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
  • C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
  • C10G47/02—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used
  • C10G47/10—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used with catalysts deposited on a carrier
  • C10G47/12—Inorganic carriers
• • 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
  • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
  • B01J21/16—Clays or other mineral silicates
• • 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
  • C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
• • 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
  • C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
  • C10G47/02—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used
  • C10G47/06—Sulfides

Definitions

• This invention relates to a hydrocarbon conversion process and, more particularly, to a process for the catalytic conversion of petroleum distillates to products boiling below the initial boiling point of the feed distillates.
• this invention is directed to the processing of hydrocarbon distillates, including heavier distillates boiling up to about 1050 F., having a high total nitrogen content, to products boiling below the initial boiling point of the feed distillates while concurrently denitrifying said feed distillates and maintaining unusually long catalyst on-stream periods.
• the process of the present invention is a type of hydrocracking process conducted in the presence of hydrogen and a catalyst composition comprising a hydrogenatingdehydrogenating component disposed on a solid, active, acidic support.
• the process is characterized by long onstream periods, for example, several months in duration, without the necessity for catalyst regeneration, conversion of the feed to the desired products with a substantial consumption of hydrogen, feed denitrification, and low pressure operation.
• a process for converting a hydrocarbon distillate feed having a total nitrogen content between 10 and 1000 parts per million and boiling in the range from about 320 to 1050 F. to produce fractions boiling below the initial boiling point of said feed in a yield of at least 20% per pass which comprises passing said feed along with at least 1500 standard cubic feet of hydrogen per barrel thereof at temperatures between 320 F.
• the 10-1000 p.p.m. total nitrogen content in the feed to the process of the present invention may be either the nitrogen content of an untreated feed to the process, or the nitrogen content resulting from subjecting a stock having a hi her nitrogen content to partial denitrification and/ or dilution with low nitrogen content stocks.
• such a hydrocracking process can be operated at pressures above 500 p.s.i.g., preferably from 500 to 3000 p.s.i.g., with feeds containing from 10 parts per million to 1000 parts per million nitrogen with a heretofore unobtainable catalyst fouling rate so low that reasonable temperatures may be maintained throughout the catalyst on-stream period and the catalyst on-stream period can be extended for an unexpectedly long time; with the process of the present invention catalyst on-stream periods of more than 750 hours are easily obtainable.
• the nitrogen compounds in the feed are relied upon as a source of ammonia, these compounds must be rapidly converted to ammonia during the first portion of the onstream period because when the ammonia is titrated onto the catalyst it thereby selectively excludes or blocks the organic nitrogen compound therefrom. While this ammonia titration is being accomplished, the temperature necessary to maintain a substantially constant conversion will rise rather rapidly; however, the ammonia titration of the catalyst will proceed only to the point where the ammonia chemisorbed on the catalyst is in equilibrium with the ammonia being produced in the reaction zone from the organic nitrogen compounds in the feed. Thereafter, the temperature necessary to maintain substantially constant conversion will increase at a much slower rate, depending upon the small but essential remaining acidity of the catalyst.
• This slower rate of temperature increase Will continue throughout substantially all of the remainder of the run.
• This slower rate of temperature increase is not only slower than the rate during the first portion of the on-stream period while the catalyst was becoming equilibrated with ammonia, but also is a slower rate than that which would have been necessary had rapid ammonia titration of the catalyst not been accomplished.
• This substantially constant rate of temperature increase during the remainder of the run will generally be in the range from 650 to 900 F., preferably from 650' to 850 F.
• the operating pressures in the present process will be at least 500 p.s.i.g., preferably 1500 to 3000 p.s.i.g. and still more preferably 1500 to 2500 p.s.i.g. Lower pressures tend to decrease run lengths and higher pressures tend to increase hydrogen consumption.
• the space velocities used in the process of the present invention are 0.2 to v./v./hr.; however, exceptionally excellent results are obtained if the space velocities are in the range from about 0.3 to 4.0 v./v./hr.
• Hydrocracking catalysts adequate for carrying out the process of the present invention will contain a hydrogenating-dehydrogenating component disposed on, i.e., intimately associated with a solid, active, acidic, cracking support.
• a hydrogenating-dehydrogenating component disposed on, i.e., intimately associated with a solid, active, acidic, cracking support.
• the hydrogenating-dehydrogenating component may be any component adequate to accomplish the desired hydrogenation and denitrification under the process operating conditions. Nickel sulfide and/or cobalt sulfide are especially suitable.
• the entire preferred catalyst composite of Scott U.S. Patent 2,944,006 will be especially suitable in the process of the present invention.
• the process of the present invention may be operated as a once-through process or in a recycle manner.
• very desirable method of operation is with separation from the hydrocracking zone effluent, of an ammoniafree hydrogen-rich gas stream which is recycled to the hydrocraclcing zone.
• Various hydrocracking fractions not converted below the initial boiling point of the feed may be recycled to advantage, particularly aromatics-rich fractions.
• the product fractions from the hydrocracking zone that boil below the initial boiling point of the feed constitute excellent gasoline blending stocks for certain purposes; however, it will be found generally more desirable to send at least the heavier portions of them to a catalytic reformer where they will serve as a most excellent preferred feed for catalytic reforming operations.
• Example 1 A light cycle oil comprising a blend of 19.9% raw cycle oil, 41.9% hydrofined cycle oil, and 46.6% of recycle bottoms having a nitrogen content of 60 parts per million based on the total light cycle oil blend was hydrocracked and concurrently denitrified in accordance with the process of the present invention over a catalyst comprising a nickel sulfide hydrogenating-dehydrogenating component on a solid silica-alumina active, acid, cracking support. The hydrocracking and denitrification were accomplished in once-through operation.
• the light cycle oil feed was accompanied by 6500 standard cubic feet of hydrogen per barrel of feed.
• the catalyst immediately after being placed on stream was rapidly titrated with ammonia derived from the nitrogen content of the cycle oil feed at temperatures between 400 F. and 750 F a pressure of 1800 p.s.i.g. and at a liquid hourly space velocity of 0.5.
• the operating temperature necessary to maintain a 50% conversion of the feed to products boiling below the initial boiling point of the feed immediately and abruptly leveled off at about 730 F.
• the hydrocracking-denitrification operation could be effectively continued for approximately 800 hours without the necessity for raising the operating temperature more than about .033 F. per hour in order to maintain said 50% conversion.
• Example 2 A raw (unhydrodenitrified) heavy straight-run Arabian gas oil, having an API gravity of 280, boiling over the range 530 F. initial to 862 F. endpoint (ASTM D-1160 distillation), and a total nitrogen content of 570 parts per million, was hydrocracked and concurrently denitrified in accordance with the present invention over the catalyst of Example 1, above.
• the oil feed was accompanied by 6500 standard cubic feet of hydrogen per barrel of oil. Beginning immediately after the catalyst-containing reactor was placed on stream, the catalyst was equilibrated with ammonia derived from the nitrogen content of the oil feed at temperatures ranging from about 700 F.
• the operating temperature necessary to maintain a 60% by volume conversion of the feed to products boiling below the initial boiling point of the feed, and to recycle reactor eflluent fractions boiling above the initial of the feedback through the reactor to extinction, gradually leveled olf at substantially 775 F. and remained constant up to a total run length of 800 hours at 0.5 liquid hourly space velocity.
• the process of the present invention solves a number of heretofore unsolved problems that have been faced by the art, particularly in that it enables a hydrocraeking process to be operated both with high nitrogen content feeds and with long catalyst life at reasonable operating temperatures.
• a catalyst which comprises a hydrogenating component selected from group consisting of cobalt sulfide and nickel sulfide intimately associated with an active acid cracking support and is susceptible to fouling and consequent deactivation by coke laydown when used to hydrocrack a hydrocarbon distillate feed boiling from 320 to 1050 F.

Landscapes

• Chemical & Material Sciences (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Engineering & Computer Science (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Organic Chemistry (AREA)
• General Chemical & Material Sciences (AREA)
• Dispersion Chemistry (AREA)
• Materials Engineering (AREA)
• Inorganic Chemistry (AREA)
• Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
• Catalysts (AREA)

Priority Applications (5)

Applications Claiming Priority (1)

Publications (1)

Family

ID=22270704

Family Applications (1)

Country Status (5)

Cited By (2)

Families Citing this family (2)

Citations (4)

Family Cites Families (1)

• 0
  • NL NL276521D patent/NL276521A/xx unknown
• 1961
  • 1961-03-28 US US98743A patent/US3117075A/en not_active Expired - Lifetime
• 1962
  • 1962-03-27 DE DEC26594A patent/DE1245524B/de active Pending
  • 1962-03-27 FR FR892429A patent/FR1318389A/fr not_active Expired
  • 1962-03-28 GB GB11883/62A patent/GB992264A/en not_active Expired

Patent Citations (4)

Also Published As

Similar Documents