US3125511A - Treatment of hydrocarbon fractions to - Google Patents

Treatment of hydrocarbon fractions to Download PDF

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Publication number
US3125511A
US3125511A US3125511DA US3125511A US 3125511 A US3125511 A US 3125511A US 3125511D A US3125511D A US 3125511DA US 3125511 A US3125511 A US 3125511A
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catalyst
pour point
feedstock
space velocity
temperature
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    • 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
    • C10G45/62—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 containing platinum group metals or compounds thereof

Definitions

  • a hydrocarbon fraction boiling above 150 C. is contacted in the presence of hydrogen with a catalyst comprising a platinum group metal on a support containing a major proportion of alumina and at least 1% wt. of halogen at a temperature of at least 600 F., a pressure of at least 100 p.s.i.g., and a space velocity not exceeding 8.0 v./v./hr., the temperature and space velocity used being correlated to give a product boiling above 150 C. having a pour point at least F. lower than the pour point of the feedstock.
  • the temperature is below that at which substantial cracking occurs, and for the purposes of the present specification 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 so converted.
  • fraction as used in this specification includes both fractions which are distillable at normal or reduced pressure, for example, gas oils and waxy distillates and also residues and portions thereof, for example deasphalted residues.
  • Particularly suitable fractions for use as feedstocks are distillate fractions boiling within the range 150 to 450 C. and more particularly within the range 250 to 450 C.
  • a part only of a particular fraction may be treated by the process according to the invention and the resulting product blended with the untreated portion to give a final product of reduced pour point.
  • the amount of halogen is preferably in the range 1 to 15% wt. and more particularly 1 to 10% wt.
  • suitable halogens are fluorine and chlorine, the former being preferred both on account of the greater effectiveness for pour point reduction and the greater stability of fluorine-containing catalysts as compared with similar chlorine-containing catalysts.
  • the halogen may be incorporated into the catalyst by treating the catalyst with a halogen compound, preferably one containing halogen, together with one or more of the elements of carbon, hydrogen or oxygen.
  • a halogen compound preferably one containing halogen
  • suitable halogen compounds are hydrogen halides and halogen derivatives of aliphatic hydrocarbons having from 1 to 4 carbon atoms.
  • the halogen is normally in- 3,125,511 Patented Mar. 17, 1964 ice corporated in the catalyst already consisting of a platinum group metal on a support and this catalyst may be halogen free or it may already contain a small amount (less than 1% wt.) of halogen. Examples of suitable ways in which the halogen may be incorporated into the catalysts are described in the specific examples.
  • the platinum group metal content of the catalyst may be within the range 0.01 to 5.0 percent weight preferably 0.1 to 1.0 percent weight.
  • the preferred platinum group metals are platinum and palladium.
  • the catalyst support material contains, as stated above, at least a major proportion of alumina, and alumina may be the only refractory oxide present in the catalyst. However, if desired the catalyst may also contain a minor proportion of one or more of the oxides of metals of groups II, III and IV of the periodic table. Preferably the amount of the group II, III or IV metal oxides is from 525% wt. of the support.
  • suitable supports include alumina, silica/ alumina, titania/ alumina, zirconia/ alumina and beryllia/alumina.
  • the support material may also contain a minor proportion of one or more compounds (including oxides) of non-metallic elements in groups III, IV and V for example boron or phosphorus, which may if desired be combined or mixed with any of the metal oxides of groups II, III and IV.
  • the amount of the compounds of the non-metallic elements is from 5 to 25% wt. of the support.
  • the catalyst may be employed as a fixed bed, a moving bed or a fluidised bed.
  • An essential requirement to obtain pour point reduction with any given catalyst and operating conditions employed is a correlation of temperature and space velocity.
  • the feedstock used, the activity of the catalyst used and the reduction of pour point required should also be taken into account when selecting the process conditions.
  • the operating conditions may be more severe (i.e. conditions of higher temperature and/ or lower space velocity) than when treating lighter feedstocks.
  • a more active catalyst for example one containing fluorine rather than chlorine, less severe conditions may be used, an equivalent reduction in pour point being obtainable at a lower temperature and/or higher space velocity.
  • the temperature will not normally exceed 950 F. and is preferably at least 700 F.
  • the space velocity will not normally be less than 0.1 v./v./hr., and more particularly not less than 0.5 v./ v./ hr. It preferably does not exceed 8 v./v/.hr. and more particularly does not exceed 5 v./v./hr.
  • the pressure may be from to 1500 p.s.i.g. and the hydrogenzhydrocarbon mole ratio from 1:1 to 20:1.
  • the process may be operated with or without a nett hydrogen consumption.
  • a net hydrogen consumption is generally favoured by increase in pressure, and for any given temperature and space velocity the pressure at which the hydrogen consumption and hydrogen production are in balance is known as the equilibrium pressure. It is generally preferred to operate at or above this pressure because this results in an increase in the on stream time before catalyst regeneration or replacement is necessary.
  • Another advantage of this type of operation is, for example, that when processing feedstocks such as gas oils for the production of diesel oils reduction of the diesel index is minimised or avoided.
  • the principal advantages of operating below the equilibrium pressure are that a reduction in the specific gravity of the distillate is minimised or avoided, and that hydrogen is produced, this by- 3 drogen being then available for use in other hydrogenconsuming processes.
  • Operation of the process using a fixed bed of catalyst is carried out in the normal manner, which is to increase the temperature gradually as the run continues in order to maintain the quality of the product at the desired level.
  • the process of the present invention will normally lower all the three points specified viz. cloud point, pour point and freezing point. Which point is taken as the criterion for any particular operation will depend on the feedstock used and the use to which the product is to be put. The freezing point is normally only of importance with the lower boiling feedstocks.
  • EXAMPLE 1 A reforming catalyst containing 0.75% wt. platinum 0.35% wt. chlorine and 0.35% wt. fluorine on an alumina support was treated with an excess of a mixture of 3 parts water and 1 part concentrated HCl at a temperature below 10 C. for 2 hours. The catalyst treated was then dried for 12 hours at 105 C. and calcined in air at 550 C. for 2 hours. The chlorine content of the catalyst was 1.2% wt. The catalyst was then used to reduce the pour point of a heavy gas oil. The heavy gas oil had been previously hydrocatalytically desulphurised over a catalyst of 2.4% wt. cobalt oxide and 14.3% wt. molybdenum oxide under the process conditions and with the results set out below:
  • the pour point of the product was 35 F.
  • the pour point was only reduced to 45 F.
  • EXAMPLE 2 The platinum/ chlorine/ fiuorine/ alumina catalyst of Example 1 was dried for 2 hours at 570 F. in nitrogen and treated in a current of anhydrous HCl vapour using nitrogen carrier gas at 570 F. for 3 hours.
  • the chlorine content of the treated catalyst was 2.0% wt.
  • Example 1 The treated catalyst when used to treat the heavy gas oil of Example 1 under the same conditions as Example 1, gave a product with a pour point of 10 F.
  • EXAMPLE 3 The platinum/ chlorine/ fiuorine/ alumina catalyst of Example 1 was dried for 2 hours at 570 F. in nitrogen and treated in a current of dry nitrogen containing carbon tetrachloride vapour at 570 F. for 2 hours. It was then flushed with N at 570 F. for 1 hours.
  • the catalyst was then used to reduce the pour point of a heavy gas oil.
  • the heavy gas oil had been previously hydro-catalytically desulphurised over a catalyst of 2.4 percent weight cobalt oxide and 14.3 percent weight molybdenum oxide on alumina under the process conditions given below:
  • EXAMPLE 5 containing 0.58 percent weight of platinum and 0.81 percent weight of chlorine was added slowly to an equal 100 ml. of commercial platinum-on-alumina catalyst, 5 Volume of 5 Percent i aqueous hlfdrogen fluoride containing 0.58 percent weight of platinum and 0.81 perand the bulk kept c001 The i was cent weight f chlorine was added Slowly to an equal allowed to stand for 30m1nutes, the excess llqllld decanted volume f 5 percent weight aqueous hydrogen fluoride oil and the catalyst dried at 105 C. for 2 hours and then Th b lk was i d and maintained at through calclned at 500 C. for 1 hour. The fluorine content of out.
  • ASTM boiling range straight run gas group metal on a support containing a major proportion oil was used to assess the activity of the above catalyst. of alumina and from 1 to 15% wt. of halog the y
  • the test was carried out over an extended period and the 2 Q hyflfflcarbon mole ratio being from 1 t0 1 20 to operating conditions and results obtained are given below: malntalmng a Selected tempfifalllre and Selected p t velocity in said zone, said selected temperature in said zone being maintained at least at 700 F. but not higher Hours on stream than about 950 F. and being a temperature at which, at
  • Feed 8M3 171477 367x369 the feedstock is converted to material boiling below 150 C. and said selected space velocity being at least 0.01
  • Gas 011 (150 C r 151 e r l u 3.
  • the catalyst cent wt 10M contains from 1 to 10% wt. of halogen.

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Crystallography & Structural Chemistry (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)
US3125511D 1960-10-28 Treatment of hydrocarbon fractions to Expired - Lifetime US3125511A (en)

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GB37124/60A GB943237A (en) 1960-10-28 1960-10-28 Improvements relating to the treatment of hydrocarbon fractions

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BE (2) BE609623A (en, 2012)
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NL (2) NL270707A (en, 2012)

Cited By (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3328119A (en) * 1963-09-18 1967-06-27 Exxon Research Engineering Co Synthetic crystalline alumino-borosilicate zeolites and preparation thereof
US3420768A (en) * 1966-02-21 1969-01-07 Chevron Res Middle distillate hydrogen treating processes
US3431194A (en) * 1966-10-14 1969-03-04 Exxon Research Engineering Co Process for lowering the pour point of a middle distillate
US3487005A (en) * 1968-02-12 1969-12-30 Chevron Res Production of low pour point lubricating oils by catalytic dewaxing
US3486993A (en) * 1968-01-24 1969-12-30 Chevron Res Catalytic production of low pour point lubricating oils
US3539468A (en) * 1968-10-25 1970-11-10 Catalysts & Chem Inc Alumina hydrate compositions
US3629096A (en) * 1967-06-21 1971-12-21 Atlantic Richfield Co Production of technical white mineral oil
US3639227A (en) * 1969-11-17 1972-02-01 Chevron Res Chloride addition during hydrogenation
US3676331A (en) * 1970-06-19 1972-07-11 Phillips Petroleum Co Upgrading of crude oils
US4420388A (en) * 1981-09-14 1983-12-13 Standard Oil Company (Indiana) Hydrotreating vacuum gas oils with catalyst and added organic fluorine compound
US4900707A (en) * 1987-12-18 1990-02-13 Exxon Research And Engineering Company Method for producing a wax isomerization catalyst
US4906601A (en) * 1988-12-16 1990-03-06 Exxon Research And Engineering Company Small particle low fluoride content catalyst
US4923588A (en) * 1988-12-16 1990-05-08 Exxon Research And Engineering Company Wax isomerization using small particle low fluoride content catalysts
US4929795A (en) * 1987-12-18 1990-05-29 Exxon Research And Engineering Company Method for isomerizing wax to lube base oils using an isomerization catalyst
US4937399A (en) * 1987-12-18 1990-06-26 Exxon Research And Engineering Company Method for isomerizing wax to lube base oils using a sized isomerization catalyst
US4959337A (en) * 1987-12-18 1990-09-25 Exxon Research And Engineering Company Wax isomerization catalyst and method for its production
US4992159A (en) * 1988-12-16 1991-02-12 Exxon Research And Engineering Company Upgrading waxy distillates and raffinates by the process of hydrotreating and hydroisomerization
US6274029B1 (en) 1995-10-17 2001-08-14 Exxon Research And Engineering Company Synthetic diesel fuel and process for its production
US6309432B1 (en) 1997-02-07 2001-10-30 Exxon Research And Engineering Company Synthetic jet fuel and process for its production
US6822131B1 (en) 1995-10-17 2004-11-23 Exxonmobil Reasearch And Engineering Company Synthetic diesel fuel and process for its production

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3318802A (en) * 1965-01-21 1967-05-09 Exxon Research Engineering Co Hydrocracking process employing a crystalline alumino-silicate activated with a chlorine compound
US3446730A (en) * 1966-06-21 1969-05-27 Gulf Research Development Co Catalytic hydrodenitrogenation of petroleum fractions
US3493517A (en) * 1967-10-02 1970-02-03 Chevron Res Metal phosphate containing catalysts and preparation thereof
US3928176A (en) * 1974-04-01 1975-12-23 Exxon Research Engineering Co Heavy crude conversion

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2888397A (en) * 1953-06-02 1959-05-26 Kellogg M W Co Hydrocarbon conversion process
US2967144A (en) * 1958-01-24 1961-01-03 Texaco Inc Method of processing lubricating oil

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2885352A (en) * 1953-06-10 1959-05-05 Socony Mobil Oil Co Inc Process for hydrodesulfurization employing a platinum-alumina catalyst
US2890167A (en) * 1953-11-16 1959-06-09 Universal Oil Prod Co Conversion process using a phosphoruscontaining platinum group metal catalyst
BE545961A (en, 2012) * 1955-03-10
US2965564A (en) * 1956-02-01 1960-12-20 Exxon Research Engineering Co Hydrodesulfurization and hydrogenation with platinum-eta alumina catalyst
US3085971A (en) * 1959-05-07 1963-04-16 Sinclair Research Inc Hydrogenation process employing hydrogen halide contaminated hydrogen

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2888397A (en) * 1953-06-02 1959-05-26 Kellogg M W Co Hydrocarbon conversion process
US2967144A (en) * 1958-01-24 1961-01-03 Texaco Inc Method of processing lubricating oil

Cited By (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3328119A (en) * 1963-09-18 1967-06-27 Exxon Research Engineering Co Synthetic crystalline alumino-borosilicate zeolites and preparation thereof
US3420768A (en) * 1966-02-21 1969-01-07 Chevron Res Middle distillate hydrogen treating processes
US3431194A (en) * 1966-10-14 1969-03-04 Exxon Research Engineering Co Process for lowering the pour point of a middle distillate
US3629096A (en) * 1967-06-21 1971-12-21 Atlantic Richfield Co Production of technical white mineral oil
US3486993A (en) * 1968-01-24 1969-12-30 Chevron Res Catalytic production of low pour point lubricating oils
US3487005A (en) * 1968-02-12 1969-12-30 Chevron Res Production of low pour point lubricating oils by catalytic dewaxing
US3539468A (en) * 1968-10-25 1970-11-10 Catalysts & Chem Inc Alumina hydrate compositions
US3639227A (en) * 1969-11-17 1972-02-01 Chevron Res Chloride addition during hydrogenation
US3676331A (en) * 1970-06-19 1972-07-11 Phillips Petroleum Co Upgrading of crude oils
US4420388A (en) * 1981-09-14 1983-12-13 Standard Oil Company (Indiana) Hydrotreating vacuum gas oils with catalyst and added organic fluorine compound
US4900707A (en) * 1987-12-18 1990-02-13 Exxon Research And Engineering Company Method for producing a wax isomerization catalyst
US4929795A (en) * 1987-12-18 1990-05-29 Exxon Research And Engineering Company Method for isomerizing wax to lube base oils using an isomerization catalyst
US4937399A (en) * 1987-12-18 1990-06-26 Exxon Research And Engineering Company Method for isomerizing wax to lube base oils using a sized isomerization catalyst
US4959337A (en) * 1987-12-18 1990-09-25 Exxon Research And Engineering Company Wax isomerization catalyst and method for its production
US4906601A (en) * 1988-12-16 1990-03-06 Exxon Research And Engineering Company Small particle low fluoride content catalyst
US4923588A (en) * 1988-12-16 1990-05-08 Exxon Research And Engineering Company Wax isomerization using small particle low fluoride content catalysts
US4992159A (en) * 1988-12-16 1991-02-12 Exxon Research And Engineering Company Upgrading waxy distillates and raffinates by the process of hydrotreating and hydroisomerization
US6274029B1 (en) 1995-10-17 2001-08-14 Exxon Research And Engineering Company Synthetic diesel fuel and process for its production
US6296757B1 (en) 1995-10-17 2001-10-02 Exxon Research And Engineering Company Synthetic diesel fuel and process for its production
US6607568B2 (en) 1995-10-17 2003-08-19 Exxonmobil Research And Engineering Company Synthetic diesel fuel and process for its production (law3 1 1)
US6822131B1 (en) 1995-10-17 2004-11-23 Exxonmobil Reasearch And Engineering Company Synthetic diesel fuel and process for its production
US6309432B1 (en) 1997-02-07 2001-10-30 Exxon Research And Engineering Company Synthetic jet fuel and process for its production
US6669743B2 (en) 1997-02-07 2003-12-30 Exxonmobil Research And Engineering Company Synthetic jet fuel and process for its production (law724)

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BE609624A (en, 2012)
GB943237A (en) 1963-12-04
NL270707A (en, 2012)
US3125510A (en) 1964-03-17
NL270706A (en, 2012)
BE609623A (en, 2012)

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