US3658690A - Gasoline upgrading - Google Patents

Gasoline upgrading Download PDF

Info

Publication number
US3658690A
US3658690A US19377A US3658690DA US3658690A US 3658690 A US3658690 A US 3658690A US 19377 A US19377 A US 19377A US 3658690D A US3658690D A US 3658690DA US 3658690 A US3658690 A US 3658690A
Authority
US
United States
Prior art keywords
gasoline
hydrocarbons
isomerization
octane
reforming
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
US19377A
Other languages
English (en)
Inventor
Richard G Graven
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.)
ExxonMobil Oil Corp
Original Assignee
Mobil Oil Corp
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 Mobil Oil Corp filed Critical Mobil Oil Corp
Application granted granted Critical
Publication of US3658690A publication Critical patent/US3658690A/en
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

Definitions

  • the present invention is directed to a processing arrangement for upgrading gasoline boiling range material of unsatisfactory octane rating to a higher octane gasoline product suitable for use in gasoline combustion engines without lead additives.
  • the present invention is directed to the combination of processing steps comprising hydrogenation, reforming, aromatic extraction and C hydrocarbon isomerization as they relate to one another in the combination for upgrading low octane constituents of the gasoline charge to acceptable higher octane product.
  • One important aspect of the processing combination of this invention relates to upgrading low octane C hydrocarbon components.
  • DESCRIPTION OF A SPECIFIC EMBODIMENT THe present invention is concerned with a processing arrangement which may be utilized in present day refinery operations to upgrade low octane gasoline material and particularly C components thereof to a much higher octane product suitable for blending with reformed gasoline product of a desired higher octane rating. More particularly the processing arrangement identified by this invention upgrades particularly C and higher boiling hydrocarbons in the gasoline boiling range by the operating arrangement of reforming, isomerization, aromatic recovery with intervening stabilization and fractionation designed to particularly upgrade, with much greater emphasis, the low octane C hydrocarbon components.
  • a relatively low octane gasoline boiling charge such as defined below and having an initial boiling point of about C hydrocarbons and an end boiling point of about 380 F. is introduced to the process by line 2 for passage to hydrogenation pretreater 4 such as desulfurization.
  • pretreater 4 the gasoline charge is subjected to hydrogenation conditions which will be effective for removing sulfur and nitrogen components found in the gasoline charge.
  • the amount of sulfur and nitrogen components in the charge will vary considerably depending upon the source of the gasoline charge. That is, the gasoline charge may be either a straight run naphtha, coker gasoline, gasoline product of hydrocracking or catalytic cracking, and/or mixtures thereof.
  • the hydrogenated charge is thereafter stabilized as by fractionation to remove undesired low boiling constituents.
  • the stabilized charge is passed by line 6 to a depentanizer tower 8.
  • the depentanizer tower 8 is maintained under operating conditions particularly selective to separate C and lower boiling hydrocarbons from a higher boiling hydrocarbon fraction comprising C and higher boiling hydrocarbons.
  • the C and lower boiling hydrocarbons are removed from the upper portion of tower 8 by line 10.
  • the C and higher boiling hydrocarbons having, for example, the composition of C and higher boiling gasoline hydrocarbons are withdrawn from the bottom of depentanizer tower 8 by line 12.
  • the separation effected in depentanizer tower 8 is designed to carry substantially all of the C and higher boiling hydrocarbons into the bottom phase and thus it is expected that some C hydrocarbons will be carried along therewith.
  • the bottom fraction in line 12 is primarily C and higher boiling hydrocarbons comprising the higher boiling components of the gasoline fraction boiling up to about 380 F.
  • Desulfurization of the gasoline boiling charge may be effected after passing through the depentanizer rather than before.
  • the thus obtained depentanized charge is passed by line 12 to a platinum reforming operation in zone 14 wherein the reforming severity conditions are selected to provide reformate product varying considerably in octane rating.
  • octane rating as high as about 104 or 106 octane numbers clear or it may be considerably lower and as low as octane clear basis.
  • the reforming operation effected in zone 14 relies upon a platinum-type reforming catalyst provided with suitable catalyst promoters to achieve the results desired.
  • a typical reforming operation known in the prior art and comprising three or more reactors with separation equipment so that the effluent obtained from reforming will pass through one or more separation zones to stabilize the reformate product and effect the recovery of normally gaseous components rich in hydrogen from a higher boiling reformate product containing C and higher boiling hydrocarbons.
  • the separated normal gaseous components not shown in the drawing and comprising a hydrogen rich recycle gas may be recycled to the reformer or used in another suitable portion of the processing sequence herein discussed.
  • the reformate product obtained from reforming zone 14 and comprising primarily C and higher boiling hydrocarbons is then passed by line 16 to a depentanizer tower 18.
  • Depentanizer tower 18 is maintained under conditions designed to permit separation and recovery of primarily C and higher boiling hydrocarbons having the characteristics identified in Table 1.
  • This C and higher boiling reformate fraction is withdrawn from the bottom portion of the tower by line 20 with primarily C hydrocarbon components and any lower boiling material being withdrawn from the upper portion of the tower by line 22.
  • the C and lower boiling hydrocarbonsrecovered from depentanizers 8 and 18 are combined and passed to a debutanizer tower 24 wherein C and lower boiling hydrocarbons are separated from C hydrocarbons.
  • the C and lower boiling hydrocarbons are withdrawn from debutanizer tower 24 by line 26.
  • the C hydrocarbon rich stream comprising about 50.4% n-C hydrocarbons are passed by line 28 to deisopentanizer tower 30.
  • deisopentanizer tower 30 a separation is made between normal pentane and isopentane so that a 95 percent rich isopentane stream may be withdrawn from the upper portion of the tower by line 32.
  • Normal pentane is recovered from the bottom of tower 30 and passed by line 34 to an isomerization zone 36.
  • lsomerization zone 36 is relied upon to convert normal pentane to isopentane and the product obtained therefrom is passed to deisopentanizer tower 30 by way of line 38 and 28.
  • the isomerization of pentanes is well known in the art and known catalyst compositions and operating conditions may be employed to effect such an isomerization. It is intended that any of the well known and reliable isomerization processes be employed and particularly one which will economically convert normal pentane to isopentane.
  • the product obtained from isomerizing step 36 is passed to tower 30 by line 38 for effecting separation of normal from isopentane.
  • the recovered isopentane in line 32 may then be employed as blending stock in gasoline product or used for other purposes known in the art.
  • the reforming effluent recovered from the bottom of depentanizer tower 18 and having the composition identified in Table 1 above is thereafter passed by line 20 to dehexanizer tower 40 wherein the operating conditions are maintained to effect a separation between a hydrocarbon fraction boiling in the range of from about C hydrocarbons up to a cut point in the range of from about F. to 225 F. from a reformate fraction boiling above the cut point selected and comprising the high octane gasoline reformate product of reforming zone 14.
  • Reformer pressure 350 psig Start-of-cycle Conditions Reformer Severity, C,
  • the light hydrocarbon fractions resulting from reformate splitting may be upgraded by processes such as hexane isomerization, shape selective processing and alkylation after conversion to suitable olefins, or disposed of as fuel.
  • the octane number of these light fractions are represented below.
  • the hydrocarbon fraction in line 44 is first treated to remove aromatics therefrom and C hydrocarbons. Since it is known that aromatics in an isomerization charge have an undesirable in- I fluence upon the isomerization reaction, the aromatics are removed such as by liquid phase extraction, molecular sieve adsorption techniques or any other available means for ac complishing the same.
  • the aromatics thus recovered are removed by line 48 for use as desired. In some instances they may be combined with the gasoline product or used in the chemical industry.
  • the aromatics may be separately recovered through line 50.
  • the aromatic freed hydrocarbon fraction comprising C hydrocarbons and possibly some C hydrocarbons is thereafter passed to tower 47 provided to effect separation of C hydrocarbons which are withdrawn from the bottom of the tower.
  • the remaining C hydrocarbon stream is then passed by line 52 to hydrogenation step 54 wherein the conditions employed are such as to hydrogenate any aromatics remaining in the charge after the treatment just discussed.
  • the hydrogenated product freed of aromatics and difficulty isomerizable C hydrocarbons is then passed by line 56 to isomerization zone 58.
  • the conditions of operation such as low temperatures are selected which will be effective in producing 2,2-dimethylbutane.
  • the products of isomerization obtained in zone 58 are then passed by line 60 to a separator tower 62 wherein separation is made, for example, to recover 2,2-dimethylbutane along with some 2,3- dimethylbutane from the upper portion of the tower by line 64.
  • Higher boiling material is withdrawn from the bottom portion of the tower by line 66 for passage, all or in part, to platinum reforming or recycle by line 68 to isomerization step 58.
  • Care must be taken to avoid build-up of naphthenes as by recycle in the charge to the isomerization zone 58 and thus conversion of this material as by platinum reforming, thermal and catalytic cracking and olefinic product thereof by alkylation is contemplated.
  • the combination of reforming and isomerization discussed herein is relied upon to upgrade the gasoline charge comprising C and higher boiling hydrocarbons.
  • the reforming opera- -tion either a regenerative type such aspowerforming or a semiregenerative type is effected in a plurality of reactors suitably connected as known in the prior art at a temperature in the range of from about 700 F up to about l,050 F. to effeet the known reforming reactions of dehydrogenation,
  • the reforming operation may be effected at a'pressure in the range offrom about 100 psig up to about 1,000'psig, it'being preferred to employ as low a pressure as possible to achieve the results desired. Generally the pressure will not be significantly above 500 psig and more usually the pressure will-be below about 350 or 400 psig.
  • a liquid hourly space velocity selected from within the range of 0.5 up to about may be employed in the presence of hydrogen in a mol ratio with hydrocarbon in the range of 0.5 up to about 20.
  • the reforming catalysts employed are usually Group Vlll metals of the platinum type dispersed on a suitable carrier material such as alumina in the eta, gamma or mixed eta-gamma form.
  • the platinum hydrogenation-dehydrogenation component may be used alone or in combination with other metal promoters known in the art.
  • the amount of platinum used varies in the range of from about 0.01 percent up to as high as about 2 or 3 percent, it being preferred to use less than about 1 percent in most cases.
  • the reforming catalyst may contain a halogen promoter and is usually of a particle form size suitable for use in a fixed bed reforming operation.
  • the isomerization of either C or C hydrocarbons may be efiected with solid type isomerization catalyst rather than the more corrosive liquid isomerization catalysts.
  • a solid type of reforming catalyst may comprise platinum disposed on alumina and promoted with an acidic agent such as halogen or boron.
  • Low temperatures are particularly desirable in the isomerization reactions.
  • the production of neohexane by aluminum chloride isomerization at temperatures above and below about 200 F. is known.
  • isomerizing with the solid type of isomerization catalyst at temperatures in the range of from about 200 F. up to about 800 F. may be employed with low temperatures in the range of 200 F. to about 350 F. preferred.
  • the isomerizing pressure may be selected from within the range of 50 psig up to about 1,000 psig but is preferably selected from within the range of l00 to about 500 psig.
  • the operating conditions will be selected so that a selective operation is pursued which minimizes cracking and other undesired side reactions. Therefore, in the interest of optimizing the selectivity of the present operation, normal pentanes are separately isomerized from the normal hexanes. The isomerization of pentanes and hexanes is discussed in the literature and the method of the present invention intends to rely upon this information to its maximum advantage.
  • C hydrocarbons isolated by the method of the present invention is particularly important since such aromatics in the charge to isomerization are known to be most undesirable. Furthermore, C hydrocarbons are isomerized only with extreme difficulty and their removal from the C hydrocarbon charge to be isomerized is also most desirable.
  • the removal of aromatics such as benzene and toluene may be accomplished by extraction, molecular sieve adsorption or any other known available method. Thereafter C hydrocarbons may be removed from normal C hydrocarbons by fractionation carefully controlled.
  • a combination process for upgrading gasoline boiling range material obtained as straight run naphtha, coker gasoline, gasoline product of hydrocracking and catalytic cracking and mixtures thereof which comprises:
  • step (e) isomerizing said rich C hydrocarbon stream from step (e) under conditions selected to produce significant quantities of C isomers and g. recovering C isomers as blending components for use in regular and premium gasoline.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
US19377A 1970-03-13 1970-03-13 Gasoline upgrading Expired - Lifetime US3658690A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US1937770A 1970-03-13 1970-03-13

Publications (1)

Publication Number Publication Date
US3658690A true US3658690A (en) 1972-04-25

Family

ID=21792866

Family Applications (1)

Application Number Title Priority Date Filing Date
US19377A Expired - Lifetime US3658690A (en) 1970-03-13 1970-03-13 Gasoline upgrading

Country Status (2)

Country Link
US (1) US3658690A (fr)
BE (1) BE763045A (fr)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3755140A (en) * 1971-08-11 1973-08-28 Universal Oil Prod Co Simultaneous production of aromatic hydrocarbons and isobutane
US3950242A (en) * 1974-04-02 1976-04-13 Mobil Oil Corporation Fluid catalytic cracking plus selective upgrading of cracked gasoline
US4594144A (en) * 1985-06-14 1986-06-10 Uop Inc. Process for making high octane gasoline
US5242576A (en) * 1991-11-21 1993-09-07 Uop Selective upgrading of naphtha fractions by a combination of reforming and selective isoparaffin synthesis
US5288393A (en) * 1990-12-13 1994-02-22 Union Oil Company Of California Gasoline fuel
US5414172A (en) * 1993-03-08 1995-05-09 Mobil Oil Corporation Naphtha upgrading
US20030173250A1 (en) * 2002-03-13 2003-09-18 Blackwood David Macdonald Unleaded gasoline compositions
US20110040136A1 (en) * 2008-04-25 2011-02-17 IFP Energies Nouvelles Elimination of chlorine compounds from hydrocarbon cuts

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2905619A (en) * 1956-06-28 1959-09-22 Universal Oil Prod Co Upgrading gasoline
US2965561A (en) * 1956-12-24 1960-12-20 Pure Oil Co Process for upgrading desulfurized naphthas
US3001927A (en) * 1958-11-03 1961-09-26 Universal Oil Prod Co Conversion of hydrocarbon distillates to motor fuel mixtures rich in aromatic and isoparaffins
US3121676A (en) * 1961-08-17 1964-02-18 Phillips Petroleum Co Up-grading hydrocarbons
US3165461A (en) * 1959-08-07 1965-01-12 Standard Oil Co Neohexane production
US3280022A (en) * 1964-02-20 1966-10-18 Phillips Petroleum Co Dehydrocyclization process for producing a high octane gasoline and aromatics

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2905619A (en) * 1956-06-28 1959-09-22 Universal Oil Prod Co Upgrading gasoline
US2965561A (en) * 1956-12-24 1960-12-20 Pure Oil Co Process for upgrading desulfurized naphthas
US3001927A (en) * 1958-11-03 1961-09-26 Universal Oil Prod Co Conversion of hydrocarbon distillates to motor fuel mixtures rich in aromatic and isoparaffins
US3165461A (en) * 1959-08-07 1965-01-12 Standard Oil Co Neohexane production
US3121676A (en) * 1961-08-17 1964-02-18 Phillips Petroleum Co Up-grading hydrocarbons
US3280022A (en) * 1964-02-20 1966-10-18 Phillips Petroleum Co Dehydrocyclization process for producing a high octane gasoline and aromatics

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3755140A (en) * 1971-08-11 1973-08-28 Universal Oil Prod Co Simultaneous production of aromatic hydrocarbons and isobutane
US3950242A (en) * 1974-04-02 1976-04-13 Mobil Oil Corporation Fluid catalytic cracking plus selective upgrading of cracked gasoline
US4594144A (en) * 1985-06-14 1986-06-10 Uop Inc. Process for making high octane gasoline
US6030521A (en) * 1990-12-13 2000-02-29 Union Oil Company Of California Gasoline fuel
US5288393A (en) * 1990-12-13 1994-02-22 Union Oil Company Of California Gasoline fuel
US5593567A (en) * 1990-12-13 1997-01-14 Jessup; Peter J. Gasoline fuel
US5653866A (en) * 1990-12-13 1997-08-05 Union Oil Company Of California Gasoline fuel
US5837126A (en) * 1990-12-13 1998-11-17 Union Oil Company Of California Gasoline fuel
US5242576A (en) * 1991-11-21 1993-09-07 Uop Selective upgrading of naphtha fractions by a combination of reforming and selective isoparaffin synthesis
US5414172A (en) * 1993-03-08 1995-05-09 Mobil Oil Corporation Naphtha upgrading
US20030173250A1 (en) * 2002-03-13 2003-09-18 Blackwood David Macdonald Unleaded gasoline compositions
US20110040136A1 (en) * 2008-04-25 2011-02-17 IFP Energies Nouvelles Elimination of chlorine compounds from hydrocarbon cuts
US8771501B2 (en) * 2008-04-25 2014-07-08 IFP Energies Nouvelles Elimination of chlorine compounds from hydrocarbon cuts

Also Published As

Publication number Publication date
BE763045A (fr) 1971-07-16

Similar Documents

Publication Publication Date Title
US5003118A (en) Isomerization of benzene-containing feedstocks
EP0334561A1 (fr) Procédé de reformage d'une fraction hydrocarbonée avec teneur limitée en C9+
US2289716A (en) Catalytic motor fuel production
WO1994002438A1 (fr) Procede de reformage permettant de produire du benzene de grande purete
US4155835A (en) Desulfurization of naphtha charged to bimetallic catalyst reforming
US3806443A (en) Selective hydrocracking before and after reforming
US3451922A (en) Method for hydrogenation
US3649520A (en) Production of lead free gasoline
US3470085A (en) Method for stabilizing pyrolysis gasoline
US3380912A (en) Combination extraction-demetalation process for heavy oils
US3658690A (en) Gasoline upgrading
US2944006A (en) Hydrocracking of a hydrocarbon distillate employing a sulfide of nickel or cobalt, disposed on an active siliceous cracking catalyst support
US4222854A (en) Catalytic reforming of naphtha fractions
US2574451A (en) Catalytic desulfurization of petroleum hydrocarbons
US3055823A (en) Multi-stage hydrofining-hydrocracking process employing an intermediate treating operation
US3457163A (en) Method for selective hydrogenation of diolefins with separation of gum formers prior to the reaction zone
US3718576A (en) Gasoline production
US2908628A (en) Hydrocarbon conversion
US2647076A (en) Catalytic cracking of petroleum hydrocarbons with a clay treated catalyst
US2880164A (en) Manufacture of anti-knock gasoline
US2968609A (en) Process for fractionating and blending a reformate to obtain a high octane gasoline
US3896025A (en) Production of improved lubricating oils
US2889263A (en) Hydroforming with hydrocracking of recycle paraffins
US3540996A (en) Split feed naphtha reforming
US3481996A (en) Process for hydrodesulfurization of cracked gas oils and the production of dimethyldecalins and fuel oil blending components