WO1993002994A1 - Procede de conversion d'hydrocarbures - Google Patents

Procede de conversion d'hydrocarbures Download PDF

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Publication number
WO1993002994A1
WO1993002994A1 PCT/GB1992/001325 GB9201325W WO9302994A1 WO 1993002994 A1 WO1993002994 A1 WO 1993002994A1 GB 9201325 W GB9201325 W GB 9201325W WO 9302994 A1 WO9302994 A1 WO 9302994A1
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WO
WIPO (PCT)
Prior art keywords
zeolite
feed
catalyst
acid
conversion
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Application number
PCT/GB1992/001325
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English (en)
Inventor
Sami Ali Ibrahim Barri
David Arthur Kidd
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The British Petroleum Company Plc
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Publication date
Application filed by The British Petroleum Company Plc filed Critical The British Petroleum Company Plc
Priority to JP5503364A priority Critical patent/JPH06509352A/ja
Priority to EP92915912A priority patent/EP0596930A1/fr
Publication of WO1993002994A1 publication Critical patent/WO1993002994A1/fr

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    • 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
    • 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
    • B01J29/7042—TON-type, e.g. Theta-1, ISI-1, KZ-2, NU-10 or ZSM-22
    • 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
    • B01J37/06—Washing
    • 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
    • B01J37/08—Heat treatment
    • B01J37/10—Heat treatment in the presence of water, e.g. steam
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/86—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon
    • C07C2/862—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon the non-hydrocarbon contains only oxygen as hetero-atoms
    • C07C2/864—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon the non-hydrocarbon contains only oxygen as hetero-atoms the non-hydrocarbon is an alcohol
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/86—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon
    • C07C2/862—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon the non-hydrocarbon contains only oxygen as hetero-atoms
    • C07C2/865—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon the non-hydrocarbon contains only oxygen as hetero-atoms the non-hydrocarbon is an ether
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/86—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon
    • C07C2/862—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon the non-hydrocarbon contains only oxygen as hetero-atoms
    • C07C2/867—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon the non-hydrocarbon contains only oxygen as hetero-atoms the non-hydrocarbon is an aldehyde or a ketone
    • 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
    • B01J2229/16—After treatment, characterised by the effect to be obtained to increase the Si/Al ratio; Dealumination
    • 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
    • B01J2229/30—After treatment, characterised by the means used
    • B01J2229/36—Steaming
    • 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
    • B01J2229/30—After treatment, characterised by the means used
    • B01J2229/37—Acid treatment
    • 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
    • C07C2529/18—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type
    • 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
    • C07C2529/65—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the ferrierite type, e.g. types ZSM-21, ZSM-35 or ZSM-38
    • 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
    • C07C2529/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups C07C2529/08 - C07C2529/65

Definitions

  • This invention relates to a process for the conversion of hydrocarbons using a zeolite catalyst and to a method of regenerating the spent zeolite catalyst.
  • EP-A-247802 discloses that zeolites Theta-1 and ZSM-23 can be used as catalysts in the restructuring of a C2-C10 olefinic feedstock.
  • the feedstock rich in linear olefins, is converted into a product enriched in branched olefins.
  • Zeolite Theta-1 is also known as Nu-10, ZSM-22, KZ-2 and ISI-1 and its systematic nomenclature is TON.
  • EP-A-65400 discloses that zeolite Nu-10 can be used for the conversion of methanol to olefins, and for alkylation of alkylbenzenes.
  • US Patent No. 4579993 discloses a process for the conversion of methanol to olefins using a zeolite catalyst wherein the catalyst is treated to both steaming and acid-extraction.
  • the preferred catalyst is ZSM-5!
  • US Patent No. 4658075 discloses a process for converting aromatic compounds using a crystalline zeolite which has been treated by contact with steam, followed by an aluminium compound followed by contact with an aqueous acid solution.
  • zeolites which can deactivate rapidly due to their unidimensional structure can be activated using a steam/acid treatment process, and their use in hydrocarbon conversion processes results in surprisingly higher conversion values and little loss in conversion values with time.
  • the present invention provides a process for the conversion of a hydrocarbon feed characterised in that the feed is contacted with a zeolite catalyst to produce a product, said zeolite having a framework structure which includes a 10- or 12-member channel that is not intersected by another 10- or
  • the process of the present invention is suitably directed to the conversion of an olefin containing feed and to the production of a hydrocarbon which is suitably an olefin which is different to that of the feed.
  • the preferred conversion reactions are the conversion of a linear olefin to a branched olefin; the alkylation of aromatics with olefins to produce alkyl benzene; dimerisation and/or oligomerisation of olefins; and the reaction of methanol, formaldehyde and/or dimethyl ether with an olefin to produce higher olefins.
  • a particularly preferred process is the reaction of C3 and/or C4 olefins with methanol, formaldehyde and/or dimethylether, to produce higher olefins.
  • the molar ratio of olefin to methanol, formaldehyde and/or dimethylether is preferably greater than 1 to 20 to 100 to 1, more preferably greater from 1:10 to 10:1, especially from 1 to 1 to 5 to 1.
  • the reaction is preferably carried out at a temperature in excess of 200"C, preferably 250 to 600 ⁇ C and may be carried out at reduced, atmospheric or elevated pressure.
  • the pressure is the total pressure of the reaction chamber.
  • a pressure of from 10-10,000 KEa absolute, preferably 50-1000 KPa absolute may be used.
  • the feedstock may be fed into the reaction chamber either with or without diluents, e.g. water, steam, alkanes or inert gas.
  • diluents e.g. water, steam, alkanes or inert gas.
  • the product of the process includes branched olefinic hydrocarbons, rich in isobutene and methylbutenes.
  • a small amount of by-products, e.g. methane, ethane, ethene and linear olefins are also present.
  • a further particularly preferred process is the conversion of a C -C_o > preferably 0 -0 , linear olefin to a branched olefin.
  • the reaction is preferably carried out at a temperature in the range of from 200 to 550 ⁇ C, especially 300-550 c C.
  • the feedstock is preferably diluted with a gas or gases inert under the reaction conditions, for example nitrogen or a alkane. When a diluent is present, it is preferably present in an amount of at least
  • the reaction is preferably carried out at a pressure of from 50 to 1000 KPa, especially 100 to 300 KPa.
  • Zeolites which may be used in the present invention include TON (Theta-1, Nu-10, ZSM-22, KZ-2, ISI-1), MTT (ZSM-23, EU-13, ISI-4, KZ-1), ZSM-48, FER (FU-9, Nu-23, ISI-6, ZSM-35), and EUO (EU-1, TPZ-3, ZSM-50), all of which contain a 10-membered channel that is not intersected by another 10- or 12-membered channel; and MTW (ZSM-12, CZH-5, Theta-3, TPZ-12) and MOR (mordenite), which contain a 12-membered channel that is not intersected by another 10- or
  • a synthetic zeolite immediately after synthesis contains cations which, depending upon the precise synthesis method used, may be hydrogen, aluminium, alkali metals, organic nitrogen cations or any combination thereof.
  • the zeolite treated by the treatment process may be in the hydrogen form.
  • the hydrogen form may be achieved by, in the case of organic containing zeolite, calcination to remove the organics followed by either ammonium ion exchange or proton exchange with an acid solution or a combination of both.
  • the hydrogen form could, if desired, be prepared by either direct ammonium ion exchange followed by calcination or proton exchange with acid solution or a combination of both. If the zeolite to be treated is not in the hydrogen form, the second step of the treatment process, the treatment with acid, will of course introduce protons into the zeolite.
  • the zeolite may, if desired, be bound in a suitable binding material.
  • the binder may suitably be one of the conventional alumina, silica, clay or aluminophosphate binders or a combination of binders.
  • the zeolite used in the process of the present invention is treated with a two step treatment process.
  • the treatment process may be applied to the zeolite at any desired point in the catalyst preparation; it may for example be applied to the zeolite in a powder form, in the form of an extrudate or in a bound form.
  • the treatment method is particularly useful for improving the long-term performance of the catalyst.
  • the first step of the zeolite treatment process is carried out at a temperature in the range of from 100 to 800°C, especially 400 to 600 ⁇ C.
  • the steam partial pressure may be 100%, or other gases may be present as desired; for example, the steam may be in admixture with a diluent, such as nitrogen or air.
  • the total pressure is not crucial; atmospheric pressure is convenient, but other pressures, for example in the range 10 to 10000 KPa may be used if desired.
  • the subsequent step of contacting the zeolite with an acid is preferably carried out using a dilute aqueous acid.
  • Acids for use in the treatment of the zeolite may be mineral acids. The preferred acids are nitric acid, hydrochloric acid or sulphuric acid.
  • the strength of the acid may be suitably from 0.01 molar, preferably 0.05 to 10 molar.
  • the contact with acid is preferably carried out at a temperature in the range of from 5 to 200 ⁇ C especially 80 to 120°C, for a period of suitably 0.1 to 10 hours, preferably 0.5 to 2 hours.
  • the zeolite is preferably washed with water, dried and calcined before being used as a catalyst.
  • a treatment process for a zeolite which comprises a first step of contacting the zeolite with steam and a subsequent step of contacting the zeolite with an acid wherein said zeolite is selected from the structure types TON, ZSM-48, FER, EUO and MTW.
  • a particular benefit of the present invention is the ability of attaining high initial conversion rates and loss of conversion with time is less rapid than prior art processes.
  • Theta-1 was synthesised using ammonia as the templating agent.
  • Sodium aluminate (30 g, ex.BDH, 40 wt% AI2O3, 30 wt% Na2 ⁇ and 30 wt% H2O) and sodium hydroxide (15.6 g ex.BDH) were dissolved in distilled water (240 g).
  • Ammonia solution (1400 g, SG 0.90 containing 25% NH3) was added with gentle mixing.
  • 1200 g of silica gel sold under the Trade Mark Ludox AS40 (ex. Du Pont) which contained 40 wt% silica was added over fifteen minutes with stirring to maintain a homogeneous hydrogel.
  • the molar composition of the hydrogel was:-
  • Theta-1 which contained both Na ⁇ and NH4 + ions was directly ion exchanged in order to remove the Na + ions by mixing forl hour with an aqueous ammonium nitrate solution (IM, zeolite to solution weight ratio of I.10).
  • IM aqueous ammonium nitrate solution
  • the zeolite was filtered, washed and the ion exchange treatment repeated.
  • the ammonium form of the zeolite was then dried at 100"C and calcined overnight in air at 550*C to convert it to the hydrogen form.
  • the X-ray diffraction pattern of the zeolite product is shown in Table 1. TABLE 1; XRD OF PRODUCT OF EXAMPLE 1
  • the H-form of the zeolite as prepared in Example 1 was pressed under 10 tonnes pressure into tablets which were broken into granules and these in turn were sieved to pass 600 micron but not 250 micron sieves.
  • the granules were placed in a tubular reactor (60 mm ID) and heated to 550°C. There was a large preheating zone on which water was converted to steam before it came into contact with the catalyst granules. Distilled water and nitrogen were passed through the preheating zone over the catalyst at the rate of 30 grams/hour and 60 ml/minute respectively. After 2 hours with the reactor temperature at 550°C, the water flow was stopped and the catalyst was cooled to ambient.
  • Example 3 Catalyst Preparation and Testing The zeolite powders as prepared in Example 2 and in Example 1 (comparative) were pressed into tablets under 10 tonnes pressure. The tablets were broken and sieved into granules to pass 600 micron but not 250 micron sieves.
  • WHSV weight hourly space velocity which is the weight of the methanol and hydrocarbon fed per weight of the catalyst per hour
  • the powder was examined by X-ray diffraction and found to be highly crystalline Theta-1 zeolite.
  • zeolite Approximately 2.5 kg of the zeolite was spread in a tray to give a bed of four inches in depth and calcined in air at 580°C for 24 hours.
  • the zeolite was ion exchanged by contacting with 1 equivalent/dm ⁇ ammonium nitrate solution (1 litre/0.1 kg zeolite) and mixing at ambient temperature for 16 hours.
  • the zeolite was filtered, washed with de-ionised water and the ion exchange treatment was repeated twice more. The last ion exchange treatment was continued for 70 hours.
  • the washed dried ion exchanged zeolite was calcined as above at 550°C for 24 hours.
  • the zeolite was mixed with a commercially available silica/alumina material sold under the Trade Mark "Hymod Excelsior PKX1" and supplied by English China Clays and the mixture extruded to give extrudates whose zeolite content -was 82% by weight.
  • a commercially available silica/alumina material sold under the Trade Mark "Hymod Excelsior PKX1" and supplied by English China Clays and the mixture extruded to give extrudates whose zeolite content -was 82% by weight.
  • Example 5 Catalyst Steaming and Acid Washing
  • the extrudates were placed in a tubular reactor (60 mm ID) and heated to 550°C. There was a large preheating zone on which water was converted to steam before it came into contact with the catalyst. Distilled water and nitrogen were passed over the catalyst at the rate of 30 grams/hour and 60 ml/minute respectively. After 2 hours the water flow was stopped and the catalyst was cooled to ambient. The catalyst was then refluxed in 1 equivalent/litre nitric acid (10 grams of catalyst/200 ml of acid solution) for 1 hour. The extrudates were filtered, washed with distilled water and refluxed as before twice more. Finally the catalyst was calcined at 550*C for 16 hours.
  • the reaction pressure and temperature were 2 bars absolute and 500°C respectively.
  • the volume of the catalyst was 5 ml and its weight was 2.02 grams.
  • the weight of the feed in grams passed over 1 gram of catalyst per hour was fixed at 38-42.
  • the comparative catalyst not treated according to the invention Example 4
  • the levels of isobutene in the total product were 16.7 wt%, 14.0 wt% and 14.3 wt% respectively.
  • the proportions of the converted linear butenes that were converted to isobutenes (selectivity) at these times were 74.4 wt%, 78.5 wt% and 81.5 wt% respectively.
  • Example 5 when the catalyst according to the invention (Example 5) was tested after 24.5 and 49.5 hours on stream the levels of isobutene in the total product were 19.5 wt% and 19.7 wt% respectively. The proportions of the converted linear butenes that were converted to isobutenes (selectivity) at these times were 73.8 wt% and 83.2 wt% respectively.
  • Example 7
  • a batch of the hydrogen form of zeolite Theta-1 was prepared as described in Example 1 and steam and acid treated as described in Example 2.
  • the zeolite was again pressed into tablets under 10 tonnes pressure, broken into granules and sieved to pass 600 micron but not 250 micron sieves.
  • the granules were tested for the structural isomerisation of n-butene in the feed to produce isobutene in a fixed bed tubular reactor (12 mm ID) with a co-axial thermocouple well (2 ram OD) .
  • the feed had the composition: Component wt% isobutane 11.59 n-butane 24.39 t-butene-2 7.28 1-butene 48.44 isobutene 0.81 c-butene-2 7.23 n-pentenes 0.09 hexenes 0.05 octenes 0.12
  • the reaction pressure and temperature were 2 bars absolute and 500°C respectively.
  • the volume of the catalyst was 5 ml and its weight was 1.83 grams.
  • the weight of the feed in grams passed over 1 gram of catalyst per hour was fixed at 45-47. After 77 hours on stream the catalyst was regenerated in 10-20% air in nitrogen at 580°C for 48 hours and then in air for an additional 12 hours. Nitrogen was passed over the catalyst and the temperature was reduced to 500°C.
  • the catalyst was tested again as described above using the same feed and at the same conditions.
  • the weight of the feed in grams passed over 1 gram of catalyst per hour was fixed at 42-44. After 24.5 and 48.0 hours on stream the levels of isobutene in the total product was 20.6 wt% and 18.2 wt% respectively.
  • the proportions of the converted linear butenes that were converted to isobutenes (selectivity) were 72.4 wt% and 80.3 wt% respectively. After 73 hours on stream the catalyst was regenerated as described before and testing was recommenced. After 24.0 and 48.0 hours on stream the levels of isobutene in the total product were 20.6 wt% and 18.2 wtX respectively. The proportions of the converted linear butenes that were converted to isobutenes (selectivity) were 74.1 wt% and 81.0 wt% respectively.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

Procédé de conversion d'une charge d'alimentation en hydrocarbure, selon lequel la charge est mise en contact avec un catalyseur à zéolithe pour former un produit, le zéolithe présentant une structure contenant un canal à 10 ou 12 membres qui n'est pas entrecoupé par un autre canal à 10 à 12 membres et ayant été traité selon un procédé qui consiste tout d'abord à mettre en contact le zéolithe avec de la vapeur, puis à le mettre en contact avec un acide.
PCT/GB1992/001325 1991-07-31 1992-07-20 Procede de conversion d'hydrocarbures WO1993002994A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
JP5503364A JPH06509352A (ja) 1991-07-31 1992-07-20 炭化水素の転換方法
EP92915912A EP0596930A1 (fr) 1991-07-31 1992-07-20 Procede de conversion d'hydrocarbures

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB9116499.6 1991-07-31
GB919116499A GB9116499D0 (en) 1991-07-31 1991-07-31 Treatment method for zeolites

Publications (1)

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WO1993002994A1 true WO1993002994A1 (fr) 1993-02-18

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EP (1) EP0596930A1 (fr)
JP (1) JPH06509352A (fr)
AU (1) AU2329692A (fr)
GB (1) GB9116499D0 (fr)
WO (1) WO1993002994A1 (fr)

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0671212A1 (fr) * 1993-09-30 1995-09-13 Sanyo Petrochemical Co. Ltd. Procede de desaluminisation partielle d'un catalyseur zeolitique
WO1998007513A1 (fr) * 1996-08-20 1998-02-26 Monsanto Company Ameliorations apportees a la stabilite d'un catalyseur utilise lors d'une hydroxylation de benzene par traitement a l'acide
FR2755958A1 (fr) * 1996-11-19 1998-05-22 Inst Francais Du Petrole Zeolithe nu-86 desaluminee et son utilisation en conversion des hydrocarbures
EP0855218A1 (fr) * 1997-01-24 1998-07-29 Institut Français du Pétrole Zéolithe IM-5 désaluminée
US5789331A (en) * 1993-09-30 1998-08-04 Sanyo Petrochemical Co., Ltd. Method for partially dealuminating a zeolite catalyst
FR2765207A1 (fr) * 1997-06-25 1998-12-31 Inst Francais Du Petrole Zeolithe nu-85, catalyseur et procede pour l'amelioration du point d'ecoulement de charges contenant des paraffines
FR2765209A1 (fr) * 1997-06-25 1998-12-31 Inst Francais Du Petrole Zeolithe eu-1, catalyseur et procede pour l'amelioration du point d'ecoulement de charges contenant des paraffines
FR2765208A1 (fr) * 1997-06-25 1998-12-31 Inst Francais Du Petrole Zeolithe nu-85, catalyseur et procede et pour l'amelioration du point d'ecoulement de charges contenant des paraffines
FR2765206A1 (fr) * 1997-06-25 1998-12-31 Inst Francais Du Petrole Zeolithe eu-1, catalyseur et procede pour l'amelioration du point d'ecoulement de charges contenant des paraffines
CN1052667C (zh) * 1995-10-06 2000-05-24 中国石油化工总公司 贵金属负载型烷基芳烃异构化催化剂
US6156938A (en) * 1997-04-03 2000-12-05 Solutia, Inc. Process for making phenol or phenol derivatives
EP1167326B2 (fr) † 2000-06-26 2007-11-14 Saudi Basic Industries Corporation Dimerisation d'isobutène
US8049054B2 (en) * 2006-05-19 2011-11-01 Shell Oil Company Process for the preparation of C5 and/or C6 olefin
US8168842B2 (en) 2006-05-19 2012-05-01 Shell Oil Company Process for the alkylation of a cycloalkene
US8822749B2 (en) 2007-11-19 2014-09-02 Shell Oil Company Process for the preparation of an olefinic product

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5321194A (en) * 1992-05-11 1994-06-14 Mobil Oil Corporation N-olefin skeletal isomerization process using dicarboxylic acid treated zeolites
FR2915113B1 (fr) * 2007-04-23 2009-06-26 Inst Francais Du Petrole Zeolithe eu-1 modifiee et son utilisation en isomerisation des composes c8 aromatiques.

Citations (3)

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Publication number Priority date Publication date Assignee Title
US4579993A (en) * 1984-08-22 1986-04-01 Mobil Oil Corporation Catalyst for methanol conversion by a combination of steaming and acid-extraction
US4658075A (en) * 1983-01-17 1987-04-14 Mobil Oil Corporation Xylene isomerization with a reactivated zeolite
EP0247802A1 (fr) * 1986-05-27 1987-12-02 The British Petroleum Company P.L.C. Isomérisation d'oléfines

Patent Citations (3)

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US4658075A (en) * 1983-01-17 1987-04-14 Mobil Oil Corporation Xylene isomerization with a reactivated zeolite
US4579993A (en) * 1984-08-22 1986-04-01 Mobil Oil Corporation Catalyst for methanol conversion by a combination of steaming and acid-extraction
EP0247802A1 (fr) * 1986-05-27 1987-12-02 The British Petroleum Company P.L.C. Isomérisation d'oléfines

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US5789331A (en) * 1993-09-30 1998-08-04 Sanyo Petrochemical Co., Ltd. Method for partially dealuminating a zeolite catalyst
EP0671212A4 (fr) * 1993-09-30 1996-03-13 Sanyo Petrochemical Co Ltd Procede de desaluminisation partielle d'un catalyseur zeolitique.
EP0671212A1 (fr) * 1993-09-30 1995-09-13 Sanyo Petrochemical Co. Ltd. Procede de desaluminisation partielle d'un catalyseur zeolitique
CN1052667C (zh) * 1995-10-06 2000-05-24 中国石油化工总公司 贵金属负载型烷基芳烃异构化催化剂
WO1998007513A1 (fr) * 1996-08-20 1998-02-26 Monsanto Company Ameliorations apportees a la stabilite d'un catalyseur utilise lors d'une hydroxylation de benzene par traitement a l'acide
US5874647A (en) * 1996-08-20 1999-02-23 Solutia Inc. Benzene hydroxylation catalyst stability by acid treatment
US6337428B1 (en) 1996-11-19 2002-01-08 Institut Francais Du Petrole Conversion of hydrocarbons with a dealuminated NU-86 zeolite catalyst
CN1110365C (zh) * 1996-11-19 2003-06-04 法国石油公司 脱铝nu－86沸石及其在烃类转化中的用途
FR2755958A1 (fr) * 1996-11-19 1998-05-22 Inst Francais Du Petrole Zeolithe nu-86 desaluminee et son utilisation en conversion des hydrocarbures
US6165439A (en) * 1996-11-19 2000-12-26 Institut Francais Du Petrole Dealuminated NU-86 zeolite and its use for the conversion of hydrocarbons
WO1998022213A1 (fr) * 1996-11-19 1998-05-28 Institut Français Du Petrole Zeolithe nu-86 desaluminee et son utilisation en conversion des hydrocarbures
FR2758810A1 (fr) * 1997-01-24 1998-07-31 Inst Francais Du Petrole Zeolithe im-5 desaluminee
EP0855218A1 (fr) * 1997-01-24 1998-07-29 Institut Français du Pétrole Zéolithe IM-5 désaluminée
US5968475A (en) * 1997-01-24 1999-10-19 Institut Francais Du Petrole Dealuminated IM-5 zeolite
US6156938A (en) * 1997-04-03 2000-12-05 Solutia, Inc. Process for making phenol or phenol derivatives
US6153548A (en) * 1997-06-25 2000-11-28 Institut Francais Du Petrole NU-85 zeolite catalyst and a process for improving the pour point of feeds containing paraffins
FR2765206A1 (fr) * 1997-06-25 1998-12-31 Inst Francais Du Petrole Zeolithe eu-1, catalyseur et procede pour l'amelioration du point d'ecoulement de charges contenant des paraffines
FR2765208A1 (fr) * 1997-06-25 1998-12-31 Inst Francais Du Petrole Zeolithe nu-85, catalyseur et procede et pour l'amelioration du point d'ecoulement de charges contenant des paraffines
FR2765209A1 (fr) * 1997-06-25 1998-12-31 Inst Francais Du Petrole Zeolithe eu-1, catalyseur et procede pour l'amelioration du point d'ecoulement de charges contenant des paraffines
US6350370B1 (en) 1997-06-25 2002-02-26 Institut Francais Du Petrole NU-85 zeolite catalyst and a process for improving the pour point of feeds containing paraffins
FR2765207A1 (fr) * 1997-06-25 1998-12-31 Inst Francais Du Petrole Zeolithe nu-85, catalyseur et procede pour l'amelioration du point d'ecoulement de charges contenant des paraffines
US6733658B2 (en) 1997-06-25 2004-05-11 Institut Francais Du Petrole EU-1 zeolite catalyst and a process for the reduction of the pour point of feeds containing paraffins
EP1167326B2 (fr) † 2000-06-26 2007-11-14 Saudi Basic Industries Corporation Dimerisation d'isobutène
US8049054B2 (en) * 2006-05-19 2011-11-01 Shell Oil Company Process for the preparation of C5 and/or C6 olefin
US8168842B2 (en) 2006-05-19 2012-05-01 Shell Oil Company Process for the alkylation of a cycloalkene
US8822749B2 (en) 2007-11-19 2014-09-02 Shell Oil Company Process for the preparation of an olefinic product

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EP0596930A1 (fr) 1994-05-18
JPH06509352A (ja) 1994-10-20
AU2329692A (en) 1993-03-02
GB9116499D0 (en) 1991-09-11

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