US3272734A - Hydrofining and hydrocracking process - Google Patents

Hydrofining and hydrocracking process Download PDF

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US3272734A
US3272734A US304163A US30416363A US3272734A US 3272734 A US3272734 A US 3272734A US 304163 A US304163 A US 304163A US 30416363 A US30416363 A US 30416363A US 3272734 A US3272734 A US 3272734A
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hydrocracking
feed
nitrogen
catalyst
hydrofining
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Donald D Maclaren
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ExxonMobil Technology and Engineering Co
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Exxon Research and Engineering Co
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Priority to DENDAT1250039D priority Critical patent/DE1250039C2/de
Application filed by Exxon Research and Engineering Co filed Critical Exxon Research and Engineering Co
Priority to US304163A priority patent/US3272734A/en
Priority to NO154369A priority patent/NO115299B/no
Priority to GB32866/64A priority patent/GB1034547A/en
Priority to GB33721/64A priority patent/GB1071467A/en
Priority to NL6409703A priority patent/NL6409703A/xx
Priority to FR985953A priority patent/FR1413162A/fr
Priority to FR985952A priority patent/FR1410457A/fr
Priority to NL646409702A priority patent/NL146529B/xx
Priority to DEE27655A priority patent/DE1297794B/de
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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
    • C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
    • C10G65/02—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only
    • C10G65/12—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including cracking steps and other hydrotreatment steps
    • 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
    • C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
    • C10G47/02—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used
    • C10G47/10—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used with catalysts deposited on a carrier
    • C10G47/12—Inorganic carriers
    • C10G47/16—Crystalline alumino-silicate carriers
    • C10G47/18—Crystalline alumino-silicate carriers the catalyst containing platinum group metals or compounds thereof
    • 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
    • C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
    • C10G47/32—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions in the presence of hydrogen-generating compounds

Definitions

  • This invention relates to a hydrocarbon oil conversion process. Particularly, it relates to a hydrocarbon oil conversion process comprising an initial hydrofining treatment of a nitrogen-containing feed stock to partially reduce its total nitrogen content, and subsequent hydrocracking of the partially hydrofined feed stock with a nitrogen-tolerant hydrocracking catalyst to produce valuable lower boiling petroleum products. More particularly, the invention is concerned with an integrated hydrofining and hydrocracking process utilizing a hydrocracking catalyst comprising a crystalline alumino-silicate zeolite containing or supporting a platinum group metal.
  • hydrocracking has recently become a subject of considerable interest within the petroleum industry because of certain particularized advantages it oiiers over conventional catalytic cracking processes. Chemically, hydrocracking may be considered as a combination of hydrogenation and catalytic cracking, and is eflected in the presence of a suitable bifunctional catalyst capable of simultaneously cracking high boiling hydrocarbons to lower boiling fractions and hydrogenating olefinic and aromatic materials into saturated paraflins and naphthenes.
  • hydrocracking Among the advantages offered by hydrocracking are the ability to selectively convert a wide variety of feed stocks, including refractive heavy aromatic feeds, to lower boiling distillates, with significantly less gas and coke yield and higher quality liquid products than are usually produced by catalytic cracking; the adjustability of hydrocracking selectivity to produce high yields of specific liquid products, e.g. gasoline, middle distillate, etc., and the ability to maintain a high selectivity to the desired products over a wide range of conversion levels up to and including extinction recycle.
  • hydrocracking finds its highest utility in cracking hydrocarbons boiling in the heavy naphtha and gas oil range; however, it may also be applied to a variety of feed stocks which may include virgin and catalytic naphthas, gas oils, kerosenes, cycle oils from conventional cracking operations, shale oils, alkyl aromatics, etc.
  • the hydrocracking process is accomplished by passing a high boiling feed stock over a suitable hydrocracking catalyst in the presence of hydrogen and at elevated temperature and pressure suflicient to produce the desired conversion to lower boiling products, e.g. products boiling within the gasoline range.
  • a fixed, moving, or fluidized catalyst bed may be used.
  • the feed stock possess certain characteristics; for example, that it be essentially free of nitrogen-containing compounds, e.g. less than about 10 p.p.m., preferably about 1-2 p.p.m. nitrogen; or that it have a substantial aromatic content, e.g. at least about 30%, so as to obtain reasonable yields of good quality gasoline.
  • the feed stocks which are most suited for hydrocracking usually contain an appreciable quantity of nitrogen, e.g.
  • the present invention is concerned with an improved hydrocarbon conversion process involving an initial hydrofining stage and a subsequent hydrocracking stage, wherein the hydrofining stage is performed under relatively mild operating conditions as compared to the severe conditions conventionally utilized, so as to obtain an essentially unconverted hydrofined efiluent containing an intermediate range of nitrogen content as opposed to a substantially nitrogen-free etfluent; and wherein the hydrocracking stage is performed in the presence of a recently developed nitrogen-tolerant hydrocracking catalyst capable of maintaining a relatively high catalytic activity in the presence of a substantial amount of nitrogen.
  • the overall performance of the process is unexpectedly improved by hydrocracking the partially hydrofined feed containing the predetermined intermedi- 3 ate nitrogen content range, as evidenced by superior selectivity and distribution of products in the efiiuent from the hydrocracking stage.
  • the process of the present invention comprises an integrated hydrofining and hydrocracking treatment of a suitable feed stock substantially (e.g. 95%) boiling above about 400 F. and initially containing at least about 100 p.p.m. nitrogen.
  • the hydrofining step is effected in the presence of hydrogen and a conventional hydrofining, i.e. hydrogenation, catalyst, at elevated temperature and pressure sufiicient to convert the desired proportion of nitrogen compounds to a readily removable form of nitrogen, e.g. ammonia, without substantial conversion of the hydrocarbon materials in the feed.
  • the hydrofined effluent produced should have an intermediate nitrogen content range of about 15 to about 200 p.p.m., preferably about 15 to about 100, more preferably about 15 to about 50 p.p.m.
  • This desired intermediate range of nitrogen content should be produced with essentially no change, e.g. less than about a 5% reduction in the total aromatics content of the feed.
  • hydrogenation of polycyclic aromatics to monocyclic aromatics is permissible, if not desirable, provided that the formation of condensed naphthenes is avoided and the total aromatics content thereby remains essentially unchanged.
  • conversion of 430 F.+ hydrocarbon fractions in the feed to fractions boiling below about 430 F. should be minimized in order to avoid overconversion in the hydrocracking stage.
  • hydrocracking is effected at elevated temperature and pressure in the presence of added hydrogen and a hydrocracking catalyst comprising a crystalline alumino-silicate zeolite having a platinum group metal deposited thereon or incorporated therein.
  • this hydrocracking catalyst is significantly more nitrogen-tolerant than the conventional hydrocracking catalysts of the prior art and is characterized by a high activity maintenance in the presence of nitrogen compounds thus enabling the initial hydrofining treatment to be conducted under less severe conditions than conventionally employed.
  • the catalyst is also characterized by a reversible nitrogen poisoning effect; i.e. it has been found that any poisoning action of a high nitrogen feed is only temporary depending upon continued contact with nitrogen and that the catalyst will recover its original activity when subsequently contacted by a lower nitrogen content or nitrogen-free feed. Additionally, the yield, distribution and quality of the products obtained with this catalyst in the presence of nitrogen are markedly superior to those obtained with conventional catalysts.
  • the zeolitic catalyst employed in the hydrocracking stage of the present process exhibits superior properties as compared to the conventional hydrocracking catalysts of the prior art, which properties include high activity and activity maintenance, nitrogen-tolerance, regenerability, and high selectivity to desired products, with accompanying economy of operation. The use of this catalyst determines to a large degree the successful operation of the process of the present invention and is, therefore, regarded as critical.
  • the process of the present invention is applicable to a variety of feed stocks having higher initial boiling points than gasoline, i.e. higher than about 400 F., and boiling ranges of about 405 to 1100 F. or higher, preferably 405 to 850 F. For certain applications, e.g. for middle distillate or jet fuel production, 5% boiling points of about 500650 P. will be desirable.
  • the feed stocks should have a nitrogen content of at least about p.p.m., preferably at least about 200 p.p.m., and most preferably at least about 500 p.p.m. While those feeds having nitrogen contents between 100 and 200 p.p.m. will already have the desired intermediate range of 15 to 200 p.p.m.
  • feed stocks include whole crudes, heavy naphthas, gas oils, kerosenes, refractory catalytically cracked cycle stocks, high boiling virgin and coker gas oils, residual oils, etc. These materials, when subjected to hydrocracking, are converted to gasoline, middle distillate, etc. as determined by control of the hydrocracking operating conditions.
  • the hydrofining stage of the present process is effected in the presence of a conventional hydrofining or hydrogenation catalyst.
  • a conventional hydrofining or hydrogenation catalyst Such catalysts are well known in the art and are characterized by their resistance to poisoning, particularly sulfur poisoning.
  • Suitable catalysts of this type include the oxides or sulfides of metals of Groups VI and VIII of the Periodic Table, either alone or in admixture with each other, composited with an inert metal oxide support, wherein the metal oxide is selected from the group consisting of silica, oxides of metals in Groups II-A, IIIA, and IV-B of the Periodic Table, and mixtures thereof.
  • Examples of the Group VI metals are tungsten and chromium, with the preferred Group VI metal being molybdenum in the form of a molybdate; examples of the Group VIII metal components are cobalt and nickel; and examples of the metal oxides in the inert support are alumina, zirconia, magnesia, titania, ceria, thoria, etc.
  • such catalysts are typified by nickel sulfide-tungsten sulfide, molybdenum sulfide or oxide, combinations of metal sulfides or oxides such as ferric oxide, molybdenum oxide or sulfide, and cobalt oxide, all of which are supported on the above inert metal oxide supports.
  • a particularly prefered catalyst is cobalt molybdate on alumina.
  • Preferred composite catalysts will contain from about 1 to about 6, preferably 3 to 4 wt. percent of a Group VIII metal oxide, e.g. cobalt oxide, and from about 9 to 18, preferably 12 to 15 wt. percent of a Group VI metal oxide, e.g. molybdenum oxide (M00 on a metal oxide support, e.g. alumina or silica-alumina.
  • the hydrofining treatment preferably involves a fixed bed operation with the oil feed flowing downwardly over the catalyst bed.
  • Suitable operating conditions for hydrofining the feed stock in accordance with the present invention will of course vary with the nitrogen content of the raw feed in order to produce the desired intermediate range of nitrogen content in the hydrofined efiluent to be fed to the hydrocracking stage.
  • nitrogen will include a temperature of from about 500 to about 800 F., preferably 625 to 725 F.; a pressure of from about 500 to about 3000 p.s.i.g., preferably 1200 to 2000 p.s.i.g.; a liquid hourly space velocity of from about 0.1 to about 10, preferably 0.1 to 3 volumes of feed per volume of catalyst per hour; and a hydrogen gas rate of from about 1,000 to about 20,000, preferably 2,000 to 12,000 standard cubic feet (s.c.f.) per barrel of feed. It will be understood that with nitrogen-containing feed stocks having nitrogen contents higher than about 3000 p.p.m. a greater degree of hydrofining will *be required to reduce the nitrogen level to within the desired range.
  • hydrofining conditions may be maintained at a suitably mild level and the hydrofined effluent recycled to the hyd-rofiner until the nitrogen content of the feed is reduced to within the desired range.
  • the ammonia and hydrogen sulfide formed from the hydrogenation of nitrogen and sulfur compounds are removed prior to introduction of the hydrofined stream into the hydrocracking stage by conventional gas separating means.
  • the partially hydrofined oil stream, freed of ammonia and hydrogen sulfide and having a nitrogen content within the aforementioned range, is then preferably passed downwardly over a fixed bed of the zeolitic hydrocracking catalyst to be hereinafter fully described.
  • Hydrocracking of the partially hydrofined feed stock is accomplished in the presence of added hydrogen and catalyst at a temperature of from about 450 to about 800 F., preferably 600 to 750 F; a pressure of from about 500 to about 3000 p.s.i.g., preferably 1200 to 1800 p.s.i.g.; a liquid hourly space velocity of from about 0.1 to about 10, preferably 0.5 to 3 volumes of feed per volume of catalyst per hour; and a hydrogen feed rate of from about 1000 to about 20,000, preferably 2000 to 12,000 s.c.f. per barrel of feed.
  • the conversion expressed as volume percent conversion of fractions boiling above about 430 F. to products boiling below about 430 F. for the production of gasoline (or to products boiling below about 500-650 F.
  • the hydrocracked efiluent is fractionated to separate the desired products, and the high boiling fractions are preferably recycled to extinction by return to the hydrocracking reactor.
  • all material boiling above the desired cut-off point is preferably eventually converted to lower boiling products with in the desired ranges.
  • the cut-01f points will, of course, vary depending upon the boiling range of the products desired; e.g. naphtha (boiling in the range of about 375 to 425 E), jet fuel (boiling in the range of about 450 to 550 F.), middle distillate (boiling in the range of about 650 to 750 F.), etc.
  • the hydrocracking catalyst specifically useful in the process of the present invention comprises a crystalline metallo alumino-silicate zeolite, well known in the art as a molecular sieve, having a platinum group metal (e.g. palladium) deposited thereon or composited therewith.
  • platinum group metal e.g. palladium
  • These crystalline zeolites are characterized by their highly ordered crystalline structure and uniformly dimensioned pores, and have an alumino-silicate anionic cage structure wherein alumina and silica tetrahedra are intimately connected to each other so as to provide a large number of active sites, with the uniform pore openings facilitating entry of certain molecular structures. It has been found that crystalline alumino-silicate zeolites having effective pore diameters of 6 to A., when composited with the platinum group metal, and particularly after base exchange to reduce the alkali metal (e.g.
  • Naturally-occurring large pore crystalline alumino-silicate zeolites may be exemplified by the mineral faujasite. Synthetically produced alumino-silicate zeolites having large pore diameters are also available and will be preferred in the present invention. In general, all crystalline alumino-silicate zeolites, in natural or synthetic form contain a substantial portion of an alkali metal oxide, normally sodium oxide.
  • the support for the hydrocracking catalyst used in the present invention is a crystalline alumino-silicate zeolite having an effective pore diameter of about 6 to 15 A., wherein a substantial portion of the alkali metal, e.g. sodium, has been replaced with a cation (either a metal cation or a hydrogen-containing cation, e.g. NHJ) so as reduce the soda (Na O) content to less than 10 wt. percent and preferably to about 1 to 5 wt. percent (based on zeolite).
  • a cation either a metal cation or a hydrogen-containing cation, e.g. NHJ
  • Me is selected from the group consisting of hydrogen and metal cations (so that the Na O content is less than 10 Wt. per-cent of the zeolite), n is its valence and X is a number from 2.5 to 14, preferably 3 to 10 and most preferably 4 to 6. Crystalline zeolites having these ratios have been found to be highly active, selective and stable.
  • the processes for synthetically producing crystalline alumino-silicate zeolites are well known in the art. They involve crystallization from reaction mixtures containing: A1 0 as sodium aluminate, alumina sol and the like; SiO as sodium silicate .and/ or silica gel and/ or silica sol; and Na O as sodium hydroxide. Careful control is kept over the soda (N 0) concentration of the mixture, as well as the proportions of silica to alumina and soda to silica, the crystallization period, etc., to obtain the desired product.
  • a conventional scheme for preparing a crystalline alumino-silicate zeolite having a silica to alumina mole ratio of about 4 to 6 is as follows:
  • Colloidal silica is mixed with a solution of sodium hydroxide and sodium aluminate at ambient temperature to produce a reaction mixture having the following molar ratios of reactants:
  • the zeolite is preferably baseexchanged with a hydrogen-containing or metal cation to reduce the soda content to below 10 wt. percent.
  • Suitable metal cations include ions of metals in Groups I to VIII and rare earth metals, and preferably metals in Groups II, III, IV, V, VI-B, VII-B, VIII, and rare earth metals.
  • a hydrogen-containing cation is used to replace the sodium
  • the hydrogen or decationized form of the zeolite is produced.
  • a convenient method of preparing the hydrogen or decationized form is to subject the zeolite to base-exchange with an ammonium cation solution followed by controlling heating at elevated temperature, eg 600 to 1000 F., to drive off ammonia and Water.
  • the base-exchanged crystalline zeolite is then composited with the platinum group metal by treatment (e.g. wet impregnation or base-exchange) with a platinum or palladium salt or ammonium complex, e.g. ammonium chlonoplatinate, palladium chloride, etc.
  • the amount of catalytic metal in the finished catalyst is ordinarily between 0.01 and about 5.0 wt. percent, preferably 0.1 to 3.0 wt. percent, based on the zeolite.
  • the catalyst is subjected to a heat or hydrogen treatment at elevated temperatures, e.g. 500 to 1500 F., to reduce the platinum group metal, at least in part, to its elemental state.
  • the zeolitic catalyst may be utilized in the abovedescribed form or may be suitably embedded in an amorphous material such as silica gel, or a cogel of silica and at least one other metal oxide wherein the metal is selected from Groups II-A, III-A, and IV-B of the Periodic Table, e.g. alumina, titania, magnesia, etc.
  • amorphous material such as silica gel, or a cogel of silica and at least one other metal oxide wherein the metal is selected from Groups II-A, III-A, and IV-B of the Periodic Table, e.g. alumina, titania, magnesia, etc.
  • alumina e.g. alumina, titania, magnesia, etc.
  • the activity of the pure crystalline zeolite is very often too high for some applications and to achieve desired selectivities in the hydrocracked product streams it is often desirable to utilize a composite form of zeolitemat-rix catalyst.
  • the crystals of zeolite are often too fine for successful fluidization due to excessive attrition and carry-over losses.
  • a composite catalyst comprising zeolite crystals embedded in a suitable matrix, e.g. a silica-alumina matrix, obviates these difiiculties since the composite material can be formed into particles of a desired size range.
  • a convenient means of forming the composite form of catalyst is to incorporate the zeolite crystals into a suitable hydrogel, erg. a silicaalumina hydrogel; subject the resulting mixture to high agitation conditions with added water, if necessary, to produce a homogeneous fluid dispersion; and finally spray dry the resulting mixture to form particles of the desired size.
  • the final composite may contain to 80 wt. percent zeolite.
  • a suitable oil feed charge is introduced through line 10 and is mixed with hydrogen being introduced through line 11.
  • the resulting admixture of feed charge and hydrogen is heated to hydrofining temperature in heater 12, and passed through line 13 into hydrofiner 14, where it fiows downwardly over hydrofining catalyst of the type hereinbefore described.
  • the hydrofining operating conditions are determined by the nitrogen content of the feed charge and will be sufiicient to reduce the nitrogen content to within the desired range without substantial conversion of the hydrocarbons in the feed.
  • hydrofiner 14 the nitrogen-containing and sulfur-containing compounds in the feed are substantially converted to ammonia and hydrogen sulfide, respectively.
  • the total effluent from hydrofiner 14 containing excess hydrogen, hydrogen sulfide, ammonia and substantially unconverted liquid petroleum hydrocarbon fractions is withdrawn through line 15, and passed to gas separator 16, to separate the gaseous phase from the liquid phase.
  • the gaseous phase including hydrogen, ammonia and hydrogen sulfide, passes through line 17 into gas treater 18, wherein the hydrogen sulfide and ammonia are removed by scrubbing or other suitable means.
  • the remaining gas stream composed substantially of hydrogen is recycled to the system via line 19 which joins line 11.
  • the hydrogen sul- 8 fide and ammonia may be removed by a gas treater in line 15.
  • the essentially unconverted liquid petroleum stream is withdrawn from gas separator 16 through line 20, and passed via lines 21 and 22 into heater 23, wherein it is heated to hydrocracking temperature.
  • the heated liquid stream passes through line 24, mixes with a hydrogen stream flowing through line 25, and the combined admixture of hydrogen and oil streams enters hydrocracker 27 through line 26, where it fiows downwardly over hydrocracking catalyst of the type hereinbefore described.
  • the hydrocracking operating conditions in hydrocracker 27 are sufficient to obtain the desired degree of conversion per pass.
  • the etliuent stream from hydrocracker 27 is withdrawn through lne 28, and passes to gas separator 29, which serves to separate the liquid and gaseous phases.
  • the gaseous phase containing hydrogen, and minor amounts of ammonia and hydrogen sulfide leaves gas separator 29 through line 30 and passes to gas treater 31, where the ammonia and hydrogen sulfide may be removed by scrubbing or other suitable means.
  • gas treater 31 is optional depending upon the amounts of ammonia and hydrogen sulfide in the recycle gas.
  • the gas stream composed substantially of hydrogen is then recycled through line 32, along with make-up hydrogen being introduced through line 33.
  • the combined hydrogen stream is heated to the desired operating temperature in heater 34, passes through line 25, and joins with the partially hydrofined oil feed in line 26 as hereinbefore described.
  • heater 34 is optional.
  • Liquid petroleum products are withdrawn from the bottom of gas separator 29 through line 35, and are conducted to fractionator 36, wherein light hydrocarbons and gases are removed as overhead through outlet 37.
  • a stabilizer can be utilized in line 35 for the removal of light hydrocarbons and gases.
  • Intermediate fractions of light naphtha, heavy naphtha and light fuel oil may be withdrawn respectively from fractionator 36 through lines 38, 39 and 40.
  • the heavy oil bottoms product is withdrawn through outlet 41 and recycled through line 42, where it joins with the hydrofined separated liquid oil stream in line 20 for recycle to hydrocracker 27 via lines 21, 22, 24 and 26.
  • the process is thus characterized by a recycle to extinction of the fractionator bottoms which are converted to lower boiling fractions in hydrocracker 27.
  • Example I A crystalline alumino-silicate zeolite hydrocracking catalyst was prepared by the following procedure:
  • a mixture of sodium aluminate, sodium hydroxide and silica sol was heated at about 212 F. in such proportion and for such time as to produce a crystalline zeolite.
  • the resulting ammonium form of the zeolite was separated by filtration and treated with a solution containing the ammonium complex of palladium chloride, in an amount suflicient to produce about a 0.5 Wt. percent palladium catalyst.
  • the catalyst was then filtered, washed, oven-dried at 212 F, and finally calcined at 1000 F. It contained 0.48% palladium, had a uniform pore size of about 15 A. and a silica to alumina mole ratio in the zeolite component of about 55:1.
  • the above catalyst was utilized in the integrated hydrofining-hydrocracking process of the present invention using the processing scheme hereinbefore described and illustrated in the accompanying drawing with the exceptions that ammonia and hydrogen sulfide gases were removed from the system by water scrubbing the streams in lines 20 and 22, and a stabilizer was used in line 35 to remove light hydrocarbons and gases (C4
  • the hydrofining catalyst utilized was a cobalt molybdate on alumina catalyst containing 16.5 wt. percent cobalt molybdate (3.9 wt. percent 000, 12.6 wt. percent M
  • the feed stock contained 758 p.p.m. nitrogen and was a blend of 28.7 vol. percent coker gas oil, 35.1 vol. percent coker heating oil and 36.2 vol. percent catalytic cycle oil.
  • Run A the feed was hydrofined to a level of 1 p.p.m. nitrogen
  • Run B it was hydrofined to a level of 28 p.p.m. nitrogen.
  • the results were compared to those obtained by hydrocracking the raw feed, designated as Run C.
  • a process for hydrocracking a hydrocarbon oil feed having a nitrogen content within the range of about 28 to about 200 parts per million comprising contacting said feed in the presence of hydrogen with a hydrocracking catalyst comprising a crystalline alumino-silicate zeolite composited with a platinum group metal, said zeolite having pore openings of about 6 to about 15 Angstrom units and containing less than about 10 wt. percent alkali metal oxide, at hydrocracking conditions sufiicient to obtain the desired conversion to lower boiling product.
  • hydrocracking conditions include a temperature of from about 450 to about 800 F., a pressure of from about 500 to about 3000 p.s.i.g., a liquid hourly space velocity of from about 0.1 to about 10 volumes of feed per volume of catalyst per hour, and a hydrogen rate of from about 1000 to about 20,000 standard cubic feet per barrel of feed.
  • a process for hydrocracking a hydrocarbon oil feed having a nitrogen content within the range of about 28 to about 200 parts per million said feed substantially boiling above about 400 F. to obtain lower boiling product which comprises contacting said feed in the presence of hydrogen with a hydrocracking catalyst comprising a crystalline alumino-silicate zeolite composited with 0.01 to 5.0 wt. percent platinum group metal, said zeolite having pore openings of about 6 to about Angstrom units and containing less than about 10 wt. percent Na O, at a temperature of from about 450 F.
  • a process for hydrocracking a hydrocarbon oil feed substantially boiling above about 400 F. and having a nitrogen content in the range of about 28 to about 50 p.p.m. nitrogen to obtain lower boiling product comprises contacting said feed in a hydrocracking zone, in the presence of hydrogen, with a hydrocracking catalyst comprising a crystalline alumino-silicate zeolite composited with a platinum group metal, said zeolite having pore openings of about 6 to about 15 Angstrom units and containing less than about 10 wt.

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US304163A 1963-08-23 1963-08-23 Hydrofining and hydrocracking process Expired - Lifetime US3272734A (en)

Priority Applications (10)

Application Number Priority Date Filing Date Title
DENDAT1250039D DE1250039C2 (de) 1963-08-23 Verfahren zum hydrocracken von stickstoffhaltigen kohlenwasserstoffoelen
US304163A US3272734A (en) 1963-08-23 1963-08-23 Hydrofining and hydrocracking process
GB32866/64A GB1034547A (en) 1963-08-23 1964-08-12 Hydrofining and hydrocracking process
NO154369A NO115299B (de) 1963-08-23 1964-08-12
GB33721/64A GB1071467A (en) 1963-08-23 1964-08-18 Hydrocracking process
NL6409703A NL6409703A (de) 1963-08-23 1964-08-21
FR985953A FR1413162A (fr) 1963-08-23 1964-08-21 Procédé d'hydrocraquage
FR985952A FR1410457A (fr) 1963-08-23 1964-08-21 Procédé d'hydrogénation douce et de craquage en présence d'hydrogène d'un hydrocarbure contenant de l'azote
NL646409702A NL146529B (nl) 1963-08-23 1964-08-21 Werkwijze voor het hydrokraken van een stikstofhoudende koolwaterstofvoeding.
DEE27655A DE1297794B (de) 1963-08-23 1964-08-22 Verfahren zum Hydrocracken von Kohlenwasserstoffen

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US30416163A 1963-08-23 1963-08-23
US304163A US3272734A (en) 1963-08-23 1963-08-23 Hydrofining and hydrocracking process

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US3272734A true US3272734A (en) 1966-09-13

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US304163A Expired - Lifetime US3272734A (en) 1963-08-23 1963-08-23 Hydrofining and hydrocracking process

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US (1) US3272734A (de)
DE (2) DE1297794B (de)
FR (1) FR1410457A (de)
GB (2) GB1034547A (de)
NL (2) NL146529B (de)
NO (1) NO115299B (de)

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3477943A (en) * 1967-04-25 1969-11-11 Atlantic Richfield Co Two-stage treatment of high sulfur content petroleum materials
US3506568A (en) * 1969-01-10 1970-04-14 Chevron Res Process of hydrofining high nitrogen hydrocarbons followed by catalytic cracking with zeolitic aluminosilicates
US3617507A (en) * 1968-02-17 1971-11-02 Basf Ag Process for hydrocracking heavy hydrocarbons
DE1767074B1 (de) * 1968-03-28 1972-05-31 Basf Ag Verfahren zur herstellung kristalliner zeolithe
US4153540A (en) * 1977-05-04 1979-05-08 Mobil Oil Corporation Upgrading shale oil
US4210521A (en) * 1977-05-04 1980-07-01 Mobil Oil Corporation Catalytic upgrading of refractory hydrocarbon stocks
US4460455A (en) * 1982-01-13 1984-07-17 Mitsubishi Oil Co., Ltd. Process for producing pitch for using as raw material for carbon fibers
US4515680A (en) * 1983-05-16 1985-05-07 Ashland Oil, Inc. Naphthenic lube oils
US4755280A (en) * 1985-07-31 1988-07-05 Exxon Research And Engineering Company Process for improving the color and oxidation stability of hydrocarbon streams containing multi-ring aromatic and hydroaromatic hydrocarbons
US20100116712A1 (en) * 2008-11-10 2010-05-13 Bart Dziabala Combination of mild hydrotreating and hydrocracking for making low sulfur diesel and high octane naphtha
US20160115400A1 (en) * 2014-10-22 2016-04-28 Uop Llc Integrated hydrotreating and slurry hydrocracking process

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Publication number Priority date Publication date Assignee Title
US2971904A (en) * 1957-02-12 1961-02-14 Exxon Research Engineering Co Petroleum process catalyst supported on a molecular sieve zeolite
US3132089A (en) * 1960-12-23 1964-05-05 Union Oil Co Hydrocracking process with pre-hydrogenation
US3132090A (en) * 1962-01-23 1964-05-05 Union Oil Co Hydrocracking process with regulation of the aromatic content of the product
US3159568A (en) * 1961-10-02 1964-12-01 Union Oil Co Low pressure hydrocracking process with hydrofining of feed

Family Cites Families (4)

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BE622012A (de) *
GB541067A (en) * 1939-04-03 1941-11-12 Standard Oil Dev Co Improvements relating to the catalytic treatment of hydrocarbons
US2962435A (en) * 1956-12-14 1960-11-29 Union Oil Co Hydrocarbon cracking process and catalyst
BE608029A (de) * 1957-02-05 1900-01-01

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2971904A (en) * 1957-02-12 1961-02-14 Exxon Research Engineering Co Petroleum process catalyst supported on a molecular sieve zeolite
US3132089A (en) * 1960-12-23 1964-05-05 Union Oil Co Hydrocracking process with pre-hydrogenation
US3159568A (en) * 1961-10-02 1964-12-01 Union Oil Co Low pressure hydrocracking process with hydrofining of feed
US3132090A (en) * 1962-01-23 1964-05-05 Union Oil Co Hydrocracking process with regulation of the aromatic content of the product

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3477943A (en) * 1967-04-25 1969-11-11 Atlantic Richfield Co Two-stage treatment of high sulfur content petroleum materials
US3617507A (en) * 1968-02-17 1971-11-02 Basf Ag Process for hydrocracking heavy hydrocarbons
DE1767074B1 (de) * 1968-03-28 1972-05-31 Basf Ag Verfahren zur herstellung kristalliner zeolithe
US3506568A (en) * 1969-01-10 1970-04-14 Chevron Res Process of hydrofining high nitrogen hydrocarbons followed by catalytic cracking with zeolitic aluminosilicates
US4153540A (en) * 1977-05-04 1979-05-08 Mobil Oil Corporation Upgrading shale oil
US4210521A (en) * 1977-05-04 1980-07-01 Mobil Oil Corporation Catalytic upgrading of refractory hydrocarbon stocks
US4460455A (en) * 1982-01-13 1984-07-17 Mitsubishi Oil Co., Ltd. Process for producing pitch for using as raw material for carbon fibers
US4515680A (en) * 1983-05-16 1985-05-07 Ashland Oil, Inc. Naphthenic lube oils
US4755280A (en) * 1985-07-31 1988-07-05 Exxon Research And Engineering Company Process for improving the color and oxidation stability of hydrocarbon streams containing multi-ring aromatic and hydroaromatic hydrocarbons
US20100116712A1 (en) * 2008-11-10 2010-05-13 Bart Dziabala Combination of mild hydrotreating and hydrocracking for making low sulfur diesel and high octane naphtha
US8066867B2 (en) * 2008-11-10 2011-11-29 Uop Llc Combination of mild hydrotreating and hydrocracking for making low sulfur diesel and high octane naphtha
US20120043257A1 (en) * 2008-11-10 2012-02-23 Uop Llc Combination of mild hydrotreating and hydrocracking for making low sulfur diesel and high octane naphtha
US8404103B2 (en) * 2008-11-10 2013-03-26 Uop Llc Combination of mild hydrotreating and hydrocracking for making low sulfur diesel and high octane naphtha
US20160115400A1 (en) * 2014-10-22 2016-04-28 Uop Llc Integrated hydrotreating and slurry hydrocracking process
US10711207B2 (en) * 2014-10-22 2020-07-14 Uop Llc Integrated hydrotreating and slurry hydrocracking process

Also Published As

Publication number Publication date
NL6409703A (de) 1965-02-24
DE1297794B (de) 1969-06-19
DE1250039C2 (de) 1973-02-22
FR1410457A (fr) 1965-09-10
GB1034547A (en) 1966-06-29
NO115299B (de) 1968-09-16
NL146529B (nl) 1975-07-15
GB1071467A (en) 1967-06-07
NL6409702A (de) 1965-02-24
DE1250039B (de) 1967-09-14

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