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WO1996018705A1 - Procede d'isomerisation d'une charge d'alimentation hydrocarbonee - Google Patents

Procede d'isomerisation d'une charge d'alimentation hydrocarbonee Download PDF

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Publication number
WO1996018705A1
WO1996018705A1 PCT/EP1995/004997 EP9504997W WO9618705A1 WO 1996018705 A1 WO1996018705 A1 WO 1996018705A1 EP 9504997 W EP9504997 W EP 9504997W WO 9618705 A1 WO9618705 A1 WO 9618705A1
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WO
WIPO (PCT)
Prior art keywords
feedstock
process according
catalyst
ppm
amorphous alumina
Prior art date
Application number
PCT/EP1995/004997
Other languages
English (en)
Inventor
Erwin Blomsma
Pierre August Jacobs
Johan Adriaan Martens
Donald Reinalda
Original Assignee
Shell Internationale Research Maatschappij B.V.
Shell Canada Limited
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Shell Internationale Research Maatschappij B.V., Shell Canada Limited filed Critical Shell Internationale Research Maatschappij B.V.
Priority to AU43457/96A priority Critical patent/AU4345796A/en
Priority to EP95942174A priority patent/EP0797650A1/fr
Priority to JP8518282A priority patent/JPH10510568A/ja
Publication of WO1996018705A1 publication Critical patent/WO1996018705A1/fr
Priority to MXPA/A/1997/004292A priority patent/MXPA97004292A/xx

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Classifications

    • 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
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/42—Platinum
    • 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
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/44—Palladium
    • 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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
    • B01J29/74—Noble metals
    • B01J29/7415—Zeolite Beta
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/22—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by isomerisation
    • C07C5/27—Rearrangement of carbon atoms in the hydrocarbon skeleton
    • C07C5/2767—Changing the number of side-chains
    • C07C5/277—Catalytic processes
    • C07C5/2791—Catalytic processes with metals
    • 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
    • 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
    • C10G45/64—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 crystalline alumino-silicates, e.g. molecular sieves
    • 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
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/20—After treatment, characterised by the effect to be obtained to introduce other elements in the catalyst composition comprising the molecular sieve, but not specially in or on the molecular sieve itself
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/16—Reducing
    • B01J37/18—Reducing with gases containing free hydrogen
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
    • C07C2521/02—Boron or aluminium; Oxides or hydroxides thereof
    • C07C2521/04—Alumina
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals
    • C07C2523/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals of the platinum group metals
    • C07C2523/42—Platinum
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals
    • C07C2523/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals of the platinum group metals
    • C07C2523/44—Palladium
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2529/00—Catalysts comprising molecular sieves
    • C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
    • C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous 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
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/02—Gasoline

Definitions

  • the present invention relates to a process for upgrading hydrocarbonaceous feedstocks more particularly for isomerisation of a feedstock substantially boiling in the gasoline range which feedstock comprises linear paraffins having at least five carbon atoms.
  • the present invention relates to a process for isomerization of a hydrocarbonaceous feedstock substantially boiling in the gasoline range which feedstock comprises linear paraffins having at least five carbon atoms wherein the feedstock is contacted in the presence of hydrogen at elevated temperature and pressure with a catalyst comprising in combination platinum and palladium each in metallic form supported on an acidic amorphous alumina or molecular sieve .
  • metal form is to the zero valent state of substantially all of both platinum (Pt) and palladium (Pd) present on the catalyst. It is to be appreciated that the catalyst may be employed without prior reduction of the metal components to the metallic state, whereby reduction is achieved in situ under the prevailing conditions including the presence of hydrogen. Accordingly reference herein to "metallic form” is to the form effective during the contacting.
  • molecular sieve is to both zeolitic and non-zeolitic types, i.e. to molecular sieves comprised of silicoaluminate or otherwise.
  • Preferred molecular sieves are of the "10 ring” or “12 ring” type, i.e. comprise 10 or 12 membered rings of oxygen atoms.
  • the process of the present invention may be employed in the upgrading by means of isomerisation of a feed comprising paraffins of varying carbon number, for example having carbon number 5 up to 8, in a single stage.
  • the process of the invention enables the isomerisation of normal paraffins to multibranched paraffins in significant yield in a single stage.
  • the process of the invention enables operation with lower total metal loading than in conventional processes without incurring yield and selectivity loss.
  • the Pt and Pd are uniformly dispersed throughout the catalyst thereby enhancing their cooperative effect. Without being limited to the following theory, it is thought that the presence of one or both metals has an effect on the other metal, in particular the presence of the Pd seems to have a positive effect on the dispersion or the state of the Pt, whereby the metals are better brought into or retained in the metallic form.
  • the Pt and Pd are both present in the same catalyst locus, more preferably on the same catalyst particle, most preferably on the same particle of amorphous alumina or molecular sieve.
  • the catalyst to be used in accordance with the present invention may comprise in addition to the amorphous alumina or molecular sieve (hereinafter the active catalyst structure) , a binder material comprising one or more refractory oxides.
  • the Pt and Pd metals may be present on the active catalyst structure or may be present on a separate carrier (e.g. the binder) comprising for instance one or more refractory oxides, e.g. alumina.
  • a separate carrier e.g. the binder
  • the Pt and Pd are present on the active catalyst structure.
  • the Pt and Pd are loaded onto the active catalyst structure by methods known in the art, for example by means of (competitive) ion-exchange, (competitive) pore volume (incipient wetness) impregnation, controlled deposition precipitation, comulling in a suitable mixing device a precursor of the metallic components onto the active catalyst structure and/or binder.
  • the metals are loaded onto the active catalyst structure by means of incipient wetness impregnation of an aqueous solution of the tetramine- dichloride salt, or by means of competitive ion exchange in the presence of ammonium as competitive ion.
  • the process of the invention is substantially independent of the manner in which the metals are loaded onto the catalyst. This is in contrast to processes using catalysts comprising only Pt or only Pd, whereby process performance can be affected by manner of loading of metal onto the active catalyst structure.
  • the present process advantageously provides improved catalyst performance which would seem to override any improvement available by manner of catalyst synthesis.
  • the catalysts employed in the process of the present invention are characterized by improved metal dispersion and reduction to the metallic state when compared with the known monometallic catalysts.
  • the metals are introduced simultaneously.
  • the metals are distributed in the active catalyst structure.
  • distribution is controlled by means of control of solution composition during introduction, for example by control of solution pH and competitive anions and cations content.
  • the metals are brought into metallic form by reduction procedures known in the art.
  • the catalyst comprises from 0.01 to 5% by weight of Pt and Pd in combination based on total weight of active catalyst structure, preferably from 0.1 to 3% by weight of combined Pt and Pd based on total weight of active catalyst structure.
  • the Pt and Pd are present in an atomic ratio of Pt/ (Pt + Pd) of between 0.0 and 1.0, preferably of substantially 0.1 to 0.8, more preferably of substantially 0.1 to 0.5.
  • Amorphous alumina catalysts which may be employed in the process of the present invention include those known in the art.
  • amorphous alumina catalysts are characterised by moderate to low surface area, preferably surface area of 100-500 m*-*/g.
  • More preferably amorphous alumina catalysts comprise eta alumina or gamma alumina, of 320-430 m 2 /g or 170-220 m 2 /g respectively.
  • the amorphous alumina may comprise an additional acidic component.
  • amorphous alumina catalysts comprise a chloride component whereby acidity is enhanced.
  • amorphous alumina catalysts are chlorided by known means including subliming AICI3 and reaction with COCI2, CCI4 etc.
  • acidic components are present at a level suitable to achieve the desired acidity.
  • eta alumina may comprise chlorine in amount of 5-15%, gamma alumina in an amount of 3-8%.
  • Molecular sieves which may be employed in the present invention include any zeolitic or non-zeolitic molecular sieves capable of selective conversion of feed molecules in the range above defined.
  • zeolites are of the "10 ring” or “12 ring” type, i.e. comprise 10 or 12 membered rings of oxygen atoms, and are preferably of the twelve ring type including as non-limiting example MCM-22 and AEL, AFI, AFR, AFS, AFY, ATO, ATS, BEA, BOG, BPH, CAV, EHT, FAU, GME, LTL, MAZ, MEI, MOR, MTW and OFF as described in "Zeolites" Vol. 12 No.
  • Non-zeolitic molecular sieves given as non-limiting example, in particular AEL, AFI, AFR, AFS, AFY, ATD and ATS, which include a metal component, suitably include a Group VIII metal component, preferably selected from magnesium, manganese, cobalt and zinc, more preferably cobalt.
  • Molecular sieves of the zeolite or non-zeolite type may be selected or modified to obtain a desired level of acidity.
  • Zeolites may be conveniently modified or synthesised in manner to attain a given ratio of Si ⁇ 2 to AI2O3, whereby the acidity is determined. Suitable ratios of Si ⁇ 2 to AI2O3 are dependent on the individual zeolite to be employed.
  • a zeolite of the MOR type may be employed with a Si ⁇ 2*Al2 ⁇ 3 ratio of 10 to 60, preferably 15 to 30, for example of approximately 20.
  • the zeolite may further be modified to optimise selectivity for example by treatment of non-selective acidic sites, typically non pore-internal acid sites, which treatment or modification is well known, and may comprise acid or base treatment or modification.
  • the process is carried out at a temperature of 50 to 400 °C, a pressure of up to 5 x 10 6 Pa (50 bar), a space velocity of 0.5 to 10 kg/kg.h and a hydrogen to feedstock molar ratio of up to 10.0.
  • an amorphous alumina catalyst When use is made of an amorphous alumina catalyst the process is suitably carried out at a temperature of from 50 to 250 °C, preferably of from 100 to 150 °C, a total pressure of 1.5 x 10 6 to 4 x 10 6 Pa (15 to 40 bar), preferably of 3 x lO*-* Pa (30 bar), a space velocity of 0.3 to 10 kg/kg.hr, preferably of 0.5 to 5 kg/kg.hr and a hydrogen to feedstock molar ratio of up to 10.0, preferably of from 0.01 to 3.0.
  • the process is suitably carried out at a temperature of from 150 to 350 °C, preferably of from 180 to 280 °C, a total pressure of 1.5 x 10 6 to 3.5 x 10 6 Pa (15 to 35 bar), for example approximately 2.5 x lO*- 5 Pa (25 bar), a space velocity of 0.5 to 5 kg/kg.hr and a hydrogen to feedstock molar ratio of up to 5.0, preferably of from 0.5 to 4.0.
  • the process is suitably carried out at a temperature of from 250 to 450 °C, preferably of from 275 to 400 °C, a total pressure of up to 1 x 10 7 Pa (100 bar), preferably of from 1 x 10 6 to 5 x 10 6 Pa (10 to 50 bar), a space velocity of from 0.5 to 10.0 kg/kg.h, preferably of from 1.0 to 5.0 kg/kg.h and a hydrogen to feedstock molar ratio of up to 5.0, preferably of from 1.0 to 3.0.
  • the hydrocarbonaceous feedstock substantially boiling in the gasoline range can suitably be obtained by fractionating any paraffinic gasoline-containing hydrocarbonaceous feedstock.
  • the feedstock substantially boiling in the gasoline range is obtained by subjecting a straight run hydrocarbon oil to a f actionation, preferably atmospheric distillation.
  • suitable hydro ⁇ carbonaceous feedstocks substantially boiling in the gasoline range include product fractions obtained from cracking processes such as catalytic cracking, thermal cracking, delayed coking, visbreaking and flexicoking.
  • Hydrocarbonaceous feedstocks containing unacceptable levels of sulphur and nitrogen may be subjected to a hydrotreatment before they are subjected to the process according to the present invention, whereby particularly advantageous results may be obtained.
  • the hydrocarbonaceous feedstock boiling in the gasoline range has a low sulphur content, preferably less than 10 ppmw on feed.
  • the hydrocarbonaceous feedstock may consist entirely of a fraction boiling in the gasoline range, i.e. in the range of C4-22O °C. While the full gasoline boiling range fraction may be included in the hydrocarbonaceous feedstock, it may be preferred to employ as hydrocarbonaceous feedstock a cut thereof having a boiling point up to 180 °C. Optionally, the hydrocarbonaceous feedstock may be blended with a reformate fraction.
  • the hydrocarbonaceous feedstock substantially boiling in the gasoline range may substantially comprise linear paraffins having at least five carbon atoms, i.e. the feedstock may substantially consist of one or more different types of linear paraffins having at least five carbon atoms.
  • the hydrocarbonaceous feedstock boiling in the gasoline range substantially comprises linear paraffins having five to ten carbon atoms. More preferably, the hydrocarbonaceous feedstock substantially comprises linear paraffins having five to seven carbon atoms. Suitably, the hydrocarbonaceous feedstock substantially comprises n-hexane and/or n-heptane.
  • the process of the present invention is characterised by an enhanced performance in the conversion of sulphur contaminated feedstocks, by virtue of the enhanced total activity observed. Moreover it would seem that the process is characterised by an enhanced resilience to the poisoning effect of sulphur contaminants present in feedstocks to be converted. It is of particular advantage to process a refinery feedstock without the need for a preliminary feed purification step, or with the possibility to reduce the duty of feed pretreatment.
  • the present invention relates in a further embodiment to a process for isomerisation of a hydrocarbonaceous feedstock substantially boiling in the gasoline range which feedstock comprises linear paraffins having at least five carbon atoms and has a sulphur content of greater than or equal to 10 ppm wherein the feedstock is contacted in the presence of hydrogen at elevated temperature and pressure with a catalyst comprising in combination Pt and Pd each in metallic form supported on an acidic amorphous alumina or molecular sieve.
  • the process comprises isomerization of a feedstock as above defined having a sulphur content in the range of 10 to 100 ppm, preferably 10 to 50 ppm, more preferably 10 to 30 ppm, for example approximately 20 ppm.
  • a feedstock as above defined having a sulphur content in the range of 10 to 100 ppm, preferably 10 to 50 ppm, more preferably 10 to 30 ppm, for example approximately 20 ppm.
  • operation with higher sulphur content feeds is performed at slightly higher severity, for example at temperatures slightly greater than required with conversion of low sulphur content feedstocks.
  • unconverted linear paraffins are separated from branched paraffins downstream of the reaction zone in which the isomerisation is carried out, and recycled to the reaction zone. Separation can suitably be carried out by means of molecular sieve or of distillation.
  • the process is suitably initiated by loading the reaction vessel with catalyst and heating the bed with simultaneous activation of the catalyst by contacting with flowing oxygen at elevated temperature and subsequently with flowing hydrogen at elevated temperature.
  • the feedstock to be isomerised is suitably preheated to elevated temperature which may be less than or equal to the operating temperature and is introduced at a desired rate together with hydrogen in desired molar ratio.
  • the reaction is suitably terminated on partial or complete deactivation of the catalyst, and catalyst regeneration performed.
  • Regeneration may be performed after terminating the feedstock supply, by introducing a suitable regeneration medium or by raising the catalyst to elevated temperature for combustion of deactivating hydrocarbonaceous deposits.
  • Suitable regeneration media include reactive or adsorptive fluids as known in the art, for example a combustion gas such as diluted air or oxygen/nitrogen mixtures.
  • the process may be carried out in any desired reactor, and is suitably carried out in a fixed bed, slurry or fluidised bed reactor, in batch, semi- continuous or continuous mode.
  • a plurality of reactors may be employed in series or parallel.
  • Regeneration of the catalyst may be carried out in one or more reactors simultaneously with operation of the process in one or more of the remaining reactors.
  • the present invention relates to isomerised paraffinic hydrocarbons whenever prepared by a process as hereinbefore described.
  • Samples of BEA zeolite of Si to Al atomic ratio of 12.5, surface area of 750 rn- ⁇ /g and crystal size of 0.1 to 0.7 micron were converted to the ammonium form by contacting the sample with an aqueous solution of ammonium chloride at a pH of 8.
  • Platinum (Pt) and palladium (Pd) were then introduced onto the samples in desired amounts by contacting the samples with a Pt/Pd tetramine dichloride solution, by known technique of competitive ion exchange in the presence of ammonium as competitive ion.
  • the samples thus obtained were activated in situ by calcination in flowing oxygen (15 mol/kg.s) at 400 °C, followed by reduction in flowing hydrogen (15 mol/kg.s) at 400 °C.
  • Catalysts A were thus obtained having both Pt and Pd present in independently varied amounts, expressed as ratio Pt/ (Pt + Pd) of between 0.0 and 1.0.
  • Total metal loading (Pt + Pd) included 0.5 wt%, 1.0 wt% and 1.5 wt% on weight of active catalyst structure for different samples.
  • Example 2 (Comparative) - Preparation of bifunctional monometallic Catalysts B and C
  • Catalysts B and C were prepared following the same procedure as given in Example 1 above, with the exception that for each sample of ammonium form BEA zeolite only one of platinum and palladium metal was introduced. Catalysts B were obtained having only Pt present in varied amounts equal to the total metal loading of Catalysts A, and Catalysts C were obtained having only Pd present in varied amounts equal to the total metal loading of Catalysts A, expressed as ratio Pt/ (Pt + Pd) of 1.0 and of 0.0 respectively.
  • Heptane conversion was carried out in a fully automated continuous flow tubular microreactor.
  • a sample of Catalyst A, B, C or mixture of B and C prepared in Example 1 or 2 above was activated in situ in the reactor as above described.
  • a stream of hydrogen saturated with heptane vapour was then generated using a thermostatted saturator.
  • the purity of heptane was at least 99%, with 1% or less impurities comprised mainly of isomers of heptane.
  • Reaction products were analysed on line by gas chromatography. Conversion was maintained at 82.5%, by means of adjusting the space velocity.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Materials Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

On décrit un procédé d'isomérisation d'une charge d'alimentation hydrocarbonée bouillant sensiblement dans la même plage de température que l'essence, cette charge comprenant des paraffines linéaires possédant au moins cinq atomes de carbone, lequel procédé consiste à mettre en contact la charge d'alimentation, en présence d'hydrogène à température et pression élevées, avec un catalyseur comprenant en combinaison du platine (Pt) et du palladium (Pd), chacun sous une forme métallique supportée par de l'alumine amorphe acide ou par un tamis moléculaire. On décrit également des hydrocarbures isomérisés préparés à l'aide de ce procédé.
PCT/EP1995/004997 1994-12-13 1995-12-12 Procede d'isomerisation d'une charge d'alimentation hydrocarbonee WO1996018705A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
AU43457/96A AU4345796A (en) 1994-12-13 1995-12-12 Process for the isomerisation of a hydrocarbonaceous feedstock
EP95942174A EP0797650A1 (fr) 1994-12-13 1995-12-12 Procede d'isomerisation d'une charge d'alimentation hydrocarbonee
JP8518282A JPH10510568A (ja) 1994-12-13 1995-12-12 炭化水素供給原料の異性化方法
MXPA/A/1997/004292A MXPA97004292A (en) 1994-12-13 1997-06-10 Process for the isomerization of a matter primahidrocarbur

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP94203628.6 1994-12-13
EP94203628 1994-12-13

Publications (1)

Publication Number Publication Date
WO1996018705A1 true WO1996018705A1 (fr) 1996-06-20

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PCT/EP1995/004997 WO1996018705A1 (fr) 1994-12-13 1995-12-12 Procede d'isomerisation d'une charge d'alimentation hydrocarbonee

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EP (1) EP0797650A1 (fr)
JP (1) JPH10510568A (fr)
AU (1) AU4345796A (fr)
CZ (1) CZ160897A3 (fr)
WO (1) WO1996018705A1 (fr)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1998056876A1 (fr) * 1997-05-29 1998-12-17 Fortum Oil And Gas Oy Procede de production de carburant diesel riche
FR2771419A1 (fr) * 1997-11-25 1999-05-28 Inst Francais Du Petrole Essences a haut indice d'octane et leur production par un procede associant hydro-isomerisation et separation
US8859832B2 (en) 2005-07-05 2014-10-14 Neste Oil Oyj Process for the manufacture of diesel range hydrocarbons
CN111229299A (zh) * 2020-03-10 2020-06-05 广西华睿能源科技有限公司 一种直链烷烃高效异构化和芳构化催化剂及其制备方法
US12203035B2 (en) 2005-07-05 2025-01-21 Neste Oyj Process for the manufacture of diesel range hydrocarbons

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Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1998056876A1 (fr) * 1997-05-29 1998-12-17 Fortum Oil And Gas Oy Procede de production de carburant diesel riche
US6399845B1 (en) 1997-05-29 2002-06-04 Fortum Oil & Gas Oy Process for producing high grade diesel fuel
FR2771419A1 (fr) * 1997-11-25 1999-05-28 Inst Francais Du Petrole Essences a haut indice d'octane et leur production par un procede associant hydro-isomerisation et separation
EP0922750A1 (fr) * 1997-11-25 1999-06-16 Institut Français du Pétrole Essences à haut indice d'octane et leur production par un procédé associant hydro-isomérisation et séparation
JPH11228976A (ja) * 1997-11-25 1999-08-24 Inst Fr Petrole 高オクタン価ガソリン、および水素化・異性化と分離とを組合わせることによるその製造方法
US9598327B2 (en) 2005-07-05 2017-03-21 Neste Oil Oyj Process for the manufacture of diesel range hydrocarbons
US8859832B2 (en) 2005-07-05 2014-10-14 Neste Oil Oyj Process for the manufacture of diesel range hydrocarbons
US10059887B2 (en) 2005-07-05 2018-08-28 Neste Oyj Process for the manufacture of diesel range hydrocarbons
US10550332B2 (en) 2005-07-05 2020-02-04 Neste Oyj Process for the manufacture of diesel range hydrocarbons
US10800976B2 (en) 2005-07-05 2020-10-13 Neste Oyj Process for the manufacture of diesel range hydrocarbons
US11473018B2 (en) 2005-07-05 2022-10-18 Neste Oyj Process for the manufacture of diesel range hydrocarbons
US12203035B2 (en) 2005-07-05 2025-01-21 Neste Oyj Process for the manufacture of diesel range hydrocarbons
CN111229299A (zh) * 2020-03-10 2020-06-05 广西华睿能源科技有限公司 一种直链烷烃高效异构化和芳构化催化剂及其制备方法

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AU4345796A (en) 1996-07-03
EP0797650A1 (fr) 1997-10-01
MX9704292A (es) 1997-09-30
JPH10510568A (ja) 1998-10-13

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