US3926779A - Upgrading of paraffinic gasoline blending components by cyclization with a platinum/magnesium oxide alumina matrix catalyst - Google Patents
Upgrading of paraffinic gasoline blending components by cyclization with a platinum/magnesium oxide alumina matrix catalyst Download PDFInfo
- Publication number
- US3926779A US3926779A US435363A US43536374A US3926779A US 3926779 A US3926779 A US 3926779A US 435363 A US435363 A US 435363A US 43536374 A US43536374 A US 43536374A US 3926779 A US3926779 A US 3926779A
- Authority
- US
- United States
- Prior art keywords
- platinum
- process according
- noble metal
- reforming
- catalyst
- 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
Links
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
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/04—Mixing
-
- 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
- C10G35/09—Bimetallic catalysts in which at least one of the metals is a platinum group metal
Definitions
- Theoctane number of paraffinic gasoline blending components may be increased by (1) cyclizing the nparaffins with hydrogen under reforming conditions in the presence of a catalyst prepared by depositing a noble metal on magnesium oxide and mixing the resulting noble metal-magnesia into an alumina gel matrix, and (2) subjecting the cyclized component to conventional catalytic reforming.
- Normal and slightly branched chain paraffinic hydrocarbons of the type contained in reforming feedstock fractions have relatively low octane ratings.
- Highly branched chain paraffinic hydrocarbons are characterized by high octane ratings.
- one objective of the reforming operation is to effect isomerization of the normal and slightly branched chain paraffins to more highly branched chain paraffins.
- aromatic hydrocarbons have much higher octane ratings than naphthenic hydrocarbons, it is also an objective of reforming simultaneously to produce aromatics in good yield.
- the production of aromatic hydrocarbons during reforming is effected by dehydrogenation of the naphthenic hydrocarbons and dehydrocyclization of the paraffinic hydrocarbons.
- Aromatic hydrocarbons are also produced by isomerization of alkyl cyclopentanes to cyclohexanes, which thereafter undergo dehydrogenation to form the desired aromatics.
- a convenient measure of the effectiveness of a reforming operation is based on a yield-octane relationship. It is desired in reforming to maximize this relationship, i.e., high depentanized yields for any given octane
- Certain hydrocarbon fractions which fall within the boiling point range for gasoline blending components are composed principally of normal and slightly branched chain paraffins. These paraffinic stocks are very low in octane number and therefore, unless they are subjected to a reforming operation, they are not suitable for inclusion in lead free gasolines.
- a further object of this invention is to develop an effective catalyst for the upgrading of highly paraffinic gasoline blending components.
- paraffinic gasoline blending components are upgraded by a two step process involving (1) cyclization of paraffins, and (2) catalytic reforming of the cyclized product in the usual manner.
- the cyclization step is accomplished by contacting the paraffinc gasoline blending component with hydrogen in the presence of a novel catalyst prepared by depositing a noble metal on magnesium oxide and then mixing this noble metal-magnesia into an alumina matrix.
- US. Pat. No. 3,654,184 issued to McCallister et al, discloses a platinum/germanium oxide/alumina gel catalyst. A soluble platinum compound is combined with an aqueous solution of germanium oxide. A halogenated alumina gel is then impregnated with the combined solution.
- the disclosure is specific to the use of a germanium oxide solution; there is no indication that magnesium or any other metal may be used in place of the germanium and, further, there is no indication that the platinum may be deposited on a solid chemical rather than being mixed with a solution.
- the paraflinic gasoline blending component which constitutes the feedstock in the process of the instant invention is typically a hydrocarbon fraction boiling within the gasoline boiling range and having a paraffin content of from about percent or higher, most of the paraffins being in straight chain or slightly branched compounds.
- suitable feedstocks are light straight run naphthas, raffinates and condensates.
- the paraffinic stock is cyclized by contacting with hydrogen under reforming conditionswith the novel catalyst of noble metal on magnesium oxide and then mixing the resultant intermediate into an alumina matrix.
- the noble metal is, for example, palladium or platinum, with platinum being preferred.
- the deposition of the noble metal on the magnesium oxide is conveniently accomplished by impregnating magnesium oxide powder with a solution of the noble metal compound.
- the noble metal compound examples include platinum chloride, chloroplatinic acid, ammonium chloroplatinate, dinitrodiamino platinum, palladium chloride, chloropalladic acid, and the like.
- the noble metal is platinum
- the preferred soluble platinum compound is chloroplatinic acid.
- the noble metal may be stabilized with a suitable metal selected from Groups IVA, VB, VIB, VIIB or VIII of the Periodic Table.
- suitable metals are: Group IVA: Ge, Sn, Pb; Group VB: V, Nb, Ta; Group VIB: Cr, Mo, W; Group VIIB: Mn, Re; Group VIII: Fe, Ni, Co, Ru, Rh, Pd, Os, Ir and Pt. (Preferred metals are underlined.)
- the magnesium oxide with the noble metal deposited on or impregnated is then, if necessary, dried prior to further processing.
- the dried impregnated magnesium powder is then mixed with an alumina gel which may contain up to about 2% silica.
- the alumina gel itself is prepared by methods well known in the art, for example, by dissolving aluminum sulfate in water and then adding concentrated ammonium hydroxide in order to precipitate aluminum hydroxide.
- the cyclization step may take place under ordinary reforming conditions in a reactor normally used for reforming operations.
- the general and preferred operating conditions for this reaction are listed below in Table I.
- This reaction cyclizes the paraffms into naphthenes and aromatics in very high depentanized yields.
- the cyclized paraffinic stock is then passed to a conventional catalytic reforming unit containing a conventional platinum or platinum bi-metalliz reforming catalyst on an alumina or alumina containing support. This second step is run according to methods well known in the art.
- the catalyst of this example consists essentially of platinum (0.75 wt. impregnated magnesia powder in an alumina gel matrix.
- MgO powder 450 grams, was impregnated with ml. of a chloroplatinic acid solution (0.05g Pt/cc, diluted to 200cc).
- the platinum impregnated magnesia powder was dried on the steam plate' at a temperature of 130-140F.
- the alumina gel was prepared by dissolving 490 grams of Al (SO 'l8 H O in 5 liters of distilled water to which 300cc of concentrated NI-I OI-I was added to effect precipitation of Al(OI-I)
- the alumina gel was washed 3 times with cold water and filtered to remove most of the sulfate.
- the Pt-MgO powder was then mixed with the alumina gel and passed through a C01- loid Mill. This material was dried on the steam plate for a sufficient amount of time to remove moisture and obtain a good extrusion mix. The dried material was crushed using a mortar and pestle and sieved to 40 mesh.
- the material was then extruded in a California Pellet Mill in the form of l/l6 inch pellets.
- the pellets were dried in air on the steam plate (l30-140F.) for 8 hours at 300F. in an oven followed by calcination for 2 hrs. at 1000F. starting at 500F. and raising the temperature F. per hour.
- the average crush strength of the pellets was 8.0 pounds.
- Example II the catalyst prepared in Example I was used to cyclize a Udex raffinate.
- the raffinate was treated in three separate runs at temperatures of 850, 900 and 950F.
- pressure was 50 psig
- hydrogen rate was 6,000 SCFB
- the liquid hourly space velocity was 1.0.
- Liquid hourly space velocity (LI-ISV) is defined as the volume of liquid hydrocarbon charge per hour per volume of catalyst contained in the reaction zone.
- Table II which also sets forth the properties of the charge stock.
- EXAMPLE 111 In this example, the product produced at 850F. in Example 11 and the raw raffinate charge stock were processed separately over a platinum on alumina catalyst in a conventional reforming operation.
- the characteristics of the catalyst used are as follows:
- affin content of from about 70 percent or higher which comprises the steps of l cyclizing the paraffins in the blending component by contacting said component under reforming conditions with hydrogen in the presence of a catalyst comprising a noble metal on magnnesium oxide in an alumina gel matrix, to obtain a cyclized blending component, and (2) catalytically reforming said cyclized blending component in the presence of a conventional platinum or platinum bi-metallic reforming catalyst of an alumina or alumina containing support.
- a process for increasing the octane number of a paraffin containing gasoline blending component boiling within the gasoline boiling range and having a parmetal is stabilized with another metal selected from Groups IV A, V B, Vl B, V11 B and VIII of the Periodic Table.
- step (1) is promoted with a halogen compound.
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Catalysts (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US435363A US3926779A (en) | 1974-01-21 | 1974-01-21 | Upgrading of paraffinic gasoline blending components by cyclization with a platinum/magnesium oxide alumina matrix catalyst |
AU86464/75A AU494707B2 (en) | 1974-01-21 | 1975-11-10 | Upgrading of paraffing gasoline blending components by cyclization with a platinum/magnesium oxide/alumina matrix catalyst |
NL7513665A NL7513665A (nl) | 1974-01-21 | 1975-11-24 | Werkwijze voor het bereiden van een koolwaterstof- conversiekatalysator, gevormde katalysatordeeltjes en werkwijze voor het cycliseren van paraffines in een benzinemengcomponent. |
FR7535850A FR2332316A1 (fr) | 1974-01-21 | 1975-11-24 | Procede pour preparer un nouveau catalyseur de conversion des hydrocarbures |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US435363A US3926779A (en) | 1974-01-21 | 1974-01-21 | Upgrading of paraffinic gasoline blending components by cyclization with a platinum/magnesium oxide alumina matrix catalyst |
AU86464/75A AU494707B2 (en) | 1974-01-21 | 1975-11-10 | Upgrading of paraffing gasoline blending components by cyclization with a platinum/magnesium oxide/alumina matrix catalyst |
NL7513665A NL7513665A (nl) | 1974-01-21 | 1975-11-24 | Werkwijze voor het bereiden van een koolwaterstof- conversiekatalysator, gevormde katalysatordeeltjes en werkwijze voor het cycliseren van paraffines in een benzinemengcomponent. |
FR7535850A FR2332316A1 (fr) | 1974-01-21 | 1975-11-24 | Procede pour preparer un nouveau catalyseur de conversion des hydrocarbures |
Publications (1)
Publication Number | Publication Date |
---|---|
US3926779A true US3926779A (en) | 1975-12-16 |
Family
ID=27424004
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US435363A Expired - Lifetime US3926779A (en) | 1974-01-21 | 1974-01-21 | Upgrading of paraffinic gasoline blending components by cyclization with a platinum/magnesium oxide alumina matrix catalyst |
Country Status (4)
Country | Link |
---|---|
US (1) | US3926779A (fr) |
AU (1) | AU494707B2 (fr) |
FR (1) | FR2332316A1 (fr) |
NL (1) | NL7513665A (fr) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20110271925A1 (en) * | 2009-10-30 | 2011-11-10 | Chevron U.S.A. Inc. | Fuel composition |
US20120012087A1 (en) * | 2009-10-30 | 2012-01-19 | Chevron U.S.A. Inc. | Fuel composition |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2457318A1 (fr) | 1979-05-22 | 1980-12-19 | Raffinage Cie Francaise | Catalyseurs d'hydrotraitement d'hydrocarbures et applications desdits catalyseurs |
Citations (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2602772A (en) * | 1949-05-27 | 1952-07-08 | Universal Oil Prod Co | Conversion of hydrocarbons with platinum composite catalyst |
US2651598A (en) * | 1951-03-17 | 1953-09-08 | Atlantic Refining Co | Reforming process and catalyst |
US2905624A (en) * | 1955-11-07 | 1959-09-22 | Universal Oil Prod Co | Manufacture of lubricating oil |
US2972644A (en) * | 1956-11-14 | 1961-02-21 | British Petroleum Co | Dehydrogenation or dehydrocyclization of non-aromatic hydrocarbons |
US3395094A (en) * | 1966-05-04 | 1968-07-30 | Mobil Oil Corp | Shape selective naphtha processing |
US3424669A (en) * | 1967-01-03 | 1969-01-28 | Exxon Research Engineering Co | Reforming-aromatization process with sulfided catalyst |
US3436335A (en) * | 1966-03-25 | 1969-04-01 | Mobil Oil Corp | Serial reforming with a rare earth metal in all but last stage |
US3455813A (en) * | 1965-07-26 | 1969-07-15 | Stamicarbon | Light naphtha conversion process |
US3554902A (en) * | 1968-08-16 | 1971-01-12 | Chevron Res | Platinum iridium |
US3558479A (en) * | 1969-06-16 | 1971-01-26 | Chevron Res | Low pressure regenerative reforming process for high paraffin feeds |
US3846281A (en) * | 1972-04-03 | 1974-11-05 | Exxon Research Engineering Co | Platinum-magnesium reforming catalyst |
-
1974
- 1974-01-21 US US435363A patent/US3926779A/en not_active Expired - Lifetime
-
1975
- 1975-11-10 AU AU86464/75A patent/AU494707B2/en not_active Expired
- 1975-11-24 NL NL7513665A patent/NL7513665A/xx not_active Application Discontinuation
- 1975-11-24 FR FR7535850A patent/FR2332316A1/fr not_active Withdrawn
Patent Citations (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2602772A (en) * | 1949-05-27 | 1952-07-08 | Universal Oil Prod Co | Conversion of hydrocarbons with platinum composite catalyst |
US2651598A (en) * | 1951-03-17 | 1953-09-08 | Atlantic Refining Co | Reforming process and catalyst |
US2905624A (en) * | 1955-11-07 | 1959-09-22 | Universal Oil Prod Co | Manufacture of lubricating oil |
US2972644A (en) * | 1956-11-14 | 1961-02-21 | British Petroleum Co | Dehydrogenation or dehydrocyclization of non-aromatic hydrocarbons |
US3455813A (en) * | 1965-07-26 | 1969-07-15 | Stamicarbon | Light naphtha conversion process |
US3436335A (en) * | 1966-03-25 | 1969-04-01 | Mobil Oil Corp | Serial reforming with a rare earth metal in all but last stage |
US3395094A (en) * | 1966-05-04 | 1968-07-30 | Mobil Oil Corp | Shape selective naphtha processing |
US3424669A (en) * | 1967-01-03 | 1969-01-28 | Exxon Research Engineering Co | Reforming-aromatization process with sulfided catalyst |
US3554902A (en) * | 1968-08-16 | 1971-01-12 | Chevron Res | Platinum iridium |
US3558479A (en) * | 1969-06-16 | 1971-01-26 | Chevron Res | Low pressure regenerative reforming process for high paraffin feeds |
US3846281A (en) * | 1972-04-03 | 1974-11-05 | Exxon Research Engineering Co | Platinum-magnesium reforming catalyst |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20110271925A1 (en) * | 2009-10-30 | 2011-11-10 | Chevron U.S.A. Inc. | Fuel composition |
US20120012087A1 (en) * | 2009-10-30 | 2012-01-19 | Chevron U.S.A. Inc. | Fuel composition |
US8747491B2 (en) * | 2009-10-30 | 2014-06-10 | Chevron U.S.A. Inc. | Fuel composition |
US9273600B2 (en) | 2009-10-30 | 2016-03-01 | Chevron U.S.A. Inc. | Fuel composition |
AU2010313431B2 (en) * | 2009-10-30 | 2016-03-03 | Chevron U.S.A. Inc. | A fuel composition |
US9376640B2 (en) * | 2009-10-30 | 2016-06-28 | Chevron U.S.A. Inc. | Fuel composition |
Also Published As
Publication number | Publication date |
---|---|
AU8646475A (en) | 1977-05-19 |
NL7513665A (nl) | 1977-05-26 |
FR2332316A1 (fr) | 1977-06-17 |
AU494707B2 (en) | 1977-05-19 |
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