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US3125507A - Hydrofining hydrocarbon fractions - Google Patents

Hydrofining hydrocarbon fractions Download PDF

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US3125507A
US3125507A US3125507DA US3125507A US 3125507 A US3125507 A US 3125507A US 3125507D A US3125507D A US 3125507DA US 3125507 A US3125507 A US 3125507A
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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
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/24—Chromium, molybdenum or tungsten
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/24—Chromium, molybdenum or tungsten
    • B01J23/28—Molybdenum
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/85—Chromium, molybdenum or tungsten
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/85—Chromium, molybdenum or tungsten
    • B01J23/88—Molybdenum

Definitions

  • This invention relates to the conversion of hydrocarbon fractions, particularly petroleum fractions, boiling above 150 C., and a 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. It is also an object to desulphurise hydrocarbon fractions containing sulphur simultaneously with the reduction in cloud, pour or freezing point.
  • FIG. 1 is a graph showing the efiect of boron content and treating temperature on the pour point reducing activity of cobalt oxide-molybdenum oxide-alumina catalysts in the treatment of a hydrocarbon fraction according to the invention.
  • FIG. 2 is a graph showing the effect of boron content and treating temperature on the desulphurization activity of cobalt oxide-molybdenum oxide catalysts in the treatment of a hydrocarbon fraction according to the invention.
  • 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.
  • Some lower boiling material is likely to be produced by, for example, dehydrogenation, desulphurization and/or cracking and since the desired product boils above 150 C. this may be separated from the product, preferably by fractionation.
  • the boron content of the catalyst maybe from 1 to 20% :wt. by wt. of total catalyst but according to a particularly preferred embodiment the boron content is from 37% wt., preferably 46% wt.
  • the refractory oxide support may be selected from the refractory oxides of metals of groups II, III, and IV of the periodic table.
  • the preferred refractory oxide is alumina and the support may consist wholly of alumina or a mixture of refractory oxides having a major proportion of alumina and a minor proportion, preferably from 5-25% wt., of one or more other refractory oxides of metals of groups II, III, and IV.
  • suitable supports thus include alumina, silica/ alumina, titania/ alumina, zirconia/ alumina and beryllia/ alumina.
  • the group VIa metal is preferably in the form of an oxide or sulphide.
  • the catalyst may also contain a group VIII metal, preferably in the form of an oxide or sulphide, in addition to the group VIa metal.
  • the presence of a group VIII metal is particularly desirable if it is desired to desulphurise 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 molybdenum may be present in from 5 to 40% wt., calculated as the oxide M00 by weight of total catalyst and the iron group metal from 0.1 to 10% wt., calculated as the divalent metal 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).
  • Active catalysts can be prepared using any convenient known technique, for example by the techniques generally known as co-precipitation, impregnation or milling. It has been found however that it is preferable to incorporate the boron at an early or intermediate point in the catalyst preparation rather than subsequently to impregnate the pre-formed catalyst particles. Preferably the boron is incorporated into a hydrogel of the hydrated refractory oxide. The group VIa metal and group VIII metal if used may be added subsequently by impregnation of the preformed support, but they are also preferably added to the hydrogel.
  • the boron may be added initially in the form of a boron compound for example in the form of a decomposable salt or in the form of an oxide or oxyacid. After calcination of the catalyst, the boron is believed to be in the formof boron oxide.
  • Compounds used for adding the group VIa metal and the group VIII metal if used may be those conventionally used.
  • the catalyst may be employed as a fixed bed, a moving bed .on 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 having from 46% wt.
  • the temperature will not normally exceed 950 F. and it is preferably at least 750 F. and may be at least 800 F.
  • the pressure may be from 100 to 1500 p.s.i.g. and the hydrogenzhydrocarbon mole ratio from 1:1 to 20:1.
  • the space velocity will not normally be less than 0.1 v./v./hr. and it is preferably from 0.5 v./v./hr. to 5.0 v./v./hr.
  • the process may be operated with or without a net 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 minimized 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 hydrogen being then available for use in other hydrogen-consuming 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.
  • the pellets were then impregnated with a solution of 12 g. boric acid dissolved in 55 ml. hot isopropyl alcohol. The pellets were allowed to soak in this solution for 1 hour before drying at C. for 2 hrs. and calcining at 550 C. for 2 hrs. This impregnation was repeated twice more using the same quantities of boric acid and isopropyl alcohol. The pellets were dried at 100 C. for 2 hrs. and calcined at 550 C. for 2 hrs. after each impregnation.
  • composition of the finished catalyst was:
  • Molybdenum oxide (expressed as M00 9% wt. Boron oxide (expressed as B 0 18% wt. (equivalent to 5.6% wt. boron). Alumina Balance.
  • the catalyst was tested for pour point reducing activity using as feedstock a desulphurised heavy gas oil having an ASTM boiling range of 298-395 C., a cloud point of +60 F. and a pour point of +50 F.
  • the process conditions used were:
  • the catalyst was regenerated.
  • the initial regeneration gas contained 2% oxygen and the remainder inert gas and the final treatment was with neat air.
  • the temperature of the catalyst was kept below 550 C. After the regeneration the catalyst was tested again with the same feedstock and under the same conditions, then regenerated again and tested again.
  • EXAMPLE 2 A catalyst containing 1.84% wt. cobalt, 10% wt. molybdenum and 5% wt. boron on a base of alumina was prepared in a similar manner to the catalyst described in Example 1.
  • the catalyst was used to treat a gas oil having an ASTM boiling range of 250 to 360 C., a sulphur content of 1.2% wt, a pour point of +15 F. and a cloud point of +18 F. under the following conditions:
  • the cake of hydrogel was divided into 4 equal portions which were treated as follows:
  • Catalyst A.-A solution was made up by dissolving 19.3 g. of ammonium molybdate in 50 ml. of de-iom'sed water and to this was added a solution of 9.8 g. cobaltous nitrate dissolved in 20 ml. de-ionised water and the mixed solutions slurried with one portion of the alumina hydrogel. The mix was then dried at 110 C. for 16 hours, calcined for 2 hours at 550 C. and the calcined material pelleted to form A x /s" pellets.
  • the calcined pellets were then impregnated with a solution of 24.3 g. of boric acid dissolved in 100 ml. of de-ionised water.
  • the impregnated pellets were then dried at 105 C. for 2 hours and calcined for 2 hours at 550 C.
  • Catalyst B.-A second portion of the alumina hydrogel was slurried with a solution of boric acid made up by dissolving 24.3 g. boric acid in 100 ml. of de-ionised water. The mix was then dried at 110 C. for 2 hours and calcined for 2 hours at 550 C., the calcined material was formed into /8 x pellets, which were then impregnated with a solution made up by dissolving 19.3 g. ammonium molybdate in 50 ml. of de-ionised Water and mixing this solution with a solution of 9.8 g. cobaltous nitrate dissolved in 20 ml. de-ionised water. The impregnated pellets were dried at 105 C. for 2 hours and calcined for 2 hours at 550 C.
  • Catalyst C.A further portion of the alumina hydrogel was slurried with 24.3 g. boric acid dissolved in 100 ml. de-ionised water and stirred for minutes, after which 19.3 g. of ammonium molybdate dissolved in 50 ml. de-ionised water was added and stirred in; 9.8 g. of cobaltous nitrate dissolved in ml. de-ionised water was then added and the whole mix stirred for 2 hours, before drying at 110 C. for 16 hours, calcining for 2 hours at 550 C. and then forming into Vs x /s pellets.
  • composition of each of the finished catalysts was:
  • Example 4 A desulphurised gas oil had the following inspection data.
  • Example 5 A series of experiments similar to those of Example 3 was carried out to investigate the effect of boron content on the desulphurisation activity of cobalt oxide-molybdenum oxide catalysts.
  • the feedstock used was a straightrun gas oil having the following inspection data.
  • the degree of desulphurisation tended to increase with increase in the content of cobalt and molybdenum and with decrease of the size of the catalyst particles.
  • 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 with a catalyst comprising a group VIa metal, a refractory oxide support, and from 37%, by weight of total catalyst, of boron, the hydrogen to hydrocarbon mole ratio being from 1 to 1 to 20 to 1; maintaining a selected temperature and a selected space velocty in said zone, said selected temperature in said zone being maintained at least about 750 F. but not higher than about 950 F. and being a temperature at which, at said selected space velocity, not more than 20% wt.
  • the selected space velocity being at least equal to the space velocity at which at said selected temperature not more than 20% wt. of the feedstock is converted to material boiling below 150 C. but not exceeding 8.0 v./v./hr.; maintaining a selected pressure in said zone in the range of -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 5 F. lower than the pour point of the feedstock, and recovering the treated distillate fraction.
  • group VIII metal is an iron group metal, present in an amount, calculated as the divalent metal oxide, of from 0.1 to 10% wt., by weight of total catalyst.
  • the refractory oxide support is a mixture containing a major proportion of alumina and a minor proportion of at least one other refractory oxide of a metal selected from groups II, III and IV of the periodic table.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Catalysts (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
US3125507D 1961-01-26 Hydrofining hydrocarbon fractions Expired - Lifetime US3125507A (en)

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GB3079/61A GB937055A (en) 1961-01-26 1961-01-26 Improvements relating to the treatment of hydrocarbon fractions

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NL (1) NL274026A (zh)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3525684A (en) * 1968-11-13 1970-08-25 Universal Oil Prod Co Catalyst and process for hydrorefining petroleum crude and residual oils
US3617532A (en) * 1968-10-23 1971-11-02 Gulf Research Development Co Hydrotreating process
US4098683A (en) * 1975-11-03 1978-07-04 Uop Inc. Process for hydrodesulfurizing or hydrogenating a hydrocarbon distillate
US4498979A (en) * 1983-09-12 1985-02-12 Exxon Research & Engineering Co. Hydrodesulfurization process with conversion of heavy hydrocarbons utilizing a catalyst containing a group IIA metal component
US5609750A (en) * 1991-06-03 1997-03-11 Akzo Nobel Nv Boron-containing catalyst
WO2010121807A1 (en) * 2009-04-21 2010-10-28 Albemarle Europe Sprl Hydrotreating catalyst containing phosphorus and boron

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2878180A (en) * 1954-06-21 1959-03-17 Universal Oil Prod Co Hydrofining process and catalyst thereof

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2878180A (en) * 1954-06-21 1959-03-17 Universal Oil Prod Co Hydrofining process and catalyst thereof

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3617532A (en) * 1968-10-23 1971-11-02 Gulf Research Development Co Hydrotreating process
US3525684A (en) * 1968-11-13 1970-08-25 Universal Oil Prod Co Catalyst and process for hydrorefining petroleum crude and residual oils
US4098683A (en) * 1975-11-03 1978-07-04 Uop Inc. Process for hydrodesulfurizing or hydrogenating a hydrocarbon distillate
US4498979A (en) * 1983-09-12 1985-02-12 Exxon Research & Engineering Co. Hydrodesulfurization process with conversion of heavy hydrocarbons utilizing a catalyst containing a group IIA metal component
US5609750A (en) * 1991-06-03 1997-03-11 Akzo Nobel Nv Boron-containing catalyst
WO2010121807A1 (en) * 2009-04-21 2010-10-28 Albemarle Europe Sprl Hydrotreating catalyst containing phosphorus and boron
EA020295B1 (ru) * 2009-04-21 2014-10-30 Альбемарл Юроп Спрл Катализатор гидроочистки, содержащий фосфор и бор
AU2010238811B2 (en) * 2009-04-21 2015-01-29 Albemarle Europe Sprl Hydrotreating catalyst containing phosphorus and boron
US11318453B2 (en) 2009-04-21 2022-05-03 Albemarle Catalysts Company B.V. Hydrotreating catalyst containing phosphorus and boron
US11986813B2 (en) 2009-04-21 2024-05-21 Ketjen Netherlands B.V. Hydrotreating catalyst containing phosphorus and boron

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GB937055A (en) 1963-09-18
NL274026A (zh)
BE612739A (zh)

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