WO2000015338A1 - Zeolite amelioree - Google Patents

Zeolite amelioree Download PDF

Info

Publication number
WO2000015338A1
WO2000015338A1 PCT/US1999/020536 US9920536W WO0015338A1 WO 2000015338 A1 WO2000015338 A1 WO 2000015338A1 US 9920536 W US9920536 W US 9920536W WO 0015338 A1 WO0015338 A1 WO 0015338A1
Authority
WO
WIPO (PCT)
Prior art keywords
recited
zeolite
composition
acid
compound
Prior art date
Application number
PCT/US1999/020536
Other languages
English (en)
Inventor
Charles A. Drake
An-Hsiang Wu
Original Assignee
Phillips Petroleum Company
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 Phillips Petroleum Company filed Critical Phillips Petroleum Company
Priority to AU58150/99A priority Critical patent/AU5815099A/en
Publication of WO2000015338A1 publication Critical patent/WO2000015338A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G35/00—Reforming naphtha
    • C10G35/04—Catalytic reforming
    • C10G35/06—Catalytic reforming characterised by the catalyst used
    • C10G35/095—Catalytic reforming 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
    • 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
    • B01J29/061—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof containing metallic elements added to the zeolite

Definitions

  • the invention relates to catalyst compositions useful in hydrocarbon upgrading processes and to methods for their production and use.
  • this invention relates to processes for converting hydrocarbons to aromatic and olefin (ethylene and propylene) hydrocarbons with an increase in BTX (benzene, toluene and xylenes) yield resulting from the conversion of such hydrocarbons in the presence of such catalyst compositions.
  • BTX benzene, toluene and xylenes
  • the inventive composition comprises a zeolite, a zinc component and a metal selected from the group consisting of Group IIIA and Group VIB of the periodic table of the elements.
  • CAS version Hawley's Condensed Chemical
  • inventive composition may be prepared by incorporating a zinc component and a metal selected from the group consisting of Group IIIA and Group VIB into a zeolite.
  • inventive composition may be used in the conversion of a hydrocarbon or hydrocarbon mixture to aromatic and olefin hydrocarbons by contacting, under conversion conditions, a hydrocarbon feedstock with the inventive composition.
  • the zeolite material used in preparing the inventive composition can be any zeolite that is effective in the conversion of non-aromatic hydrocarbons to aromatic hydrocarbons when contacted under suitable reaction conditions with non-aromatic hydrocarbons.
  • the zeolite has a constraint index (as defined in U.S. Patent 4.097,367, the disclosure of which is incorporated herein by reference) in the range of from about 0.4 to about 12, preferably from about 2 to about 9.
  • the molar ratio of SiO 2 to Al 2 O 3 in the crystalline framework of the zeolite is at least about 5:1 and can range up to infinity.
  • the molar ratio of SiO, to Al 2 O 3 in the zeolite framework is in the range of from about 8:1 to about 200:1, more preferably in the range of from about 12:1 to about 100:1.
  • Preferred zeolites include, but are not limited to, ZSM-5, ZSM-8, ZSM-11, ZSM-12, ZSM-35, ZSM-38, and mixtures of any two or more thereof. Some of these zeolites are also known as "MFI" or "Pentasil" zeolites. The presently more preferred zeolite is ZSM-5.
  • Any suitable means or method can be used to treat the zeolite starting material with acid to give an acid-leached zeolite. It is preferred for the zeolite to be soaked with an acid solution by any suitable means known in the art for contacting the zeolite with such acid solution.
  • the acid solution used to treat the zeolite can be a solution of any acid that suitably provides for the leaching of aluminum atoms from the zeolite particles. Preferably, the acid concentration in this solution is about 1-10 equivalents per liter. Examples of such suitable acids include sulfuric, phosphoric, nitric and hydrochloric.
  • the preferred acid solution is aqueous hydrochloric acid.
  • the zeolite is soaked in the acid solution (preferably at a temperature of about 50-100°C) for a period upwardly to about 15 hours, but, preferably from 0.1 hour to 12 hours. After soaking, the resultant acid-leached zeolite is washed free of the acid and then can be dried or calcined, or both.
  • the acid solution preferably at a temperature of about 50-100°C
  • the inventive composition is a material that comprises a zeolite which may or may not have been acid-leached, a zinc component and a metal selected from the group consisting of Group IIIA and Group VIB.
  • the zinc component and metal can be incorporated into the acid-leached zeolite by any suitable means or method known in the art for incorporating metallic elements into a substrate material.
  • a preferred method is the use of any standard incipient wetness technique for impregnating the zeolite substrate with the metal promoters.
  • the preferred method uses a liquid impregnation solution containing the desirable concentrations of zinc and the metal selected from the group consisting of Group IIIA and Group VIB so as to ultimately provide the final inventive composition having the required concentrations of zinc and the metal selected from the group consisting of Group IIIA and Group VIB.
  • the impregnation of the zeolite which may or may not have been acid-leached, an aqueous solution containing the zinc component and the metal.
  • the preferred impregnation solution is an aqueous solution formed by dissolving a compound comprising zinc and a metal selected from the group consisting of Group IIIA and Group VIB in water. It is preferable to use somewhat of an acidic solution to aid in the dissolution of the compound.
  • the acid used to acidify the impregnation solution is preferably nitric acid.
  • Suitable compounds comprising zinc and a metal selected from the group consisting of Group IIIA and Group VIB for incorporating into the zeolite, which may or may not have been acid-leached include, but are not limited to, zinc borate, zinc molybdate, zinc chromate, zinc tungstate and zinc aluminate.
  • the amounts of zinc and the metal selected from the group consisting of Group IIIA and Group VIB incorporated or impregnated into the zeolite, which may or may not have been acid-leached, should be such as to give concentrations effective in providing the desirable properties of increased BTX yield when the inventive composition is employed in the conversion of a hydrocarbon feed.
  • the weight percent of the compound comprising zinc and the metal selected from the group consisting of Group IIIA and Group VIB present in the impregnated zeolite, which may or may not have been acid-leached, is generally in the range upwardly to about 10 weight percent based on the total weight of the impregnated zeolite.
  • the preferred concentration of the compound in the impregnated zeolite is in the range of from about 0.05 to about 9 weight percent and, most preferably, from 0.1 to 8 weight percent based on the total weight of the impregnated zeolite.
  • the impregnated zeolite which may or may not have been acid- leached, can be dried or calcined, or both.
  • the drying step is generally performed in the presence of air at a temperature in the range of from about 20°C to about 125°C and over a time period of from about 0.1 hour to about 4 hours.
  • the calcination temperature is generally in the range of from about 300°C to about 1000°C.
  • the calcination can be performed in either an air atmosphere or an inert atmosphere or a combination thereof for a time period of from about 0.1 hour to about 30 hours.
  • Any suitable hydrocarbon feed which comprises paraffins (alkanes) and/or olefins (alkenes) and/or naphthenes (cycloalkanes), wherein each of these hydrocarbons contains from 2 to 16 carbon atoms per molecule can be used as a feed to be contacted with the inventive composition under suitable process conditions for obtaining a reaction product comprising alkenes containing from 2 to 5 carbon atoms per molecule and aromatic hydrocarbons. Frequently, these feedstocks also contain aromatic hydrocarbons.
  • Non-limiting examples of suitable, available feedstocks include gasolines from catalytic oil cracking (e.g., FCC and hydrocracking) processes, pyrolysis gasolines from thermal hydrocarbon (e.g., ethane, propane, and naphtha) cracking processes, naphthas, gas oils, reformates, straight-run gasoline and the like.
  • the preferred feed is a gasoline-boiling range hydrocarbon feedstock suitable for use as at least a gasoline blend stock generally having a boiling range of about 30-210°C.
  • the content of paraffins exceeds the combined content of olefins, naphthenes and aromatics (if present).
  • the hydrocarbon feed stream can be contacted in any suitable manner with the inventive compositions described herein contained within a conversion reaction zone.
  • the contacting step can be operated as a batch process step or, preferably, as a continuous process step. In the latter operation, a solid catalyst bed or a moving catalyst bed or a fluidized catalyst bed can be employed. Any of these operational modes has advantages and disadvantages, and those skilled in the art can select the one most suitable for a particular feed and catalyst.
  • the contacting step is preferably carried out within a conversion reaction zone, wherein is contained the inventive composition, and under reaction conditions that suitably promote the formation of aromatics, preferably BTX, from at least a portion of the hydrocarbons of the hydrocarbon feed.
  • the reaction temperature of the contacting step is generally in the range of from about 400°C to about 800°C, preferably, from about 450°C to about 750°C and, most preferably, from 500°C to 700°C.
  • the contacting pressure can range from subatmospheric pressure upwardly to about 500 psia, preferably, from about atmospheric to about 450 psia and, most preferably, from 20 psia to 400 psia.
  • the flow rate at which the hydrocarbon feed is charged to the conversion reaction zone is such as to provide a weight hourly space velocity ("WHSV") in the range of from exceeding 0 hour "1 upwardly to about 1000 hour "1 .
  • WHSV weight hourly space velocity
  • the preferred WHSV of the feed to the conversion reaction zone can be in the range of from about 0.25 hour “1 to about 250 hour “1 and, most preferably, from 0.5 hour "1 to 100 hour "1 .
  • a commercially available ZSM-5 catalyst (provided by United Catalysts Inc., Louisville, KY, under product designation "T-4480") was treated by acid-leaching. To acid-leach the catalyst, it was soaked in an aqueous HCl solution, having a concentration of 38 weight percent HCl (approximately 6N), for two hours at a constant temperature of about 90°C. After soaking, the catalyst was separated from the acid solution and thoroughly washed with water and dried.
  • a 20.0 gram quantity of the above-described acid-leached ZSM-5 catalyst was impregnated by an incipient wetness technique with a solution containing 1.4 grams zinc molybdate, 20 grams water and 2.8 grams nitric acid. This impregnated, acid-leached ZSM-5 catalyst was dried and then calcined at a temperature of about 500°C for three hours.
  • Example II This example illustrates the use of the zeolite materials described in Example I as catalysts in the conversion of a gasoline feed to benzene, toluene and xylenes (BTX) and olefins (ethylene, propylene).
  • BTX benzene, toluene and xylenes
  • olefins ethylene, propylene
  • Example I a 5.0 g sample of the catalyst materials described in Example I, that is, Catalysts A, B, C and D, respectively, was placed into a stainless steel tube reactor (length: about 46 cms (about 18 inches); inner diameter: about 1-3 cms (about 0.5 inch)).
  • Gasoline boiling range feedstock from a catalytic cracking unit of a refinery was passed downwardly through the reactor at a flow rate of about 14 ml/hour, at a temperature of about 600°C and at atmospheric pressure (about 0 psig).
  • the formed reaction product exited the reactor tube and passed through several ice-cooled traps.

Landscapes

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

Abstract

On prépare une composition par un procédé consistant à mettre en contact une zéolite avec un composé contenant du zinc et un métal sélectionné dans le groupe formé par les éléments du groupe IIIA et du groupe VIB du tableau périodique des éléments. On utilise la composition ainsi obtenue comme catalyseur dans la conversion d'hydrocarbures en produits aromatiques.
PCT/US1999/020536 1998-09-16 1999-09-08 Zeolite amelioree WO2000015338A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU58150/99A AU5815099A (en) 1998-09-16 1999-09-08 An improved zeolite

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US15430198A 1998-09-16 1998-09-16
US09/154,301 1998-09-16

Publications (1)

Publication Number Publication Date
WO2000015338A1 true WO2000015338A1 (fr) 2000-03-23

Family

ID=22550805

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1999/020536 WO2000015338A1 (fr) 1998-09-16 1999-09-08 Zeolite amelioree

Country Status (2)

Country Link
AU (1) AU5815099A (fr)
WO (1) WO2000015338A1 (fr)

Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4548914A (en) * 1983-08-26 1985-10-22 Mobil Oil Corporation Zeolite catalysts of improved activity and para-selectivity
US4720602A (en) * 1986-09-08 1988-01-19 Mobil Oil Corporation Process for converting C2 to C12 aliphatics to aromatics over a zinc-activated zeolite
US4751339A (en) * 1987-01-23 1988-06-14 Mobil Oil Corporation Zeolite catalysis process for conversion of diene-containing olefins to aromatic hydrocarbons
US4849568A (en) * 1987-12-31 1989-07-18 Mobil Oil Corporation Stabilization of zinc on catalysts
US4983274A (en) * 1986-12-04 1991-01-08 Mobil Oil Corp. Shape selective crystalline silicate zeolite containing intermetallic component and use as catalyst in hydrocarbon conversions
US5002654A (en) * 1989-12-28 1991-03-26 Mobil Oil Corporation Reducing NOx emissions with zinc catalyst
US5349113A (en) * 1993-02-25 1994-09-20 Mobil Oil Corp. Shape selective hydrocarbon conversion over pre-selectivated, activated catalyst
US5476823A (en) * 1993-05-28 1995-12-19 Mobil Oil Corp. Method of preparation of ex situ selectivated zeolite catalysts for enhanced shape selective applications and method to increase the activity thereof
US5591421A (en) * 1994-07-11 1997-01-07 Chevron U.S.A. Inc. Zeolite SSZ-41
US5603821A (en) * 1989-07-07 1997-02-18 Chevron Research Company Low-aluminum boron beta zeolite
US5800696A (en) * 1996-11-12 1998-09-01 Phillips Petroleum Company Method for inhibiting the rate of coke formation during the zeolite catalyzed aromatization of hydrocarbons

Patent Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4548914A (en) * 1983-08-26 1985-10-22 Mobil Oil Corporation Zeolite catalysts of improved activity and para-selectivity
US4720602A (en) * 1986-09-08 1988-01-19 Mobil Oil Corporation Process for converting C2 to C12 aliphatics to aromatics over a zinc-activated zeolite
US4983274A (en) * 1986-12-04 1991-01-08 Mobil Oil Corp. Shape selective crystalline silicate zeolite containing intermetallic component and use as catalyst in hydrocarbon conversions
US4751339A (en) * 1987-01-23 1988-06-14 Mobil Oil Corporation Zeolite catalysis process for conversion of diene-containing olefins to aromatic hydrocarbons
US4849568A (en) * 1987-12-31 1989-07-18 Mobil Oil Corporation Stabilization of zinc on catalysts
US5603821A (en) * 1989-07-07 1997-02-18 Chevron Research Company Low-aluminum boron beta zeolite
US5002654A (en) * 1989-12-28 1991-03-26 Mobil Oil Corporation Reducing NOx emissions with zinc catalyst
US5349113A (en) * 1993-02-25 1994-09-20 Mobil Oil Corp. Shape selective hydrocarbon conversion over pre-selectivated, activated catalyst
US5574199A (en) * 1993-05-28 1996-11-12 Mobil Oil Corporation Para-selective aromatization process with ex situ selectivated zeolite catalyst
US5476823A (en) * 1993-05-28 1995-12-19 Mobil Oil Corp. Method of preparation of ex situ selectivated zeolite catalysts for enhanced shape selective applications and method to increase the activity thereof
US5675047A (en) * 1993-05-28 1997-10-07 Mobil Oil Corporation Method of preparation of ex situ selectivated zeolite catalysts for aromatic alkylation applications
US5591421A (en) * 1994-07-11 1997-01-07 Chevron U.S.A. Inc. Zeolite SSZ-41
US5800696A (en) * 1996-11-12 1998-09-01 Phillips Petroleum Company Method for inhibiting the rate of coke formation during the zeolite catalyzed aromatization of hydrocarbons

Also Published As

Publication number Publication date
AU5815099A (en) 2000-04-03

Similar Documents

Publication Publication Date Title
US6077984A (en) Process for making zeolite containing zinc borate composition, the composition and the use thereof in hydrocarbon conversion
US6080901A (en) Zeolite based catalyst containing zinc, boron and phosphorus and method of making such zeolite based catalyst
US5976356A (en) Acid treated zeolite containing boron and silver used as a catalyst for converting hydrocarbons and a method of making and using such catalyst
AU731283B2 (en) Improved catalyst composition useful for conversion of non-aromatic hydrocarbons to aromatics and light olefins
US5981417A (en) Method of making an improved catalyst containing an acid-treated zeolite, a boron component, and a zinc component, a product from such method, and the use thereof in the conversion of hydrocarbons
AU689414B1 (en) Process for aromatization of hydrocarbons
EP1060021B1 (fr) Composition servant a transformer des hydrocarbures et comprenant une zeolite siliconee traitee a l'acide qui contient du zinc et du bore et procede de fabrication de ce catalyseur
US6395949B1 (en) Acid treated zeolite containing phosphorus used as a catalyst in processes for converting hydrocarbons, and use of binary hydrocarbon mixtures as diluents in processes for converting hydrocarbons
US6034020A (en) Zeolite-based catalyst material, the preparation thereof and the use thereof
US6090990A (en) Method of making an improved catalyst containing zeolite treated with boron trichloride, the product from such method, and the use thereof in the conversion of hydrocarbons
US6048815A (en) Zeolite material, a method of making such improved zeolite material and the use thereof in the conversion of non-aromatic hydrocarbons to aromatics and light olefins
US5873994A (en) Process for aromatization of a cracked gasoline feedstock using a catalyst containing an acid leached zeolite and tin
AU696630B2 (en) Composition useful in converting non-aromatic hydrocarbons to aromatics and olefins
US6013849A (en) Toluene disproportionation process using a zeolite/tungsten carbide catalyst
WO2000015338A1 (fr) Zeolite amelioree
US6090272A (en) Process for converting a cracked gasoline using a zeolite-based catalyst material
AU705513B2 (en) Composition useful in converting non-aromatic hydrocarbons to aromatics and olefins
AU722437B2 (en) Composition useful in converting non-aromatic hydrocarbons to aromatics and olefins
WO1998057744A1 (fr) Composition a base de zeolite et son utilisation dans la transformation des hydrocarbures
MXPA99010178A (en) Improved catalyst composition useful for conversion of non-aromatic hydrocarbons to aromatics and light olefins
WO2000024509A1 (fr) Procede de fabrication d'un catalyseur aux zeolithes et utilisation de ce catalyseur dans un procede de conversion des hydrocarbures
US20020004623A1 (en) Zeolite material and the use thereof in the conversion of non-aromatic hydrocarbons to aromatics and light olefins
MXPA97008554A (en) Composition useful in the conversion of non-aromatic hydrocarbons to aromaticos and olefi

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AE AL AM AT AU AZ BA BB BG BR BY CA CH CN CR CU CZ DE DK DM EE ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MD MG MK MN MW MX NO NZ PL PT RO RU SD SE SG SI SK SL TJ TM TR TT UA UG US UZ VN YU ZA ZW

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): GH GM KE LS MW SD SL SZ UG ZW AM AZ BY KG KZ MD RU TJ TM AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE BF BJ CF CG CI CM GA GN GW ML MR NE SN TD TG

121 Ep: the epo has been informed by wipo that ep was designated in this application
REG Reference to national code

Ref country code: DE

Ref legal event code: 8642

122 Ep: pct application non-entry in european phase
CR1 Correction of entry in section i

Free format text: PAT. BUL. 09/2001 UNDER (30) REPLACE "GB" BY "EP"