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
  • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
  • C10G45/44—Hydrogenation of the aromatic hydrocarbons
  • C10G45/46—Hydrogenation of the aromatic hydrocarbons characterised by the catalyst used
  • C10G45/52—Hydrogenation of the aromatic hydrocarbons 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
  • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
  • C10G2400/08—Jet fuel

Definitions

• Paraffins including isoparaffins, have a relatively high smoke point and gravity which makes them desirable components. However, they have relatively low heating value (B.t.u./lb.). Moreover, most natural kerosene boiling range fractions contain substantial amounts of aromatics and naphthene compounds making the production of entirely paraffinic fuels economically unattractive.
• Aromatics on the other end of the scale, have low smoke point and API gravity properties but high heating value.
• Naphthenes fall in between. They have relatively high heating value and relatively poor smoke point and gravity properties.
• feasible jet fuels must be a balanced composition containing at least paraffins and naphthenes.
• Aromatics may or may not be included depending on the quality of the other components.
• Polynaphthene compounds are also usually present in the kerosene distillates and are much like aromatics, i.e., have poor gravity and smoke point characteristics.
• the process involves simultaneous aromatic hydrogenation and ring opening in a single reaction zone.
• the present invention is a process for the hydrogenation/ring opening of kerosene boiling range hydrocarbon fractions, having substantial amounts of cyclic compounds, characterized by contacting a kerosene fraction in the presence of hydrogen with a catalyst comprising at least 1 w/o platinum group metal and 0.5 w/o fluoride on alumina, the process being further characterized by maintaining the kerosene feed water content to below about ppm. by weight.
• Kerosene boiling range fractions suitable for the process of the present invention may be derived from a variety of sources. In general, fractions in the boiling range from about 300 to 600 C. are suitable. Examples of suitable feeds are, for example, straight run, catalytically cracked, or hydrocracked fractions and combinations thereof. The fractions for which the present process is advantageous have APl gravities lower than 39 and smoke points which are usually below about 20. Such fractions contain substantial amounts of aromatic and naphthenic ring compounds, i.e., a suitable straight run fraction from a naphthenic crude which may con tain on the order of 10 to percent aromatics and 40 to 70 percent naphthenes. Hydrocracked kerosene fractions usually have higher aromatics content in the range of 30 to 60 percent.
• the kerosene feed contains relatively high contents of heteroatomic impurities such as nitrogen, sulfur or metallic compounds, hydrotreating to reduce or remove these impurities is desirable. Sulfur compounds are especially undesirable since they tend to poison the platinum group metal in the hydrogenation ring opening catalyst.
• Such catalysts generally comprise one or more of the various Group Group V] and Group VIII metals as well as the oxides and sulfides thereof supported on a porous carrier.
• nickel molybdenum sulfide on alumina is an example of a useful, commercially available catalyst.
• Hydrofining can be carried out over a wide range of conditions that depend upon the particular hydrocarbon feed and catalyst used. Temperatures in the range of 625 to 750 F., pressures in the range of 400 to 1,500 p.s.i.g., liquid hourly space velocities of about 0.5 to 5 and hydrogen to oil ratios of about 500 to 10,000 standard cubic feet of H per barrel of feed are customary conditions. Partial hydrogenation of aromatics in the kerosene boiling range may be effected in the hydrotreating reaction but is neither required for nor forms a part of the present invention.
• the present process uses a catalyst composite which has certain critical concentrations of components.
• the predominant portion of the catalyst is a porous alumina support.
• Suitable alumina supports include activated alumina, gamma alumina, eta alumina, pseudo-alumina and the like.
• the catalyst contains at least 1 w/o of a platinum group metal and preferably about 1.5 w/o platinum.
• the catalyst must also contain at least 0.5 w/o fluorine and preferably about 1 percent weight fluorine.
• Fluorine is customarily added to such catalyst composites to promote acid catalyzed reactions.
• the desired hydrogenation/ring opening reactions of the present invention are known to be metal catalyzed.
• the addition of a halogen would not be expected to aid in these reactions but instead to lead to undesirable hydrocracking.
• Platinum metal and fluorine may be added to the alumina support by various means known to the art.
• a convenient method involves competitive ion exchange of discrete particles (spheres, extrudates, etc.) of alumina with an aqueous solution of chloroplatinate ions and ammonium ions such as a dilute solution of chloroplatinic acid and ammonium mitrate.
• Nitrate and chloride ions are removed by washing and the composite is impregnated with a suitable fluoride compound such as a solution of ammonium bifluoride. Calcination decomposes the ammonium ion.
• the process may be carried out in any suitable equipment but preferably in a fixed bed reaction system where the catalyst is disposed as discrete particles in a reaction zone and the hydrocarbon feed passed therethrough in upward, downward or radial flow.
• Reaction conditions for the present invention depend upon the kerosene feed composition properties and the catalyst composition and degree of activation.
• Suitable conditions are temperatures in the range of 500 to 800 F., pressure in the range of 500 to 1,500 p.s.i.g., liquid hourly space velocities of from 0.5 to 5 volumes of feed per volume of catalyst per hour and hydrogen to hydrocarbon mole ratios of about 5 to 20.
• the moisture content of the kerosene feed is especially important and should be maintained below about p.p.m. by weight and preferably at about 2 p.p.m. by weight. The importance of low water content will be demonstrated in the examples.
• EXAMPLE 1 Catalysts were prepared with platinum contents of0.1, 0.68 and 1.5 w/o and 0.6 w/o fluorine by uniformly dispersing platinum on porous alumina. The metal was incorporated by competitive ion exchange of chloroplatinate ions in dilute ammonium nitrate solution. Fluorine was incorporated by impregnation of the catalyst with ammonium bifluoride solution. The catalysts were washed free of unreacted ions, dried, calcined and reduced in dry hydrogen. These catalysts were tested with a hydrotreated naphthenic kerosene fraction (310 to 540 F. boiling range) at 665 F., 1.5 liquid hourly space velocity (LHSV) and 10 H jhydrocarbon mole ratio. The results are shown in table 1.
• LHSV liquid hourly space velocity
• EXAMPLE 2 A catalyst prepared by competitive ion exchange of platinum and impregnation with fluoride of a commercial catalytic reforming catalyst was used to study the effect of moisture in the process. Platinum and fluoride were added as described in example 1 to give a catalyst having 1.5 w/o' platinum and 1 w/o fluorine. Prior to use the catalyst was calcined in a reactor with dry air, purged with nitrogen and reduced with dry hydrogen for 1 hour at atmospheric pressure.
• the catalyst was used for ring opening a kerosene fraction like that in example 1.
• Conditions were 850 p.s.i.g., 660 F., 2 LHSV and 10 H joil ratio (mole).
• the kerosene was dried to a water level of 10 p.p.m. by weight by passing it over molecular sieves. After hours of processing the product AP] gravity was about 39.7. After 200 hours of operation of feed water level was increased to 570 p.p.m. and the product APl gravity immediately fell to 38.8. On returning to 10 p.p.m. water the product API gravity increased to 39.5.
• EXAMPLE 3 A catalyst substantially the same as the 1.5 w/o platinum catalyst described in example 2 was used for ring opening the 310-540 F. kerosene fraction of example 1 at 850 p.s.i.g., 660 F., 2 LHSV and 10 H loil ratio (mole). The kerosene was dried to 2 p.p.m. by weight water with molecular sieves. During 1,000 hours of operation (after which the run was terminated without evidence of catalyst deactivation) the product API gravity was 40 or above. Yield of product during this time was about 96 percent volume of 310 F. plus kerosene.
• a process for hydrogenating/ring-opening a feed consisting essentially of kerosene boiling range hydrocarbons wherein the feed substantially free of heteroatomic impurities is contacted in the presence of hydrogen with a catalyst comprising at least about 1.0 w/o of a platinum group metal and at least 0.5 w/o by weight fluorine on an alumina support at temperature in the range of about 500 to 800 F., a pressure in the range of about 500 to 1,500 p.s.i.g. and a hydrogen to hydrocarbon mole ratio of from about 5 to 20 and wherein the water content of the contacted hydrocarbons is below about 10 p.p.m. by weight.
• the catalyst comprises about 1.5 w/o platinum and about 1 W10 fluorine on the alumina support.

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• 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)
• Catalysts (AREA)

Applications Claiming Priority (1)

Publications (1)

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Family Applications (1)

Country Status (7)

Cited By (9)

• 1969
  • 1969-04-07 US US814520A patent/US3607729A/en not_active Expired - Lifetime
• 1970
  • 1970-01-19 CA CA072,486A patent/CA940856A/en not_active Expired
  • 1970-04-06 GB GB1296772D patent/GB1296772A/en not_active Expired
  • 1970-04-06 DE DE2016358A patent/DE2016358C3/de not_active Expired
  • 1970-04-06 FR FR7012352A patent/FR2038298B1/fr not_active Expired
  • 1970-04-06 JP JP45028976A patent/JPS4918443B1/ja active Pending
  • 1970-04-06 NL NL7004885.A patent/NL165210C/xx not_active IP Right Cessation

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