US2856349A - Two stage regeneration of platinum containing catalyst composite employed in hydroforming - Google Patents

Two stage regeneration of platinum containing catalyst composite employed in hydroforming Download PDF

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Publication number
US2856349A
US2856349A US343198A US34319853A US2856349A US 2856349 A US2856349 A US 2856349A US 343198 A US343198 A US 343198A US 34319853 A US34319853 A US 34319853A US 2856349 A US2856349 A US 2856349A
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bed
temperature
range
flue gas
free
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Expired - Lifetime
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US343198A
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English (en)
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Robert M Love
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ExxonMobil Technology and Engineering Co
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Exxon Research and Engineering Co
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Priority to BE527396D priority Critical patent/BE527396A/xx
Application filed by Exxon Research and Engineering Co filed Critical Exxon Research and Engineering Co
Priority to US343198A priority patent/US2856349A/en
Priority to GB7024/54A priority patent/GB787575A/en
Priority to FR1096790D priority patent/FR1096790A/fr
Priority to ES0214265A priority patent/ES214265A1/es
Priority to US584475A priority patent/US2856380A/en
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
    • C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D311/04—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring
    • C07D311/58—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring other than with oxygen or sulphur atoms in position 2 or 4
    • C07D311/70—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring other than with oxygen or sulphur atoms in position 2 or 4 with two hydrocarbon radicals attached in position 2 and elements other than carbon and hydrogen in position 6
    • C07D311/72—3,4-Dihydro derivatives having in position 2 at least one methyl radical and in position 6 one oxygen atom, e.g. tocopherols
    • 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
    • B01J23/90—Regeneration or reactivation
    • B01J23/96—Regeneration or reactivation of catalysts comprising metals, oxides or hydroxides of the noble metals
    • 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
    • C10G35/10—Catalytic reforming with moving catalysts
    • C10G35/14—Catalytic reforming with moving catalysts according to the "fluidised-bed" technique
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts

Definitions

  • the present invention is directed to a method for reconditioning a platinum hydroforming catalyst. More particularly, the invention is directed to the maintenance of activity of a platinum on alumina hydroforming catalyst. In its more specific aspects, the invention is directed to a fixed bed hydroforming operation in which naphthenic hydrocarbons are hydroformed employing a platinum catalyst.
  • the temperature of the flue gas is then adjusted to a temperature in the range between 700 and 800 F., and the flue gas is diluted with a free oxygen-containing gas in an amount suflicient to support a combustion operation in the bed wherein there is a flame front advancing through the bed in the direction of flow at a temperature not in excess of 1100 F. until the carbonaceous material and carbon are burned from the bed.
  • the free oxygen content of the flue gas is then increased to a partial pressure of at least one atmosphere while the temperature of the flue gas is increased to a temperature between 1050 and 1100 F.
  • This free oxygen-containing gas is then cooled to a temperature in the range between 800 and 900 F., and the flow of the free oxygen-containing gas is continued until the bed has been cooled to a temperature in the range between 800 and 900 F.
  • the flow of the free oxygen-containing gas is then terminated, and flue gas is flowed over the bed at a temperature in the range between 800 and 900 F. to remove free oxygen from the bed.
  • a free hydrogen-containing gas is flowed over the bed at a temperature in the range between 800 and 900 F., and the temperature of the bed is then increased to a temperature in the range between 900 and 1000 P. which is reaction temperature wherein a conversion operation is conducted by introducing into contact with the bed a naphthenic hydrocarbon boiling in the range between 150 and 500 F.
  • the hydroforming operation is conducted at a temperature in the range from about 900 to 1000 F. Desirable results are obtained at about 950 F.
  • the regeneration operation is conducted at a temperature in the range from 1050 to 1100 F. in a combustion operation in which non-volatile carbonaceous deposits and carbon are removed from the catalyst by burning in the presence of free oxygen.
  • the amount of hydrogen employed will range from about 1000 cubic feet to about 10,000 cubic feet per barrel of feed.
  • the preferred operation will employ about 5000 cubic feet of hydrogen per barrel of feed. While pure hydrogen may be used ordinarily, I would preferably employ a free hydrogen-containing gas.
  • I may employ air as the free oxygencontaining gas
  • I may suitably use other gases, such as flue gas, which has been diluted with air or free oxygen;
  • the amount of free oxygen in the flue gas be increased so that the partial pressure of the oxygen is at least one atmosphere during the time that the flue gas containing the oxygen is heated to a temperature of from 1050 to 1100 F. and when the free oxygen-containing flue gas is being passed Over the catalyst bed to cool it to a temperature between 800 and 900 F.
  • the following table of data is given for varying operating pressures:
  • the hydrocarbon employed as the feed stock of my invention is a naphthenic hydrocarbon boiling in the range from about to about 500 F.
  • Such naphthenic hydrocarbons may be obtained from crude petroleums, such as the Coastal crude oils, the California type crudes and particularly those from naphthenic base crude petroleum.
  • I may also employ as a feed stock, either alone or in admixture with the crude petroleum fractions, the naphthenic fractions boiling in the range from 150 to 500 F. obtained in catalytic conversion operations, such as catalytic cracking operations. It is preferred, however, to employ the crude petroleum fractions.
  • the catalyst employed in the practice of the present invention preferably will be a platinum on alumina catalyst containing from about 0.1% to 3.0% by weight of platinum, preferably 0.2% to 1.0% by weight. It is desirable that the alumina on which the platinum is deposited be a purified alumina, such as a gamma alumina derived from boehmite. Although gamma alumina or purified alumina is preferred, I may use a platinum on alumina derived from other sources. There are numerous aluminas on the market which are available as supports for catalysts and I intend that I may use a platinum on alumina catalyst of the type available. I also intend that other supported platinum catalysts may be used such as platinum on zirconia, magnesia, and magnesiaalumina mixtures, and the like.
  • the cooled catalyst may be contacted with hydrogen or with a mixture of hydrogen and hydrocarbon after purging free oxygen from the cooled catalyst. It may be desirable, for example, to contact the cooled catalyst with hydrogen and then bring the temperature of the hydrogen and catalyst mixture up to reaction temperature before the hydrocarbon is admixed therewith. Desirable results, however, are obtained by contacting the cooled catalyst with hydrogen and hydrocarbon and bringing the hydrogen-hydrocarbon mixture and the catalyst up to reaction temperature.
  • a naphthenic hydrocarbon such as one boiling in the range from about 200 to 300 F.
  • the naphthenic hydrocarbon is introduced into a heater or furnace 19 provided with a heating coil 20 and with burners 21.
  • the heater 19 the' temperature of the naphthenic hydrocarbon is raised to a temperature in the range between 900 and 1000 F. which serves to vaporize the hydrocarbon.
  • the heated vaporized hydrocarbons leave furnace 19 by way .of line 22 and has admixed with it a free hydrogen-containing gas which is introduced by line 23 from a source which will be described further.
  • the mixture 'of vaporized hydrocarbon and free hydrogencontaining gas discharges from line 22 into branch line 24 controlled by valve 25 into reaction zone 11 and passes downwardly therethrough and the naphthenic hydrocarbons are hydroforrned or converted to aromatic hydrocarbons, the reaction temperature in bed 11 being in the range from about 900 to about 1000 F. and preferably at an average temperature of 950 F. i
  • the products in reaction zone 11 are withdrawn by line 26. controlled by valve 27 into line 28 and then flowed through a cooler 29 and the cooled reaction products are hen introduced into a separator zone 30 which serves to separate the liquid products from the fixed gases which include hydrogen.
  • the liquid products are withdrawn from separator 30 by line 31 to be further separated by fractional distillation.
  • the fixed gas containing a substantial amount of free hydrogen is withdrawn from separator 30 by line 23 containing a compressor 32 and a heater 33, the free hydrogen-containing gas being suitably compressed and heated before introduction into line 22 as has been described.
  • the catalyst in reaction zone 13 loses its activity toward converting hydrocarbons to an extent it resists restoration by the burning operation and/ or becomes fouled with carbonaceous material and carbon which is deposited on the catalyst during the operation and it, therefore, becomes necessary to take the reaction zone 11 out of the reaction cycle and put it on the regeneration cycle which will be described in further detail.
  • the heated naphthenic hydrocarbon in vaporous form in admixture with the free hydrogen-containing gas is then routed into reaction zone 12 by opening valve 36 in branch line 37 which discharges the reaction mixture downwardly through the bed 14.
  • the reaction products issue from the bed 14 by line 38 controlled by valve 39 which then 4 routes them by line 28 through cooler 29 and into separator 30 for recovery of the product and the free hydrogen-containing gas.
  • the flue gas is then diluted with a free oxygen-containing gas, such as air, which is introduced into line 42 by line 60 controlled by valve 61 which connects to a source of compressed air.
  • a free oxygen-containing gas such as air
  • the amount of air or free oxygencontaining gas introduced into line 42 by line 60 is a suflicient amount to support a combustion operation in bed 13.
  • this amount of air which is used to dilute the flue gas is of suflicient amount to provide as much as 3% by volume of oxygen in the flue gas.
  • the factor which governs the amount of oxygen is the temperature of the advancing flame front which is in the direction of flow downwardly in bed 13 such that the temperature of the flame front does not exceed 1100 F. Ordinarily an amount of oxygen of about 2% by volume will be sufficient.
  • the temperature of the fl-ue gas containing oxygen is maintained at about 700 to 800 F. such that the relatively cool flue gas serves to remove heat from the burning bed and maintains the temperature of the flame front not over l
  • This operation is continued with the dilute flue gas until the carbonaceous material and carbon are burned from the catalyst in the bed.
  • the free oxygen content of the flue gas is then increased to provide an oxygen partial pressure at least equivalent-to one atmosphere. by adding more air through line ,60 While the temperature of the flue gas is increased to a temperature in the range from 1050 to 1100 F. This is suitably done by closing valve ,59 and allowing the flue gas diluted with air to W through the heater 45 whichis adjusted tointroduce more heat to the flue gas flowing through heater 45.
  • the free oxygen-containing flue gas is cooled to a temperature in the range between 800 and 900 F. and the flow of the cooled free oxygencontaining flue gas continued over the bed until the temperature of the bed is in the range between 800 and 900 F.
  • this may readily be achieved by closing valve 49 in by-pass line 48 and allowing the flue gas tobe routed from line 47 through cooler 62 and then by opening valve 63 in line 50 into manifold 51 and thence into bed 13. This operation is continued until the bed is at a temperature between 800 and 900 F.
  • This operation results in maintenance of activity and reconditioning of the catalyst to allow obtaining of high octane number products.
  • the particular treatment for restoring catalyst activity need not be performed after each burning or regeneration operation but may be performed when the activity of the catalyst after regeneration has fallen to a point where the operation is unattractive.
  • the invention will be illustrated by an example in which a platinum on alumina catalyst containing 0.6% by weight of platinum was employed for about 1200 hours in a fixed bed unit charging a 200 to 300 F. boiling range naphtha from a Coastal crude at a pressure of 275 p. s. i. g. and a recycle gas to feed ratio of 5000 standard cubic feet per barrel, the recycle gas containing 85% of hydrogen.
  • the temperature in the inlet to the bed was 975 F.
  • the naphtha was charged at a space velocity at 2 volumes of feed per volume of catalyst per hour.
  • a product having a 95 Research clear octane number was obtained at 83 to 84 volume percent debutanized yield.
  • Air at 290 p. s. i. absolute (about 60 p. s. i. absolute partial pressure of oxygen) was passed over the catalyst while heating the system to 1100 F. where it was maintained for 24 hours.
  • the catalyst bed at 1100 F. was then purged with nitrogen and the temperature reduced to 950 F.
  • Hydrogen was introduced when the catalyst had reached 950 F. and the reaction period was started by introducing the feed hydrocarbon again. After 50 hours on operation it was found that the octane number of the product had dropped to 86 with a debutanized yield of 81 volume percent as compared to a yield with fresh catalyst at this octane level of 91 volume percent.
  • the catalyst being regenerated by burning with 0.5 to 1% oxygen.
  • oxygen at 35 to 45 p. s. i. absolute was passed over the catalyst while it was heated to 1100 F., and this temperature was held for 24 hours.
  • the catalyst was then cooled to 800 F. while continuing the flow of oxygen over the catalyst.
  • the oxygen was purged from the catalyst with nitrogen, and hydrogen flow was initiated.
  • the catalyst was heated to reaction temperature to 950 F. in the presence of hydrogen and the reaction was begun by introducing the naphthenic hydrocarbon feed.
  • standard operating conditions including an average temperature of 930 F., a pressure of 275 p. s. i. g.
  • flue gas as the inert gas
  • other inert gases such as pure nitrogen, carbon dioxide, and mixtures thereof, may be used.
  • a method for conditioning a fixed bed of supported platinum on purified alumina catalyst which has lost activity and has become fouled with carbonaceous material and carbon in a conversion operation at a temperature in the range between 900 and 1000 F. in which naphthenic hydrocarbon and hydrogen are contacted with said bed which comprises flowing an inert gas over the bed of catalyst at a temperature in the range between 600 and 1000 F. to purge said naphthenic hydrocarbon and hydrogen from said bed, adjusting the temperature of the inert gas to a temperature in the range between 700 and 800 F. and continuing to flow inert gas over said bed until the temperature of the bed is in the range between 700 F.
  • a method for obtaining high yields of high octane number product in which -a fixed bed of platinum on purified alumina catalyst whichhas lost activity and has become fouled with"carbonaceous"material and carbon in a hydroformihgoperation at a temperature in the range between 900 and 1000 F. by contact with a vaporized naphthenic hydrocarbon boiling in the range between 150 and 500 F. and hydrogen is'conditioned to produce said yields and product which comprises flowing flue gas over said bed of catalyst-at a temperature in the range between 600 and 1000 F.'to purge said naphthenic hydrocarbon and.
  • a method for obtaining high yields; of high octane number product in which a fixed bed of platinum on purified alumina catalyst which has lost activity and has become fouled with carbonaceous material and carbon in a hydroforming operation at a temperature in the range between 900 and- 1000" F. by contact with a vaporized naphthenic hydrocarbon boiling in the range between and 500 F. and'hydrogen is conditioned toproduce said yields andproduct which comprises flowing flue gas over said bed of catalyst at a temperature in the range between 600 and 1000 F. to purge said naphthenic hydrocarbon and hydrogen from said bed, adjusting the temperature of the flue gas to a temperature in the range between 700 and 800 F.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Catalysts (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
US343198A 1953-03-18 1953-03-18 Two stage regeneration of platinum containing catalyst composite employed in hydroforming Expired - Lifetime US2856349A (en)

Priority Applications (6)

Application Number Priority Date Filing Date Title
BE527396D BE527396A (enrdf_load_stackoverflow) 1953-03-18
US343198A US2856349A (en) 1953-03-18 1953-03-18 Two stage regeneration of platinum containing catalyst composite employed in hydroforming
GB7024/54A GB787575A (en) 1953-03-18 1954-03-10 Improvements in or relating to process for the treatment of platinum catalyst
FR1096790D FR1096790A (fr) 1953-03-18 1954-03-12 Procédé de reconditionnement d'un catalyseur d'hydroformation en platine
ES0214265A ES214265A1 (es) 1953-03-18 1954-03-18 Un método de tratar catalizador de platino
US584475A US2856380A (en) 1953-03-18 1956-05-14 Soil stabilization

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US343198A US2856349A (en) 1953-03-18 1953-03-18 Two stage regeneration of platinum containing catalyst composite employed in hydroforming

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US2856349A true US2856349A (en) 1958-10-14

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BE (1) BE527396A (enrdf_load_stackoverflow)
ES (1) ES214265A1 (enrdf_load_stackoverflow)
FR (1) FR1096790A (enrdf_load_stackoverflow)
GB (1) GB787575A (enrdf_load_stackoverflow)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2939897A (en) * 1958-08-15 1960-06-07 Pure Oil Co Process and catalyst for the isomerization of light paraffin
US3270790A (en) * 1964-03-09 1966-09-06 Plastronics Inc Detachable tube to bag connector means and method of making same
DE2754857A1 (de) * 1976-12-13 1978-06-15 Chevron Res Verfahren zur wasserstoffbehandlung eines katalysators

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2603044B1 (fr) * 1986-08-25 1988-11-04 Inst Francais Du Petrole Procede de regeneration d'un catalyseur d'hydroconversion d'hydrocarbures

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2368507A (en) * 1940-12-31 1945-01-30 Standard Oil Dev Co Regeneration of catalysts
US2641582A (en) * 1950-10-03 1953-06-09 Universal Oil Prod Co Regeneration of a platinumcontaining catalyst
US2662861A (en) * 1951-08-15 1953-12-15 Kellogg M W Co Platinum and palladium catalysts
US2664404A (en) * 1949-08-18 1953-12-29 Standard Oil Dev Co Regeneration of selective hydrogenation catalyst
US2701230A (en) * 1949-07-01 1955-02-01 Standard Oil Dev Co Hydroforming process and apparatus

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2368507A (en) * 1940-12-31 1945-01-30 Standard Oil Dev Co Regeneration of catalysts
US2701230A (en) * 1949-07-01 1955-02-01 Standard Oil Dev Co Hydroforming process and apparatus
US2664404A (en) * 1949-08-18 1953-12-29 Standard Oil Dev Co Regeneration of selective hydrogenation catalyst
US2641582A (en) * 1950-10-03 1953-06-09 Universal Oil Prod Co Regeneration of a platinumcontaining catalyst
US2662861A (en) * 1951-08-15 1953-12-15 Kellogg M W Co Platinum and palladium catalysts

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2939897A (en) * 1958-08-15 1960-06-07 Pure Oil Co Process and catalyst for the isomerization of light paraffin
US3270790A (en) * 1964-03-09 1966-09-06 Plastronics Inc Detachable tube to bag connector means and method of making same
DE2754857A1 (de) * 1976-12-13 1978-06-15 Chevron Res Verfahren zur wasserstoffbehandlung eines katalysators

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FR1096790A (fr) 1955-06-24
GB787575A (en) 1957-12-11
BE527396A (enrdf_load_stackoverflow) 1900-01-01
ES214265A1 (es) 1954-07-01

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