US3374167A - Preparation of motor fuels having an octane number above 100 - Google Patents
Preparation of motor fuels having an octane number above 100 Download PDFInfo
- 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
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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)
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 (de) |
DE (1) | DE1545224B2 (de) |
FR (1) | FR1504192A (de) |
GB (1) | GB1160258A (de) |
Cited By (3)
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)
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)
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 |
-
1966
- 1966-03-01 US US530989A patent/US3374167A/en not_active Expired - Lifetime
- 1966-11-28 GB GB53155/66A patent/GB1160258A/en not_active Expired
- 1966-12-02 DE DE19661545224 patent/DE1545224B2/de not_active Withdrawn
- 1966-12-08 FR FR86685A patent/FR1504192A/fr not_active Expired
Patent Citations (1)
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)
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 |
---|---|
GB1160258A (en) | 1969-08-06 |
FR1504192A (fr) | 1967-12-01 |
DE1545224A1 (de) | 1969-07-10 |
DE1545224B2 (de) | 1976-04-15 |
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