Classifications

• • 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
  • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
  • B01J27/14—Phosphorus; Compounds thereof
  • B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
  • B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
  • B01J27/19—Molybdenum
• • 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
  • C10G45/58—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins
  • C10G45/60—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins characterised by the catalyst used

Definitions

• the distillate is contacted in the presence of hydrogen with a catalyst containing a group VIa metal on a refractory oxide support at a temperature of at least 750 F. but below the temperature at which substantial cracking occurs, a pressure which is greater than the equilibrium pressure and a space velocity of the liquid feedstock not exceeding 3 .0 v./v./hr., the temperature and space velocity being correlated so that the cloud point, pour point or freezing point of the stabilized distillate is at least 10 F. lower than the cloud point, pour point or freezing point of the feedstock.
• substantial cracking is understood to occur when more than 20% wt. of the feedstock is converted to material boiling below 150 C. Preferably not more than 15% wt. of the feedstock is converted to material boiling below 150 C.
• the temperature employed is preferably above 800 F. and will not usually exceed 900 F. and in general the lower the temperature, the lower the space velocity.
• the pressure employed will normally be between 100 and 1500 p.s.i.g. and the hydrogen to hydrocarbon mole ratio will normally be from 5 to 1 to 20 to l.
• the process of the present invention will normally lower all the three points specified, viz. cloud point, pour point and freezing point.
• the point to be taken as the criterion in any given operation will depend on the boiling range of the material being treated and the use to which it is to be put. In general the freezing point is only of significance with the lighter distillates.
• the distillate fraction used as feedstock may have a low initial sulfur content, for example 0.1% wt. sulfur or less.
• Such low sulfur feedstocks may be straight-run materials or the products of previous refining treatments, for example, products of a hydrocatalytic desulfurization process.
• the process according to the invention may result in a considerable reduction in the sulfur content.
• the process may be accompanied by an increase in specific gravity.
• Some lower boiling material will be produced by, for example dehydrogenation, desulfurization and/or a small amount of cracking, and this is separated from the product, preferably by fractionation, to stabilized it and give a material of the required boiling range and flash point.
• 'A convenient cut point is in the region of 130- 170 C.
• the catalyst contains a group VIa metal preferably in the form of an oxide or sulfur on a refractory oxide support.
• the catalyst may also contain a group VIII metal, preferably in the form of an oxide or sulfur, in addition to the group VIa metal.
• the presence of a group VIII metal is particularly desirable if it is desired to desulfurize as well as to reduce the pour point.
• the preferred group VIa metal is molybdenum and the preferred group VIII metal is an iron group metal particularly cobalt.
• the group VIa metal may be present in from 5 to 30% wt. (expressed as oxide), by weight of total catalyst, and the group VIII metal from 0.1 to 5% wt. (expressed as oxide), by weight of total catalyst.
• a particularly preferred catalyst contains the oxides of cobalt and molybdenum (as such, or in combined form or both).
• the refractory oxide support is preferably acidic and may be one or more of the refractory oxides of elements from group II, IE1 or IV.
• Silica may be excepted from the suitable group IV refractory oxides. It may also contain from 0.1 to 6% wt., by weight of total catalyst, of a halogen, particularly fluorine or chlorine, or 1 to 25% wt. by weight of total catalyst, of phosphorus.
• suitable supports are alumina, with or without the stated quantity of halogen or phosphorus, titaniaalumina, zirconia-alumina and beryllia-alurnina.
• the catalyst may be employed as a fixed bed, a moving bed, or in the fluidized state.
• the degree of reduction in pour point is a function of the catalyst activity and in the case of a fixed bed process
• Hydrogen may be added on a once-through basis, or it may be recycled.
• the operating temperature may be gradually increased to compensate for loss of activity.
• continuous catalyst regeneration may be employed, using either a moving or fluidized catalyst bed process.
• a part only of a particular distillate may be treated by the process according to the invention and the resulting product blended with the untreated portion of the distillate to give a final product of reduced pour point.
• EXAMPLE 1 A straight run gas oil having a boiling range of 249 of 2.7% wt. cobalt oxide ((300) and 15.5% wt. molybdenum oxide (M on alumina and promoted with 3.34% wt. fluorine, in the presence of recycled hydrogen.
• the process conditions employed and the results obtained 4
• EXAMPLE 3 A vacuum gas oil having a boiling range of 327 C. to 400 C. ASTM was processed over a catalyst consisting are Set out in Table 1 below! 5 of 3.2% wt. cobalt oxide (C00) and 15.0% wt. molyb- Table 1 denum oxide (M00 on alumina and promoted with 3.1% wt. fluorine, in the presence of recycled hydrogen.
• a process for the treatment of distillate petroleum fractions boiling within the range 150-450 C. to lower the pour point at least 10 F. without material reduction in the specific gravity .and diesel index of said distillate fractions comprising contacting the distillate fraction as feedstock in a treating zone and in the presence of hydrogen with a catalyst containing a group VIa metal on a silica-free, refractory oxide support, the hydrogen to hydrocarbon mole ratio being from 5 to 1 to 20 to 1; maintaining a selected temperature and a selected space velocity in said zone, said selected temperature in said zone being maintained above 800 F. but not higher than about 900 F. and being a temperature at which, at said selected space velocity, not more than 20% wt. of the feedstock is converted to material boiling below 150 C.
• said selected space velocity being at least equal to the space velocity at which at said selected temperature selected space velocity but not greater than about 1500 p.s.i. ga., said selected temperature and said selected space velocity being correlated to reduce the pour point of the feedstock such that the pour point of the material of the treated distillate fraction boiling above C. is at least 10 F. lower than the pour point of the feedstock, and recovering the treated distillate fraction.
• refractory oxide support is selected from the class of supports consisting of the silica-free refractory oxides of elements from group II, III and 1V.
• a process as claimed in claim 8 wherein the support is zirconia-alumina.

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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)
• Crystallography & Structural Chemistry (AREA)
• General Chemical & Material Sciences (AREA)
• Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
• Catalysts (AREA)

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Cited By (3)

Citations (4)

• 0
  • NL NL257081D patent/NL257081A/xx unknown
  • US US3125508D patent/US3125508A/en not_active Expired - Lifetime
• 1959
  • 1959-10-20 GB GB35490/59A patent/GB908288A/en not_active Expired
• 1960
  • 1960-10-15 DE DE19601470461 patent/DE1470461A1/de active Pending

Patent Citations (4)

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