US3125510A - Treatment of hydrocarbon fractions - Google Patents

Treatment of hydrocarbon fractions Download PDF

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Publication number
US3125510A
US3125510A US3125510DA US3125510A US 3125510 A US3125510 A US 3125510A US 3125510D A US3125510D A US 3125510DA US 3125510 A US3125510 A US 3125510A
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feedstock
pour point
space velocity
temperature
zone
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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

  • This invention relates to the treatment of hydrocarbon fractions, particularly petroleum fractions, boiling above 150 C., and the principal object of the invention is to provide a process by means of which the cloud point, pour point or freezing point of such fractions may be lowered.
  • a hydrocarbon fraction boiling above 150 C. is contacted with a catalyst comprising a platinum group metal on a refractory oxide support in the presence of hydrogen and added halogen at a temperature of at least 600 F. and a pressure of at least 100' p.s.i.g., the temperature and space velocity used being correlated to give a product boiling above 150 C. having a pour point at least 5 F. lower than the pour point of the feedstock.
  • 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 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.
  • the added halogen may be added to the reaction zone in any convenient manner, for example by injecting it directly into the reaction zone, by adding it to the hydrogen-containing gas used, or, preferably, by adding it to the feedstock.
  • suitable halogens are fluorine,
  • halogen may be added as such, or as a halogen compound which is decomposable to halogen under the reaction conditions.
  • Preferred halogen compounds are those having halogen together with one or more of the elements carbon, hydrogen or oxygen, for example hydrogen halides and halogen derivatives of aliphatic hydrocarbons having from 1 to 4 carbon atoms.
  • the halogen is preferably added in an amount from 0.001 to 1% wt. by weight of feedstock.
  • the platinum group metal content of the catalyst may be within the range 0.01 to 5% wt., preferably 0.11.0% wt.
  • the preferred platinum group metals are platinum and palladium.
  • the refractory oxide support may be one or more of the oxides of metals of group II, III and IV of the periodic table. Preferably it contains a major proportion of alumina and it may also contain a minor proportion of one or more of the other 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 5-25% 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 halogen free or it may contain less than 1% wt. of halogen as disclosed in the complete specification of cognate UK. patent applications Nos. 28,788/ 60, 37,123/ 60 and 5,774/61, or it may contain at least 1% Wt. of halogen as disclosed in the complete specification of UK. patent application No. 37,126/60, in addition to the halogen present in the reaction zone by the addition of halogen.
  • the catalyst may be employed as a fixed bed, a moving bed, or in the fluidised state.
  • 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.
  • 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 C. Prefen ably not more than 15% wt. of the feedstock is so converted.
  • 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. Preferably it does not exceed 8 v./
  • the pressure may be from 100 to 1500 p.s.1.g. and 5 Prewure p Sig 1000 the hydrogen:hydrocarbon mole ratio from 1:1 to 20:1.
  • Temppratu'rg 730 The process may be operated with or without a net S pace velocity v./v./hr 2.0 hydrogen consumption.
  • a net hydrogen consumption Gas recycle rate s.c.f./b 1000 is generally favoured by increase in pressure and for any given temperature and space velocity the pressure at R ul which the hydrogen consumption and hydrogen production are in balance is known as the equilibrium pres- Feed Product sure. It is generally preferred to operate at or above this pressure because this results in an increase in the onspecific Gravity 0 13/600 F M76 0850 stream time before catalyst regeneration or replacement 15 i t is necessary.
  • Another advantage of this type of oper- 051j'g555ggg5555; jjj 52 atlon is, for example, that when processing feedstocks 3g? g gg g such as gas oils for the production of diesel oils, reducll fffi?
  • the process of the present invention will normally Platinum 0.75 lower all the three points specified, viz. cloud point, pour Fluorine 0.35 point and freezing point. Which point is taken as the 9 Chlorine 0.35 criterion for any particular operation will depend on the Al ina Balance feedstock used and the use to which the product is to be Four runs were carried out In the first run them was P The freezlng P 1S normally only of lmponance no addition of a halogen compound to the reaction zone;
  • the second carbon tetrachloride was added to the feed- In c pendlng PP a 3/ 61 a procstock in an amount to give 0.1% wt. of chlorine by weight ess for the treatment of hydrocarbon fractions boiling of feedstock; in the third the amount of carbon tetraabove 150 C. to reduce their cloud point, pour point, or chloride was sufficient to give 0.5% wt. chlorine, and in freezing point is described, in which the fractions are the fourth tertiary butyl chloride was added in an amount first treated to reduce content of aromatic hydrocarbons, g Wt. lorm or nitrogen compounds or both.
  • Feed Feed Feed Feed Product (Boiling 150 0.):
  • Percent wt 100 92 100 100 100 90 cation Nos. 28,788/60, 37,123/60 and 5,774/61 and in the complete specification of UK. application No. 37,126/ 60.
  • feedstock such that the pour point of the material of the Pressure, p.s.i.g 500 500 500 500 Space velocity, v./v./hr. 1.0 1.0 1.0 1.0 1.0 1.0
  • a process for the treatment of distillate petroleum fractions boiling within the range 150450 C. to lower the pour point at least 5 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 and of halogen added to the treating zone in an amount from about 0.001 to 1% by weight of feedstock with a catalyst comprising a platinum group metal on a refractory oxide support, the hydrogen to hydrocarbon mole ratio being from 1 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 at least at 700 F. but not higher than about 950 F.
  • halogen is added in the form of a compound of halogen in which halogen is combined with at least one of the elements carbon, hydrogen and oxygen.

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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)
US3125510D 1960-10-28 Treatment of hydrocarbon fractions Expired - Lifetime US3125510A (en)

Applications Claiming Priority (1)

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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 (ja)
GB (1) GB943237A (ja)
NL (2) NL270707A (ja)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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

Families Citing this family (21)

* 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
US3318802A (en) * 1965-01-21 1967-05-09 Exxon Research Engineering Co Hydrocracking process employing a crystalline alumino-silicate activated with a chlorine compound
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
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
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
US4959337A (en) * 1987-12-18 1990-09-25 Exxon Research And Engineering Company Wax isomerization catalyst and method for its production
US4923588A (en) * 1988-12-16 1990-05-08 Exxon Research And Engineering Company Wax isomerization using small particle low fluoride content catalysts
US4906601A (en) * 1988-12-16 1990-03-06 Exxon Research And Engineering Company Small particle low fluoride content catalyst
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
US5689031A (en) 1995-10-17 1997-11-18 Exxon Research & 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
US5766274A (en) 1997-02-07 1998-06-16 Exxon Research And Engineering Company Synthetic jet fuel and process for its production

Citations (6)

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Publication number Priority date Publication date Assignee Title
US2793984A (en) * 1955-03-10 1957-05-28 British Petroleum Co Preparation and use of desulphurisation catalysts
US2885352A (en) * 1953-06-10 1959-05-05 Socony Mobil Oil Co Inc Process for hydrodesulfurization employing a platinum-alumina catalyst
US2888397A (en) * 1953-06-02 1959-05-26 Kellogg M W Co Hydrocarbon conversion process
US2890167A (en) * 1953-11-16 1959-06-09 Universal Oil Prod Co Conversion process using a phosphoruscontaining platinum group metal catalyst
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

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2967144A (en) * 1958-01-24 1961-01-03 Texaco Inc Method of processing lubricating oil

Patent Citations (6)

* 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
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
US2793984A (en) * 1955-03-10 1957-05-28 British Petroleum Co Preparation and use of desulphurisation catalysts
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

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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

Also Published As

Publication number Publication date
BE609624A (ja)
BE609623A (ja)
NL270706A (ja)
NL270707A (ja)
US3125511A (en) 1964-03-17
GB943237A (en) 1963-12-04

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