not intended to be limitations thereon.
  • the reforming zone contained a typical platinum metal on an alumina base and was operated at conditions to produce a C5-tplatformate of about 85.0 Research Clear Octane Number (RON).
  • the eluent from the low severity reforming zone was separated into a hydrogen rich stream, a CTC.; light hydrocarbon stream, a C/CS gasoline stream and a Cq-lgasoline stream, the Cq-treformate stream was passed into a solvent extraction zone which separated the Cq-I- reformate into an aromatic rich stream and a saturate rich stream with the saturate stream being passed into the saturate cracking zone for conversion to cracked gasoline and lower molecular weight light hydrocarbons.
  • a material balance for the process flow according to FIG. 2. is shown in Table II and the various stream compositions are indicated in Table III both following.
  • C l' SOC I cracked gasoline may be recycled back to the cracking mmglm, ffxclight hydrocarbons Mm.; 5,6 19'2 zone 18, and where this is desired, recycle material passes Totlggsgtggsolm@ 1?/ ggg through line 33 into feed line 27 to the cracking zone.
  • Aromatic rich stream saturate rich stream
  • an extraction zone was employed to effect separation of saturated material from aromatic material present in the C74- reformatc stream fed to the extraction zone. This is not a requirement of the process to effect cracking of the saturate material where the saturate cracking zone is adapted to selectively convert saturates when large quantities of aromatic hydrocarbons are also contacting the saturate cracking zone catalyst. It is anticipated that the yields from the saturate cracking zone will not be substantially altered when large quantities of aromatics are fed to the saturate cracking zone.
  • EXAMPLE II In this example, a higher severity reforming zone was employed without subsequent cracking of the reformate saturate materials.
  • the catalyst used was the same as the reforming catalyst used in Example I. The severity was such that the C5 434 F. EP. gasoline produced in the reforming zone was maintained at 92.0 RON.
  • the higher octane reformate produced by these operations was much higher in aromatic content than the C54- reformate having an 85.0 RON of Example I.
  • the 92.0 Octane reformate contained 69 vol. percent aromatics
  • the 85.0 Octane reformate contained only about 45 vol. percent aromatics.
  • the higher octane reformate consequently was also lower in saturate content because of the higher quantity of saturates converted to aromatics via dehydrogenation of cycloparains and dehydrocyclization and/or cracking of parains.
  • the reforming zone effluent was separated into a hydrogen-rich gas stream, a C1C4 light hydrocarbon stream and a C5 434 F. E.P. gasoline material. Analysis of the products and material balance are shown in Table 1V.
  • Feed stock to reformer 25, 899. 7 280, 710 Hydrogen rich separator gas 16, 285 (l1-C4 light hydrocarbons 18, 981 05+' retormate gasoline 21, 828 0 251,445 Properties of 05+ reformate gaso API at 60F 47.7 Specific gravity at 60 F.. 7896 R P 2. 9 Distillation, F.
  • the reforming zone which was operated at 92.0 RON severity level yielded 21,828 barrels per day (BPD) of C5 to 434 F.
  • E.P. gasoline on a feed stock of about 25,900 (Barrels per Day) BPD feed rate as seen from Table IV.
  • the only other valuable gasoline component recovered from the light hydrocarbons produced by this reforming zone was about 523.5 BPD of isobutane which is an excellent feed material for an alkylation zone to produce a C3 or C4 gasoline alkylate having RON ratings of 92.0 and 98.0 respectively.
  • about 17,483 BPD of gasoline was produced directly from the combination reforming-extraction-saturate cracking process of this invention, as shown in Example I, Table II.
  • the gasoline pool comprised cracked gasoline from the saturate cracking zone, C5/C5 gasoline derived directly from the reforming zone and an aromatic concentrate which was also obtained from the reforming zone after the C74- gasoline therefrom was solvent extracted to remove its aromatic hydrocarbons prior to the cracking operation.
  • the C5/C6 gasoline was found to possess a RON of 71.0, the cracked gasoline possessed a RON of 95.0 and the aromatic rich gasoline from the solvent extraction zone was 115.0 RON quality.
  • the C54- gasoline pool from the combination process of this invention totaled 17,483 BPD and had an overall pool RON of 104.7 which is substantially higher than the pool octane of 92.0 obtained from the high severity reforming zone by itself.
  • the advantage of employing the combination process of this invention resides in the production of light hydrocarbons consisting of C3 and C4 molecular size which, when further reacted by alkylation, polymerization, hydrolysis or other octane improving processes, yield a gasoline component which improves the overall gasoline pool in octane number and in addition provides additional volumetric yield on the fresh feed.
  • isobutane of which 865 1b./hr. was derived from the reforming zone, 15,139 1b./hr. of propylene and 22,441 lb./hr. of butene which was derived from the saturate cracking zone.
  • isobutane of which 865 1b./hr. was derived from the reforming zone, 15,139 1b./hr. of propylene and 22,441 lb./hr. of butene which was derived from the saturate cracking zone.
  • they were passed into an alkylation zone to produce C3 and C4 alkylate gasoline. Because of the large amounts of propylene and butylene produced, it was required that a certain amount of outside isobutane be used to fully react all of the C3 and C4 olens. A total of about 36,822 lb./hr.
  • the overall octane rating of the gasoline pool of Table V was 101.8 RON.
  • the liquid yied of C-lgasoline produced including the C3 and C4 alkylate gasoline based on the reforming zone feed plus the outside isobutane required, was found to be 25,573.3 BPD of C45- ⁇ - gasoline (25,899.7 BPD of reforming zone feed -l- 3477 BPD of outside isobutane) 87.0 liquid volume percent or 87.0 barrels of 101.8 RON gasoline produced per 100 total barrels of feed to the combination process.
  • the high severity reforming zone gasoline yield was calculated taking account of the isobutane produced by that reformer as being converted to a C4 alkylate gasoline.
  • the 92.0 RON reforming zone produced only isobutane light hydrocarbons which were potentially alkylateable and consequently to take advantage of this high octane precursor outside butene was used in such quantity to convert all of the isobutane from this reforming zone to C4 alkylate gasoline.
  • the outside butylene was chosen to allow production of the high octane C4 alkylate.
  • Table VI shows the total gasoline pool produced by the high severity reforming zone.
  • the overall pool gasoline octane rating of the above gasoline which included the C4 alkylate produced from the isobutane was 92.3 RON.
  • the increase in octane was due to the addition of the 98 RON C4 alkylate gasoline component to the pool gasoline.
  • the liquid volume yield of gasoline based on the reforming zone feed -ithe outside butene need to alkylate the isobutane was 22,655.5 BPD of C5
  • gasoline (25,899.7 BPD of reforming zone feed -i- 476.5 BPD of outside butene) 89.4% or 89.4 barrels of 92.3 RON gasoline per 100 barrels of total feed used.
  • EXAMPLE III In this example, a reforming catalyst similar to the catalyst used in the previous examples was employed. The reforming zone was operated at conventional conditions to effect production of a C5-
  • the overall RON of the above gasoline pool which comprised both C54- reformate and C4 alkylate gasoline was about 101.6.
  • the overall yield on the basis of the total fresh feed including reformate feed-i-butene required to alkylate the isobutane recovered from the reforming zone in the C4-C4 light hydrocarbon stream was about 77.3 L.V. percent versus 87.0 for the combination of this invention. It can be seen that in attempting to produce the higher octane reformate gasolines that reforming alone inherently creates volumetric losses greater than those of the combination of this invention.
  • a process for the production of a high octane gasoline which process comprises the steps of: (a) converting at least a portion of a heavy naphtha in a reforming zone, at relatively low severity reforming conditions, to produce a gasoline reformate containing aromatic and saturated hydrocarbons; (b) passing at least a portion of said saturated hydrocarbons to a saturate cracking zone and cracking said saturated hydrocarbons at conditions to effect the production of saturated and unsaturated light hydrocarbons and gasoline; and, (c) converting a portion of said saturated and unsaturated light hydrocarbons to a gasoline component.
  • a process for the production of an aromatic gasoline, and saturated and unsaturated light hydrocarbons having from 3 to 4 carbon atoms per molecule which process comprises the steps of (a) converting at least a portion of a heavy naptha containing alkanes and naphthenes in a reforming zone, at low severity reforming conditions including greater than about mol percent conversion of said naphthenes to aromatics and less than about 40 mol percent conversion of said alkanes to aromatics, to produce a reformate containing aromatic and saturated hydrocarbons;
US00885859A 1969-12-17 1969-12-17 High octane gasoline production Expired - Lifetime US3714023A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US88585969A 1969-12-17 1969-12-17

Publications (1)

Publication Number Publication Date
US3714023A true US3714023A (en) 1973-01-30

Family

ID=25387844

Family Applications (1)

Application Number Title Priority Date Filing Date
US00885859A Expired - Lifetime US3714023A (en) 1969-12-17 1969-12-17 High octane gasoline production

Country Status (16)

Country Link
US (1) US3714023A (cs)
AR (1) AR212954A1 (cs)
CA (1) CA943484A (cs)
CS (1) CS153570B2 (cs)
DE (1) DE2061945C3 (cs)
DK (1) DK137765B (cs)
EG (1) EG10506A (cs)
ES (1) ES386517A1 (cs)
FR (1) FR2070902B1 (cs)
GB (1) GB1338612A (cs)
IL (1) IL35865A (cs)
NL (1) NL7018328A (cs)
PL (1) PL81513B1 (cs)
TR (1) TR17194A (cs)
YU (1) YU35270B (cs)
ZA (1) ZA708450B (cs)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3873439A (en) * 1973-02-26 1975-03-25 Universal Oil Prod Co Process for the simultaneous production of an aromatic concentrate and isobutane
US3928175A (en) * 1973-05-24 1975-12-23 Mobil Oil Corp Upgrading crude oil by combination processing
US4053388A (en) * 1976-12-06 1977-10-11 Moore-Mccormack Energy, Inc. Process for preparing aromatics from naphtha
US4067798A (en) * 1976-02-26 1978-01-10 Standard Oil Company (Indiana) Catalytic cracking process
US5292976A (en) * 1993-04-27 1994-03-08 Mobil Oil Corporation Process for the selective conversion of naphtha to aromatics and olefins
US20190210942A1 (en) * 2018-01-08 2019-07-11 Swift Fuels, Llc Processes for an improvement to gasoline octane for long chain paraffin feed streams
US10941357B2 (en) 2018-04-16 2021-03-09 Swift Fuels, Llc Process for converting C2—C5 hydrocarbons to gasoline and diesel fuel blendstocks
US11965136B2 (en) * 2021-01-15 2024-04-23 Saudi Arabian Oil Company Cyclization and fluid catalytic cracking systems and methods for upgrading naphtha

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3650943A (en) * 1970-07-10 1972-03-21 Universal Oil Prod Co High octane unleaded gasoline production

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2908629A (en) * 1955-05-31 1959-10-13 Sun Oil Co High octane gasoline manufacture
US3060116A (en) * 1959-11-06 1962-10-23 Socony Mobil Oil Co Inc Combination reforming and cracking process

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3873439A (en) * 1973-02-26 1975-03-25 Universal Oil Prod Co Process for the simultaneous production of an aromatic concentrate and isobutane
US3928175A (en) * 1973-05-24 1975-12-23 Mobil Oil Corp Upgrading crude oil by combination processing
US4067798A (en) * 1976-02-26 1978-01-10 Standard Oil Company (Indiana) Catalytic cracking process
US4053388A (en) * 1976-12-06 1977-10-11 Moore-Mccormack Energy, Inc. Process for preparing aromatics from naphtha
US5292976A (en) * 1993-04-27 1994-03-08 Mobil Oil Corporation Process for the selective conversion of naphtha to aromatics and olefins
US10899684B2 (en) * 2018-01-08 2021-01-26 Swift Fuels, Llc Processes for an improvement to gasoline octane for long chain paraffin feed streams
US20190210942A1 (en) * 2018-01-08 2019-07-11 Swift Fuels, Llc Processes for an improvement to gasoline octane for long chain paraffin feed streams
EP3737734A4 (en) * 2018-01-08 2022-01-26 Swift Fuels, LLC METHODS FOR ENHANCING OCTANE FOR LONG CHAIN PARAFFIN FEED STREAMS
US11306042B2 (en) 2018-01-08 2022-04-19 Swift Fuels, Llc Processes for an improvement to gasoline octane for long-chain paraffin feed streams
US10941357B2 (en) 2018-04-16 2021-03-09 Swift Fuels, Llc Process for converting C2—C5 hydrocarbons to gasoline and diesel fuel blendstocks
US10995282B2 (en) 2018-04-16 2021-05-04 Swift Fuels, Llc Process for converting C2-C5 hydrocarbons to gasoline and diesel fuel blendstocks
US11407949B2 (en) 2018-04-16 2022-08-09 Swift Fuels, Llc Process for converting C2-C5 hydrocarbons to gasoline and diesel fuel blendstocks
US11965136B2 (en) * 2021-01-15 2024-04-23 Saudi Arabian Oil Company Cyclization and fluid catalytic cracking systems and methods for upgrading naphtha

Also Published As

Publication number Publication date
PL81513B1 (cs) 1975-08-30
DK137765B (da) 1978-05-01
DE2061945C3 (de) 1974-06-27
IL35865A0 (en) 1971-02-25
DK137765C (cs) 1978-10-09
CS153570B2 (cs) 1974-02-25
DE2061945A1 (de) 1971-06-24
GB1338612A (en) 1973-11-28
ZA708450B (en) 1971-11-24
EG10506A (en) 1977-03-31
ES386517A1 (es) 1973-03-16
CA943484A (en) 1974-03-12
YU35270B (en) 1980-10-31
FR2070902B1 (cs) 1973-12-07
TR17194A (tr) 1974-04-25
FR2070902A1 (cs) 1971-09-17
NL7018328A (cs) 1971-06-21
AR212954A1 (es) 1978-11-30
IL35865A (en) 1973-11-28
YU306070A (en) 1980-04-30
DE2061945B2 (de) 1973-11-29

Similar Documents

Publication Publication Date Title
US4645585A (en) Production of fuels, particularly jet and diesel fuels, and constituents thereof
US5350504A (en) Shape selective hydrogenation of aromatics over modified non-acidic platinum/ZSM-5 catalysts
US4181599A (en) Naphtha processing including reforming, isomerization and cracking over a ZSM-5-type catalyst
US4457832A (en) Combination catalytic reforming-isomerization process for upgrading naphtha
US8933283B2 (en) Process for the preparation of clean fuel and aromatics from hydrocarbon mixtures catalytic cracked on fluid bed
US3883418A (en) Lead free motor fuel production
KR20100093601A (ko) 고옥탄 가솔린의 생성 및 방향족기의 공생성을 최적화하기 위한 신규 시스템
US2944005A (en) Catalytic conversion of hydrocarbon distillates
US2396331A (en) Conversion of naphthene hydrocarbons
US3714023A (en) High octane gasoline production
US3719586A (en) Naphtha conversion process including hydrocracking and hydroreforming
US4222854A (en) Catalytic reforming of naphtha fractions
US3714022A (en) High octane gasoline production
US3699035A (en) Production of gasoline by averaging and reforming
US2792336A (en) Production of lighter hydrocarbons from petroleum oils involving hydrogenation and catalytic cracking
US3328289A (en) Jet fuel production
US3650943A (en) High octane unleaded gasoline production
US3003949A (en) Process for manufacturing 104-106 r.o.n. leaded gasoline
US3847792A (en) High octane motor fuel production
US2729596A (en) Production of diesel and jet fuels
US3676522A (en) Disproportionation and isomerization for isopentane production
US2400795A (en) Hydrocarbon conversion process
US2918422A (en) Reforming-hydroforming system
US4036735A (en) Process for upgrading motor gasoline
US3153627A (en) Catalytic process

Legal Events

Date Code Title Description
AS Assignment

Owner name: UOP, DES PLAINES, IL, A NY GENERAL PARTNERSHIP

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNOR:KATALISTIKS INTERNATIONAL, INC., A CORP. OF MD;REEL/FRAME:005006/0782

Effective date: 19880916

AS Assignment

Owner name: UOP, A GENERAL PARTNERSHIP OF NY, ILLINOIS

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNOR:UOP INC.;REEL/FRAME:005077/0005

Effective date: 19880822