US3125510A - Treatment of hydrocarbon fractions - Google Patents
Treatment of hydrocarbon fractions Download PDFInfo
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- 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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- Prior art keywords
- feedstock
- pour point
- space velocity
- temperature
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- 239000004215 Carbon black (E152) Substances 0.000 title claims description 7
- 229930195733 hydrocarbon Natural products 0.000 title claims description 7
- 150000002430 hydrocarbons Chemical class 0.000 title claims description 7
- 238000000034 method Methods 0.000 claims description 24
- 229910052736 halogen Inorganic materials 0.000 claims description 21
- 150000002367 halogens Chemical class 0.000 claims description 21
- 239000003054 catalyst Substances 0.000 claims description 19
- 238000009835 boiling Methods 0.000 claims description 16
- 239000001257 hydrogen Substances 0.000 claims description 16
- 229910052739 hydrogen Inorganic materials 0.000 claims description 16
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical class [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 15
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 15
- 239000000463 material Substances 0.000 claims description 11
- 230000005484 gravity Effects 0.000 claims description 4
- 239000003208 petroleum Substances 0.000 claims description 4
- 230000002596 correlated effect Effects 0.000 claims description 3
- 239000007789 gas Substances 0.000 description 17
- 239000003921 oil Substances 0.000 description 15
- 239000000047 product Substances 0.000 description 13
- 229910052751 metal Inorganic materials 0.000 description 10
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 239000000460 chlorine Substances 0.000 description 7
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 6
- 229910052801 chlorine Inorganic materials 0.000 description 6
- 150000002366 halogen compounds Chemical class 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 238000007710 freezing Methods 0.000 description 4
- 230000008014 freezing Effects 0.000 description 4
- 229910052697 platinum Inorganic materials 0.000 description 4
- NBRKLOOSMBRFMH-UHFFFAOYSA-N tert-butyl chloride Chemical compound CC(C)(C)Cl NBRKLOOSMBRFMH-UHFFFAOYSA-N 0.000 description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000005336 cracking Methods 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- FCBJLBCGHCTPAQ-UHFFFAOYSA-N 1-fluorobutane Chemical group CCCCF FCBJLBCGHCTPAQ-UHFFFAOYSA-N 0.000 description 2
- LTPBRCUWZOMYOC-UHFFFAOYSA-N Beryllium oxide Chemical compound O=[Be] LTPBRCUWZOMYOC-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- -1 hydrogen halides Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 230000000737 periodic effect Effects 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- RKSOPLXZQNSWAS-UHFFFAOYSA-N tert-butyl bromide Chemical compound CC(C)(C)Br RKSOPLXZQNSWAS-UHFFFAOYSA-N 0.000 description 2
- 241001156002 Anthonomus pomorum Species 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 150000001649 bromium compounds Chemical class 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- 229910017464 nitrogen compound Inorganic materials 0.000 description 1
- 150000002830 nitrogen compounds Chemical class 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
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
- C10G45/58—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)
Description
3 125 510 TREATMENT or HrnnocAnnoN FRACTIONS Kenneth Tupman and Peter Thomas White, Snnhury-on- Thames, England, assignors to The British Petroleum Company Limited, London, England, a British joint-.
stock corporation No Draw'mg. Filed Oct. 24, 1961, Ser. No. 147,182 Claims priority, application Great Britain Oct. 28, 1960 10 Claims. (Cl. 208264) 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.
According to the present invention 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.
It has been found that the presence of added halogen gives a markedly greater reduction in pour point compared with a similar operation without the halogen. In the case of the treatment of a heavy gas oil feedstock having a pour point of 50 F. with a platinum-aluminahalogen catalyst for example, the presence of an added halogen compound gave a reduction in pour point of 75 F. compared with a reduction of F. for a similar operation without the halogen compound. The reduction of pour point of 75 F. was achieved with a yield of product (boiling above 150 C.) of 80% wt.
The term 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.
It has been found that it is not necessary to desulphurise the feedstock prior to submitting it to the pour point reduction process, although such a preliminary desulphurisation may be given if desired. When operating with a sulphur-containing feedstock (-for example one with more than 0.1% Wt. of sulphur) the process will normally effect considerable desulphurisation simultaneously with the lowering of the cloud point, pour point or freezing point. It has also been found that the process can be operated in the presence of considerable quantities of hydrogen sulphide, so that, for example, the process can be operated on the total effluent of a previous hydrocatalytic desulphurisation process.
If desired, 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. Examples of suitable halogens are fluorine,
3,125,510 Patented Mar. 17, 1964 chlorine, and bromine, the former being preferred because corrosion difliculties are minimised. The 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. Examples of 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. Preferably 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. In general the higher the temperature, the higher the space velocity that can be employed, the upper limit of temperature, at any given space velocity, being determined by the amount of cracking occurring. 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. When treating the heavier feedstocks, for example, the operating conditions may be more severe (i.e. conditions of higher temperature and/or lower space velocity) than when treating lighter feedstocks.
When using a more active catalyst or when using a greater quantity of added halogen, less severe conditions may be used, an equivalent reduction in pour point being obtainable at a lower temperature and/or higher space velocity.
Preferably 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. In practice the temperature will not normally exceed 950 F. and is preferably at least 700 F. Similarly in practice 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./
used and inspection data on the feed and product were as follows:
Operating Conditions o ul 'cee v /hr and m re part1c arly it does not ex d v /v Catalyst co Mo/alumma hr. 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; jjjj 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? f 1:: I: 395 tion of the diesel index is minimised or avoided. The lg u ggg h 8g principal advantage of operating below the equilibrium 20 clogd f pjj""""' II: I: Q pressure is that a reduction in the specific gravity of the Your Point, F 50 50 distillate is minimised or avoided. P the FY0965S 115mg a d f 0f P y The hydrofined product was then processed over a is carried out in the normal manner, whicn 13 to increase platinum Catalyst to reduce its pour point The Catalyst the temperature gradually as the run continues in order composition to maintain the quality of the product at the desired level. Percent wt 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;
. g With the lower bolllng f 1n 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. go After the processing the product was stabilised to re- Such a process may if desired, be Combined with the move a small proportlon of material boning below 150 0 process of the present invention, as may the processes FE gave a gas 9f the requlred flash Pomt (1 50 disclosed in the copending applications referred to earlier, 5913 g used and results Obtained are viz. in the complete specification of cognate UK. appliglven a e e TABLE 1 Pressure, p.s.i.g 500 500 500 500 Space Velocity, v./v./hr 1.0 1.0 1.0 1.0 Hydrogen Rate (once through), s.c.f./b. 5000 5000 5000 5000 Feedstock DcsulphurisedHcavy Dcsulphurised Heavy Gas Desulphuriscd Heavy Gas Desulphuriscd Heav Ga Gas Oil Oil containing 0.1% Wt. Oil containing 0.5% wt. Oilcontaining0.5%wt.01 01 (added as carbon tctra- C1 (added as carbon tetra- (added as tertiary butyl chloride) chloride) chloride) Operating Temperature,
F 775 800 825 775 800 825 775 800 825 775 800 825 Product (Unstabllised):
Cloud Point, F 54 50 44 42 26 12 28 16 12 24 s -4 Pour Point, F 50 40 3o 20 10 25 15 -15 20 20 4.5
Feed Feed Feed Feed Product (Boiling 150 0.):
Cloud Point, F 60 66 60 60 26 12 -s Pour Point, F 50 50 20 -5 -25 Yield (based on feed),
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.
The invention is illustrated by the following examples.
EXAMPLE 1 A heavy gas oil was hydrocatalytically desulphurised over a catalyst of 2.4% wt. cobalt oxide and 14.3% wt.
The results show the very much greater reduction in pour point obtainable when operating in the presence of a halogen compound.
EXAMPLE 2 A comparison of the effects of fluorides, chlorides and bromides on the pour point reduction of desulphurised heavy gas oil was carried out using the same catalyst,
molybdenum oxide on alumina. The process conditions 7 feedstock and feedstock preparation as those used in Ex- O ample 1. Three runs Were carried out, in the first tertiary butyl chloride was added to the feedstock in an amount to give 0.1 percent weight chlorine by weight of feedstock; in the second tertiary butyl bromide was added to the 6 is converted to material boiling below 150 C. and said selected space velocity being at least 0.01 v./v./hr. but not higher than 8.0 v./v./hr. at which, at said selected temperature, not more than 20% wt. of the feedstock is feedstock to give 0.1 percent of bromine; in the third converted to material boiling below 150 C.; maintaining tertiary butyl fluoride was added to the feedstock to give a selected pressure in said zone in the range 1001 500 0.1 percent weight fluorine. p.s.i.g.a., said selected temperature and said selected space The process conditions used and results obtained were velocity being correlated to reduce the pour point of the as follows: 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
Hydrogen rate through), s.c.f./b Feedstock (once 5,000 Desulphurised Heavy Gas Oil 5,000 Desulphurised Heavy Gas Oil containing 0.1 percent wt. 01 (added as 5,000 Desulphurised Heavy Gas Oil containing 0.1 percent wt. F (added as tertiary 5,000 Desulphuriscd Heavy Gas Oil containing 0.1 percent wt. Br (added as tertiary butyl chloride) tertiary butyl bromide) butyl fluoride) Operating Temperature, F 775 800 8 5 775 800 825 775 800 825 775 800 825 Feed Product Data:
Cloud Point, F 60 54 50 44 40 14 48 38 18 48 42 20 Pour Point, F 50 50 45 40 15 5 30 5 45 40 5 EXAMPLE 3 treated distillate fraction boiling above 150 C. is at least The same feedstock, feedstock preparation and catalyst as that of Example 1 were used to study the effect of changes in process variables on the pour point reduction of desulphurised heavy gas oil containing carbon tetrachloride in an amount to give 0.1 percent weight chlorine by weight of feedstock.
The process conditions used and results obtained were as follows:
Hours on Stream 10-12 34-36 84-86 100-102 116-118 140-142 Operating Conditions:
Feedstock Desulphurised Heavy Gas Oil Containing 0.1% wt. 01 Catalyst Pt/Alumina Reactor Pressure p 750 750 750 750 750 750 Reactor temperature, F 775 775 825 825 675 7 5 Space velocity, v./v./hr, 1.0 2. 5 1. 0 2. 5 1.0 2. 5 Gas recycle rate, s.c.f./b 10,000 10,000 10, 000 10, 000 10, 000 10,000
Feed
Product (150 0.):
Yield, percent wt 90. 2 94. 9 86. 6 93. 0 97. 7 97.6 Cloud Point, F 60 28 46 6 36 58 60 Four Point, F 20 40 15 30 50 50 This example illustrates the necessity of correlating the temperature and space velocity to give a reduction in pour point. At 675 F. and 1 v./v./hr., and 725 and 2.5 v./v./hr., the temperature is too low, at the space velocity used, to give pour point reduction. However, if the temperature is raised to 775, pour point reduction is obtained at both space velocities, being greater at the lower space velocity. Raising the temperature to 825 F. further reduces the pour point.
We claim:
1. 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. and being a temperature at which, at said selected space velocity, not more than 20% wt. of the feedstock 5. A process as claimed in claim 1 wherein the 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.
6. A process as claimed in claim 1 wherein the catalyst contains from 0.01 to 5.0% wt. of the platinum group metal.
7. A process as claimed in claim 1 wherein the platinum group metal is platinum.
8. A process as claimed in claim 1 wherein the space velocity is at least 0.5 v./v./ hr.
9. A process as claimed in claim 1 wherein the space velocity does not exceed 5 v./v./hr.
10. A process as claimed in claim 1 wherein the pressure is from to 1500 p.s.i.g., and the hydrogenzhydrocarbon mole ratio is from 1:1 to 20:1.
References Cited in the file of this patent UNITED STATES PATENTS 2,793,984 Northcutt et al. May 28, 1957 2,885,352 Ciapetta et al. May 5, 1959 2,888,397 Burton et a1. May 26, 1959 2,890,167 Haensel June 9, 1959 2,965,564 Kirshenbaum et al Dec. 20, 1960 3,085,971 Mooi et a1 Apr. 16, 1963 UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No, 3 125 510 March I7 1964 Kenneth Tupman et al., It is hereby certified that error appears in the above numbered patent req'liring correction and that the said Letters Patent should read as corrected below.
Column 3 line 35, for "No, 8238/61" read No, 8248/61 Signed and sealed this 8th day of September 1964.,
SEA L) Attest:
ERNEST W. SWIDER Attesting Officer EDWARD J. BRENNER Commissioner of Patents
Claims (1)
1. A PROCESS FOR THE TREATMENT OF DISTILLATE PETROLEUM FRACTIONS BOILING WITHIN THE RANGE 150-450*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. 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. AND SAID SELECTED SPACE VELOCITY BEING AT LEAST 0.01 V./V./HR. BUT NOT HIGHER THAN 9,0 V./V./HR. AT WHICH, AT SAID SELECTED TEMPERATURE, NOT MORE THAN 20% WT. OF THE FEEDSTOCK IS CONVERTED TO MATERIAL BOILING BELOW 150*C.; MAINTAINING A SELECTED PRESSURE IN SAID ZONE IN THE RANGE 100-1500 P.S.I.G.A., 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 150*C. IS AT LEAST 5*F. LOWER THAN THE POUR POINT OF THE FEEDSTOCK, AND RECOVERING THE TREATED DISTILLATE FRACTION.
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB37124/60A GB943237A (en) | 1960-10-28 | 1960-10-28 | Improvements relating to the treatment of hydrocarbon fractions |
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US3125510A true US3125510A (en) | 1964-03-17 |
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ID=10393926
Family Applications (2)
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US3125510D Expired - Lifetime US3125510A (en) | 1960-10-28 | Treatment of hydrocarbon fractions | |
US3125511D Expired - Lifetime US3125511A (en) | 1960-10-28 | Treatment of hydrocarbon fractions to |
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US3125511D Expired - Lifetime US3125511A (en) | 1960-10-28 | Treatment of hydrocarbon fractions to |
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BE (2) | BE609624A (en) |
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Cited By (3)
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)
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 |
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 |
US4900707A (en) * | 1987-12-18 | 1990-02-13 | Exxon Research And Engineering Company | Method for producing a wax isomerization 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 |
US4906601A (en) * | 1988-12-16 | 1990-03-06 | Exxon Research And Engineering Company | Small particle low fluoride content catalyst |
US6296757B1 (en) | 1995-10-17 | 2001-10-02 | Exxon Research And Engineering Company | Synthetic diesel fuel and process for its production |
US5689031A (en) | 1995-10-17 | 1997-11-18 | Exxon Research & 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 |
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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 |
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US3085971A (en) * | 1959-05-07 | 1963-04-16 | Sinclair Research Inc | Hydrogenation process employing hydrogen halide contaminated hydrogen |
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US2967144A (en) * | 1958-01-24 | 1961-01-03 | Texaco Inc | Method of processing lubricating oil |
-
0
- BE BE609623D patent/BE609623A/xx unknown
- US US3125510D patent/US3125510A/en not_active Expired - Lifetime
- US US3125511D patent/US3125511A/en not_active Expired - Lifetime
- BE BE609624D patent/BE609624A/xx unknown
- NL NL270707D patent/NL270707A/xx unknown
- NL NL270706D patent/NL270706A/xx unknown
-
1960
- 1960-10-28 GB GB37124/60A patent/GB943237A/en not_active Expired
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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 |
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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 |
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BE609624A (en) | |
US3125511A (en) | 1964-03-17 |
GB943237A (en) | 1963-12-04 |
NL270706A (en) | |
BE609623A (en) | |
NL270707A (en) |
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