US3374167A - Preparation of motor fuels having an octane number above 100 - Google Patents

Preparation of motor fuels having an octane number above 100 Download PDF

Info

Publication number
US3374167A
US3374167A US530989A US53098966A US3374167A US 3374167 A US3374167 A US 3374167A US 530989 A US530989 A US 530989A US 53098966 A US53098966 A US 53098966A US 3374167 A US3374167 A US 3374167A
Authority
US
United States
Prior art keywords
octane number
reforming
reformate
catalyst
heartcut
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
US530989A
Other languages
English (en)
Inventor
Robert G Craig
Friedman Lee
William A Schwartz
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.)
Air Products and Chemicals Inc
Original Assignee
Air Products and Chemicals Inc
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 Air Products and Chemicals Inc filed Critical Air Products and Chemicals Inc
Priority to US530989A priority Critical patent/US3374167A/en
Priority to GB53155/66A priority patent/GB1160258A/en
Priority to DE19661545224 priority patent/DE1545224B2/de
Priority to FR86685A priority patent/FR1504192A/fr
Application granted granted Critical
Publication of US3374167A publication Critical patent/US3374167A/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
    • 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
    • C10G35/00—Reforming naphtha
    • C10G35/04—Catalytic reforming
    • C10G35/06—Catalytic reforming characterised by the catalyst used
    • C10G35/085—Catalytic reforming characterised by the catalyst used containing platinum group metals or compounds thereof
    • 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
    • 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

  • This invention relates to the use of platinum catalyst for reforming at nonregenerative conditions for the prepzlgztion of liquid fuels having an octane number above
  • technologists have been aware of methods for preparing selected fractions of hydrocarbons having an octane number above 100. For example, con centration of aromatics by fractionation or extraction can provide a fraction having an octane number above 100.
  • Refiners are primarily interested, however, in a full range stabilized gasoline making effective use of the components available in the raw petroleum.
  • Nonregenerative reforming of virgin naphtha over platinum catalyst in the presence of a recycle gas containing a predominant volume of hydrogen has been a preferred route toward upgrading the octane number of virgin naphtha.
  • a motor fuel having an octane number (F clear) above 100 is prepared by subjectng a virgin naphtha to reforming at con ditions providing an octane number of the reformate within the range from about 85 to about 93 F clear octane number, and this reformate is subjected to distilla tion to prepare a heartcut having the approximately 72- 162 C. boiling point range, subjecting such heartcut to the severe reforming hereinafter specified, and blending the thus prepared fuel with the bottorns and forecut from the distillation of the reformate from the first stage of reforming.
  • the thus blended fuel is ;a stabilized, full range gasoline having an octane number above 100.
  • this cut can be readily re forrned at the indicated high severity without undue loss of catalyst activity and without necessitating frequent catalyst regeneration.
  • the selected reformate heartcut subjected to further severe reforming is one having an initial boiling point within the range from about C. to about C. whereby normal hexane and lower boiling paraflns are substantially excluded; and an end boiling point in the range from about C. to C., whereby polycyelic hydrocarbons are substantially excluded.
  • the process conditions include: controlling the hydrogen to hydrocarbon unit mol ratio within the range from 3 to 8, wherein the hydrogen purty of the recycled gas is rnaintained by withdrawing a portion of the efiuent gas; controlling the space velocity within the range of 1 to 3 volumes of liquid hydrocarbon per volume of catalyst per hour whereby the capital investment in catalyst is not prohibitive; controlling the pressure of the reforming zone within the range from 15 to 30 atmospheres, whereby operation for periods longer than 60 days between regenerations are feasible; and controlling the temperature within the range from 480 C. to 550 C., whereby the catalyst stability is maintained throughout a series of regenerations, permtting the ultimate useful life of the platinum catalyst to be adequate.
  • the invention is further clarified by reference to a plurality of examples illustrating a few of the permssible varables within the broadest concept of the invention.
  • Example 1 A crude petroleum is distilled to provide a virgin naphtha having characteristics as follows.
  • This naphtha is subjected t0 reforming over a platinum on alumina catalyst to produce a reformate havng an F octane rating of about 90.5.
  • T his full range reformate is distilled to separate it into 3 ractions, a forerun containing hydrocarbons having an end boiling point of about 70 C. and heartcut having a bolling point range from 70 C. to 165 C., and a bottoms fraction having an initial boilng point of about 165 C.
  • the characteristics of the full range reformate and three fractions are approximately as follows:
  • HEAR'ICUI Volume Percent oi Heartcu 90.5 F1 reiormate O6 parafns 1. 0 0.61 0 paraflns.- 10.6 6. 51 0x paraflns...- 13. 3 8.17 09 paraflns 11.9 7. 31 010 params... 5. 5 3.38 011 paraffins 0.5 0.31 012 parafins.- O ring naphthenes 7. 0 4. 30 C ring naphthenes. 0. 6 0. 37 0. 5 0.31 10.1 6. 20 20. 7 12. 70 17.1 10. 79 0. 8 0. 49 Indane 0. 4 0.25
  • the reforming catalyst employed consists of alumina pellets about 1.6 mm. diameter and about 4 to 5 mm. long, having a platinum content of 0.50%, 21 packed bulk density of 840 g. per liter, a su-rface area of 260 rn./g., a pore volume of 0.40 cc./g., ar1 average pore radius of about 31 angstroms, a crushing strength of 4.4 kg. and an ignition loss at 760 C. of 2.5%.
  • the 103-163 C. heartcut is subjected to severe nonregenerative reforrning over a platinum on alumina catalyst at a temperature of 500 C. at a space rate of one and at a hydrogen to hydrocarbon ratio of 8 to 1.
  • the reformate obtained by such severe reforming is admixed with the forecut and bottorns from the previous distillation, and the blend is a full range gasoline having -an octane number above 100.
  • Examples II-V A heartcut from a reformate having characteristics re sernbling the heartcut of Example I was subjected to high g conditons permit clear octane of at least As prevously explained, the operatin greater severty, whereby an F III IV dicated in the followng table Example No Hrs. on Cat tor Run Tota1 Hrs. on Catal Operatng Conditi 75 the catalyst fewer than six t1mes per year (nonregenera tive operation for more than 60 days) are attainable at the 103.8 octane level appropriate for achieving a blend having an F octane number of at least 100.
  • Example VI A virgin naphtha is distilled to separate a heartcut having a boiling point range from about 75 C. to about 160 C. This heartcut is mixed with 3 mols of hydrogen and passed at a temperature of 520 C. at a pressure of 15 atmospheres over a platinum on alumina catalyst at a space rate of about one. The reformate thereby produced has an octane rating of about 103 F clear. The forerun and bottoms are separately reformed at conditions milder than required for the heartcut, and the blend with the severely reforrned heartcut is a full range gasoline having an F clear octane number of 100.1.
  • the same vrgin naphtha is reformed to provide a refor-mate having a 93 F clear octane, and the 75- 160 C. heartcut is subjected to severe reforming to provide a fraction having an F clear octane of 103, and blended with the forecut and bottoms to provide a blend having an F clear octane number of 100.1.
  • the yield of 100 octane gasoline is greater when the reformate heartcut is subjected to the severe reforming than when the naphtha is subjected to such severe conditions.
  • the deactivation rate for the catalyst inventory is more favorable if the full range naphtha is first reformed to the 93 F clear reformate prior to separating the heartout for severe reforming.
  • Example VII A variety of reformates derived from a variety of naphthas are evaluated to estimate the suitability of the severe reforming method.
  • Each full range reformate has an F clear octane number within the range from 85 to 93.
  • the heartcut from 75 C. to 160 C. from each reformate is subjected to severe reforming to provide an upgracled fraction having an F clear octane number within the range from 102 to 105. Higher octane number of the severely reformed heartcut is necessary when the initial reformate is closer to the lower limit.
  • a blend having an F clear octane in the range from 100.1 to 101 is acheved.
  • the quantity of C C hydrocarbons produced at the high severity reforming is quite large, especially in relation to the quantity of hydrogen generated.
  • supplemental hydrogen must be introduced to preserve an adequately high hydrogen purty.
  • the costs of rnaintainng a hydrogen to liquid hydrocarbon ratio such as 8 become excessve if the hydrogen purty is quite low, such as 33% by volume of recycle gas.
  • the recycle gas for the severe reformer can have an acceptable proportion of hydrogen.
  • supplemental hydrogen can be directed through the severe re former if r1ot operating in close proximity to the first stage reforrner.
  • the hydrogen to liquid hydrocarbon unit ratio is thus maintained between 3 and 8.
  • the total pressure is maintained within the range from 15 to 30 atmospheres.
  • the reforming temperature is at least 480 C. but less than 550 C.
  • Space rate is regulated from 1 to 3 volumes of heartcut per volume of catalyst per hour.
  • the improvement which consists of the combination of: fractionating a primary full range reformate of liquid hydrocarbons of 85 to 93 octane (F clear) to provide a heartcut haviug an initial boiling point of at least C., whereby normal hexane and lower boiling paraflins are substantially excluded, said cut having an end boiling point below 170 C., whereby polycyclic aromatics are substantially excluded; reforming said heartcut over supported platinum catalyst at severe conditions including hydrogen to liquid hydrocarbon unit ratio in the range from 3 to 8, space velocity from 1 to 3 volumes of liquid per volume of catalyst per hour, temperature in the range of 480 C.

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)
US530989A 1966-03-01 1966-03-01 Preparation of motor fuels having an octane number above 100 Expired - Lifetime US3374167A (en)

Priority Applications (4)

Application Number Priority Date Filing Date Title
US530989A US3374167A (en) 1966-03-01 1966-03-01 Preparation of motor fuels having an octane number above 100
GB53155/66A GB1160258A (en) 1966-03-01 1966-11-28 Preparation of Motor Fuels Having and Octane Number Above 100
DE19661545224 DE1545224B2 (de) 1966-03-01 1966-12-02 Verfahren zur erhoehung der octanzahl eines fluessigen kohlenwasserstoffgemisches
FR86685A FR1504192A (fr) 1966-03-01 1966-12-08 Procédé et installation pour la fabrication de carburant pour moteur à indice d'octane élevé

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US530989A US3374167A (en) 1966-03-01 1966-03-01 Preparation of motor fuels having an octane number above 100

Publications (1)

Publication Number Publication Date
US3374167A true US3374167A (en) 1968-03-19

Family

ID=24115810

Family Applications (1)

Application Number Title Priority Date Filing Date
US530989A Expired - Lifetime US3374167A (en) 1966-03-01 1966-03-01 Preparation of motor fuels having an octane number above 100

Country Status (4)

Country Link
US (1) US3374167A (fr)
DE (1) DE1545224B2 (fr)
FR (1) FR1504192A (fr)
GB (1) GB1160258A (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3516924A (en) * 1968-04-19 1970-06-23 Universal Oil Prod Co Catalytic reforming process
US3664949A (en) * 1969-11-10 1972-05-23 Standard Oil Co Platinum reforming with a mordenite containing support using two reactors
US3883418A (en) * 1973-01-02 1975-05-13 Phillips Petroleum Co Lead free motor fuel production

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
USRE31647E (en) * 1980-03-17 1984-08-14 Mobil Oil Corporation Startup procedure for reforming catalysts

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2905621A (en) * 1956-03-02 1959-09-22 Phillips Petroleum Co Two stage reforming with noble metal catalyst

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2905621A (en) * 1956-03-02 1959-09-22 Phillips Petroleum Co Two stage reforming with noble metal catalyst

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3516924A (en) * 1968-04-19 1970-06-23 Universal Oil Prod Co Catalytic reforming process
US3664949A (en) * 1969-11-10 1972-05-23 Standard Oil Co Platinum reforming with a mordenite containing support using two reactors
US3883418A (en) * 1973-01-02 1975-05-13 Phillips Petroleum Co Lead free motor fuel production

Also Published As

Publication number Publication date
DE1545224A1 (de) 1969-07-10
GB1160258A (en) 1969-08-06
DE1545224B2 (de) 1976-04-15
FR1504192A (fr) 1967-12-01

Similar Documents

Publication Publication Date Title
US3726789A (en) Hydrocarbon conversion process for the production of olefins and aromatics
KR0136582B1 (ko) 한정된 c9+탄화수소 함량을 갖는 탄화수소 분류물의 개질 방법
US7485768B1 (en) Processes for making higher octane motor fuels having a low reid vapor pressure from naphtha boiling range feedstocks
US4673488A (en) Hydrocarbon-conversion process with fractionator overhead vapor recycle
US2289716A (en) Catalytic motor fuel production
US4067798A (en) Catalytic cracking process
US3172842A (en) Hydrocarbon conversion process includ- ing a hydrocracking stage, two stages of catalytic cracking, and a reform- ing stage
US2360463A (en) Hydrocarbon conversion
US4798665A (en) Combination process for the conversion of a distillate hydrocarbon to maximize middle distillate production
US2534025A (en) Production of aviation or motor fuels
US3389075A (en) Process for producing aromatic hydrocarbons and liquefied petroleum gas
US3037930A (en) Two-stage conversion process for the production of aromatic product fractions
US3699035A (en) Production of gasoline by averaging and reforming
US3374167A (en) Preparation of motor fuels having an octane number above 100
US2908628A (en) Hydrocarbon conversion
US3172841A (en) Process for upgrading natural sas condensates
US3304340A (en) Aromatics production
US3328289A (en) Jet fuel production
US2932611A (en) Process of catalytic desulfurization and hydrocracking of hydrocarbons followed by catalytic cracking
US3714022A (en) High octane gasoline production
US3280022A (en) Dehydrocyclization process for producing a high octane gasoline and aromatics
US2987466A (en) Process for the production of high octane gasolines
US3185639A (en) Hydrocarbon conversion process
US3714023A (en) High octane gasoline production
US2400795A (en) Hydrocarbon conversion process