WO2005123251A1 - Fluoride-modified zeolite catalyst and method - Google Patents

Fluoride-modified zeolite catalyst and method Download PDF

Info

Publication number
WO2005123251A1
WO2005123251A1 PCT/US2005/020213 US2005020213W WO2005123251A1 WO 2005123251 A1 WO2005123251 A1 WO 2005123251A1 US 2005020213 W US2005020213 W US 2005020213W WO 2005123251 A1 WO2005123251 A1 WO 2005123251A1
Authority
WO
WIPO (PCT)
Prior art keywords
catalyst
fluoride
zeolite catalyst
zsm
zeolite
Prior art date
Application number
PCT/US2005/020213
Other languages
French (fr)
Inventor
Ashim Kumar Ghosh
Pamela Harvey
Original Assignee
Saudi Basic Industries Corporation
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 Saudi Basic Industries Corporation filed Critical Saudi Basic Industries Corporation
Publication of WO2005123251A1 publication Critical patent/WO2005123251A1/en

Links

Classifications

    • 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
    • C07C2/54—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition of unsaturated hydrocarbons to saturated hydrocarbons or to hydrocarbons containing a six-membered aromatic ring with no unsaturation outside the aromatic ring
    • C07C2/64—Addition to a carbon atom of a six-membered aromatic ring
    • C07C2/66—Catalytic processes
    • 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
    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • 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
    • B01J37/22—Halogenating
    • B01J37/26—Fluorinating
    • 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
    • C07C2/54—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition of unsaturated hydrocarbons to saturated hydrocarbons or to hydrocarbons containing a six-membered aromatic ring with no unsaturation outside the aromatic ring
    • C07C2/64—Addition to a carbon atom of a six-membered aromatic ring
    • C07C2/66—Catalytic processes
    • C07C2/68—Catalytic processes with halides
    • 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
    • B01J35/615—
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Definitions

  • the invention relates generally to the alkylation of aromatic compounds and catalysts used for such reactions.
  • Para-xylene is a valuable substituted aromatic compound because of its great demand for its oxidation to terephthalic acid, a major component in forming polyester fibers and resins. It can be commercially produced from hydrotreating of naphtha (catalytic reforming), steam cracking of naphtha or gas oil, and toluene disproportionation.
  • Thermodynamic equilibrium compositions of o-, m-, and p-xylenes may be around 25, 50 and 25 mole%, respectively, at a reaction temperature of about 500 °C. Such toluene methylation may occur over a wide range of temperatures, however.
  • Para-xylene can be separated from mixed xylenes by a cycle of adsorption and isomerization. Byproducts such as C9+ and other aromatic products can be produced by secondary alkylation of the xylene product.
  • a significantly higher amount of p-xylene can be obtained in toluene methylation reaction if the catalyst has shape selective properties.
  • Shape selective properties can be obtained in modified zeolite catalysts by narrowing zeolite pore opening size, inactivation of the external surface of the zeolite or controlling zeolite acidity. Toluene methylation may occur over a modified ZSM-5 or ZSM-5-type zeolite catalyst giving xylene products containing significantly greater amounts of p- xylene than the thermodynamic concentration.
  • Phosphoric acid and other phosphorus-containing compounds have been used to modify ZSM-5 zeolite catalysts to provide shape selective properties.
  • a procedure of making a ZSM-5 catalyst by incorporating 5% phosphorus was described in which the catalyst was impregnated with a solution of diphenylphosphinous acid in toluene.
  • the ZSM-5 catalyst thus modified showed toluene methylation activity with 84-90% para isomer in the xylene product.
  • a catalyst was modified by incorporating 8.51% phosphorus from an aqueous phosphoric acid reagent. The catalyst showed p-xylene selectivity as high as 97%, however, the catalyst showed a decreasing activity within hours due to coke deposition.
  • ZSM-5-type zeolite catalysts after treating with a fluoride-containing compound.
  • ZSM-5-type is meant to refer to those zeolites that are isostructurally the same as ZSM-5 zeolites. Additionally, the expressions "ZSM-5" and “ZSM-5-type” may also be used herein interchangeably to encompass one another and should not be construed in any limiting sense.
  • the ZSM-5 zeolite and its preparation is described in U.S. Patent No. 3,702,886, which is herein incorporated by reference.
  • the ZSM-5 zeolite may include those having a silica/alumina molar ratio of from 25 or more prior to modification, more particularly a silica/alumina molar ratio of from about 25 to about 1000 prior to modification.
  • the modified catalyst in toluene methylation, for which the modified zeolite is particularly well suited, it will be apparent to those skilled in the art that the catalyst may have application for use in other types of reactions, such as transalkylation and other aromatic alkylation reactions. In particular, the catalyst of the invention may have application to such reactions to provide increased selectivity for para-isomer in mixed dialkylated aromatic products.
  • the fluorided-zeolite catalyst may be made by incorporating fluoride in zeolite by vapor phase fluoridation or liquid impregnation. See A.K. Ghosh and R.A. Kydd, Fluorine-Promoted Catalysts, Catal. Rev.-Sci. Eng., 1985, pp. 539-589 Vol. 27(4), which is herein incorporated by reference.
  • vapor phase fluoridation the zeolite is maintained in contact with vapors of a fluoride-containing compound at a temperature between 100 °C and 500 °C.
  • Impregnation is carried out by saturating the zeolite with a solution containing an appropriate amount of fluoride-containing compound and then evaporating the liquid.
  • the fluoride-containing compound may include F 2 , HF, BF 3 , NH 4 F, NH 4 BF 4 , CF 4 , CHF 3 , CH 2 F 2 , CF 3 COOH, CF 3 OH, CF 3 OCF 3 , CF3CH2OH, SF 6 , SO2F2, SOF 2 or NH 4 SiF 6 .
  • One or more different fluoride-containing compounds may be used to treat the zeolite catalyst, either simultaneously, as a single mixture or sequentially.
  • the amount of fluoride used may provide a fluoride content of the treated catalyst of from 0.05 wt% F or more as measured by using ASTM E-442 (Oxygen Flask Combustion and Ion-Selective Electrode) method.
  • the starting zeolite may be an NH - or H-fdrm ZSM-5 zeolite, which may be in the form of a powder or any other form.
  • the zeolite catalyst may be prepared by treating a slurry of the zeolite with an aqueous solution of the fluoride-containing compound. All liquid in the zeolite slurry with the fluoride containing compound may be evaporated at a temperature between room temperature to about 70 °C, although higher temperatures may be used. The slurry may also be stirred or agitated during this step to ensure uniform treatment. The slurry may be heated until all liquids are evaporated.
  • the fluoride-modified zeolite catalyst may be used unbound or be bound with a binder.
  • suitable binders include such materials as alumina, clay, and silica. Those techniques used for preparing the bound catalyst are well known in the art.
  • the catalyst, bound or unbound, may be calcined at a temperature between 400 °C and 570 °C in an environment containing oxygen, typically air.
  • the resulting fluoride-treated ZSM-5 zeolite catalyst may show a slight decrease in both BET surface area (SA) and total pore volume (PN), as measured by ⁇ 2 adsorption, compared to the same untreated ZSM-5 zeolite catalyst.
  • SA BET surface area
  • PN total pore volume
  • the fluoride treated catalyst may have a BET surface area of 350 m 2 /g or less, more particularly 330 m 2 /g or less, and still more particularly 300 m 2 /g or less, and may have a pore volume of about 0.25 ml/g or less.
  • the modified catalyst may be contacted with an appropriate feed under alkylation reaction conditions to carry out aromatic alkylation.
  • alkylation reactions for which the invention has application include toluene alkylation with an alkylating agent such as methanol.
  • alkylation reactions may include transalkylation, such as gas phase toluene disproportionation in the presence of hydrogen to produce benzene and mixed xylenes.
  • the reactor pressure for toluene methylation or other aromatic alkylation may vary, but typically ranges from about 10 to about 1000 psig.
  • the reaction may be carried in a variety of different reactors that are commonly used for carrying out aromatic alkylation reactions. Single or multiple reactors in series and/or parallel are suitable for carrying out the toluene methylation or other aromatic alkylation reactions.
  • the modified catalyst is useful in toluene methylation for preparing a xylene product from a feed of toluene and methanol that has increased selectivity for p-xylene.
  • water may be introduced with the feed in an amount of at least 0.1 moles water per mole of toluene/methanol feed, as described in US. Patent Application Serial No. 10/675,780, filed September 30, 2003, which is herein incorporated by reference.
  • a hydrogen cofeed is also used. The hydrogen may be used in an amount of at least 1.0 mole per mole of toluene/methanol feed.
  • the fluoride-treated zeolite catalyst may exhibit at least a 50% increase in selectivity for para-isomers in aromatic alkylation reactions compared to the same zeolite catalyst without such treatment under similar aromatic alkylation reaction conditions.
  • ZSM-5-type zeolite catalysts modified in accordance with the invention are used in toluene methylation, a mixed xylene product having a p-xylene content of 50%, 60%, 70% or more by total moles of xylene may be obtained.
  • the following examples further illustrate the invention. EXAMPLES CATALYST PREPARATION Catalyst A-D
  • each catalyst a slurry of HZSM-5 zeolite powder having a SiO 2 /Ai 2 ⁇ 3 mole ratio of about 280 in deionized water was prepared in a beaker.
  • the beaker was placed on a hot plate and the zeolite suspension was stirred using a magnetic stir bar.
  • Hydrofluoric acid (40% in water) was slowly added to the slurry.
  • the HF solution was further diluted by adding water prior to adding to the zeolite slurry.
  • the temperature of the zeolite suspension (or slurry) was maintained at ⁇ 70°C. All liquid was evaporated at a temperature below 70 °C.
  • a series of catalysts A-D were prepared using the above technique by varying the amount of hydrofluoric acid with respect to the amount of starting HZSM- 5 powder.
  • the amount of zeolite, water (to form slurry), aqueous HF and additional water (to dilute HF further, if any) are shown Table 1.
  • the BET surface area and total pore volume (measured by N 2 adsorption) for catalysts A-D are presented in Table 1 below. Comparative Catalyst E
  • a non-modified HZSM-5 zeolite catalyst (Catalyst E) was also tested.
  • the starting material was an NH 4 -ZSM-5 zeolite powder having a SiO 2 /Al 2 O 3 mole ratio of 280.
  • the zeolite powder was calcined at 530 °C under air for 10 hr and then pressed and sized using 20 and 40 mesh screens for use in a reactor for toluene methylation reaction.
  • BET surface area and total pore volume (measured by N 2 adsorption) for catalyst E are presented in Table 1 below. Comparative Catalyst F
  • a H 2 SO 4 treated NH 4 -ZSM-5 zeolite catalyst (Catalyst F) was also tested.
  • the starting material was an NH 4 -ZSM-5 zeolite powder having a SiO 2 /Al 2 O 3 mole ratio of 280.
  • a zeolite slurry was made by adding 25.33 g of the zeolite and 50 ml water. The slurry was heated and continuously stirred. 10.41 g of H 2 SO 4 (95-98%) was added to the zeolite slurry when its temperature was about 90 °C. All liquid was evaporated by heating the slurry at 90-100 °C.
  • the acid modified zeolite was dried at 90 °C and then calcined at a temperature between 500 and 530 °C under air for 10 hr.
  • the calcined zeolite was then pressed and sized using 20 and 40 mesh screens for use in a reactor for toluene methylation reaction.
  • BET surface area and total pore volume (measured by N 2 adsorption) for catalyst F are presented in Table 1 below.
  • the catalysts A-E as referenced in Table 1 and prepared as described above, were used in toluene methylation reactions. The reactions were each carried out in a fixed bed, continuous flow type reactor. In each case, the catalyst used was dried by slowly raising the catalyst bed temperature (about 5 °C/min) to 200 °C under hydrogen (H 2 ) flow for at least one hour. A premixed toluene and methanol feed (molar ratio 2/1) was added to the reactor at 200 °C and the catalyst bed inlet temperature was increased to about 500 °C.
  • the fluoride-modified HZSM-5 zeolite showed an increase in p-xylene selectivity.
  • fluoride-modified HZSM-5 Catalysts A, B, C and D showed a 55%, 70%, 71% and 72% p-xylene content, respectively, in total xylenes compared to 31% p-xylene for non-modified ZSM-5 Catalyst E, when used in toluene methylation under the same reaction conditions.
  • increases in selectivity for para-isomers by as much as 80%, 100% or more compared to the same zeolite catalyst without such treatment used under similar aromatic alkylation reaction conditions can be obtained.
  • the sulfuric acid-modified Catalyst F did not show a significant increase in p-xylene selectivity, as compared to the non-modified Catalyst E
  • the fluoride-modified zeolite showed a reduction in BET surface area, while the total pore volume remained generally unchanged compared to the non-modified zeolite.
  • the BET surface area of non-fluorided ZSM-5 catalyst (E) is 375 m 2 /g, and that of fluorided ZSM-5 catalyst (D) 280 m 2 /g.

Abstract

A method of modifying a ZSM-5-type zeolite catalyst to increase selectivity of the catalyst for para-isomers in aromatic alkylation reactions is provided. The method includes contacting a ZSM-5-type zeolite catalyst with a fluoride-containing compound. The fluoride-containing zeolite catalyst can be used in aromatic alkylation to provide di-alkyl aromatic products. A method of preparing a xylene product is also accomplished by providing a fluoride-treated ZSM-5-type zeolite catalyst within a reactor. The fluoride-treated ZSM-5 zeolite catalyst is contacted with a toluene/methanol feed under reaction conditions conditions suitable for toluene methylation to form a xylene product containing at least 50% para-xylene by total mixed xylenes.

Description

FLUORIDE-MODIFIED ZEOLITE CATALYST AND METHOD
TECHNICAL FIELD
[0001] The invention relates generally to the alkylation of aromatic compounds and catalysts used for such reactions.
BACKGROUND
[0002] Para-xylene is a valuable substituted aromatic compound because of its great demand for its oxidation to terephthalic acid, a major component in forming polyester fibers and resins. It can be commercially produced from hydrotreating of naphtha (catalytic reforming), steam cracking of naphtha or gas oil, and toluene disproportionation.
[0003] Alkylation of toluene with mefhanol, which is also known as toluene methylation, has been used in laboratory studies to produce para-xylene. Toluene methylation has been known to occur over acidic catalyst, particularly over zeolite or zeolite-type catalyst. In particular, ZSM-5-type zeolite, zeolite Beta and silicaaluminophosphate (SAPO) catalysts have been used for this process. Generally, a thermodynamic equilibrium mixture of ortho (o)-, fneta (m)- and para (p)-xylenes can be formed from the methylation of toluene, as is illustrated by the reaction below.
Figure imgf000003_0001
TOLUENE
Figure imgf000003_0002
[0004] Thermodynamic equilibrium compositions of o-, m-, and p-xylenes may be around 25, 50 and 25 mole%, respectively, at a reaction temperature of about 500 °C. Such toluene methylation may occur over a wide range of temperatures, however. Para-xylene can be separated from mixed xylenes by a cycle of adsorption and isomerization. Byproducts such as C9+ and other aromatic products can be produced by secondary alkylation of the xylene product.
[0005] A significantly higher amount of p-xylene can be obtained in toluene methylation reaction if the catalyst has shape selective properties. Shape selective properties can be obtained in modified zeolite catalysts by narrowing zeolite pore opening size, inactivation of the external surface of the zeolite or controlling zeolite acidity. Toluene methylation may occur over a modified ZSM-5 or ZSM-5-type zeolite catalyst giving xylene products containing significantly greater amounts of p- xylene than the thermodynamic concentration. [0006] Phosphoric acid and other phosphorus-containing compounds have been used to modify ZSM-5 zeolite catalysts to provide shape selective properties. U.S. Patent No. 6,504,072, for instance, discloses the treatment of ZSM-5 zeolite catalyst with phosphorus to control the reduction of diffusivity and pore volume prior to severe steaming to provide a para-selective catalyst. U.S. Patent No. 4,554,394 discusses the treatment of ZSM-5 zeolites with a vapor phase organophosphorus reagent to provide para-selective properties. In Kaeding, et al, Selective Alkylation of Toluene with Methanol to Produce para-Xylene, Journal of Catalysis, Vol. 67, pp. 159-174 (1981), a procedure of making a ZSM-5 catalyst by incorporating 5% phosphorus was described in which the catalyst was impregnated with a solution of diphenylphosphinous acid in toluene. The ZSM-5 catalyst thus modified showed toluene methylation activity with 84-90% para isomer in the xylene product. In another procedure, a catalyst was modified by incorporating 8.51% phosphorus from an aqueous phosphoric acid reagent. The catalyst showed p-xylene selectivity as high as 97%, however, the catalyst showed a decreasing activity within hours due to coke deposition.
[0007] Unfortunately, there are a number of technical hurdles for toluene methylation to be commercially successful and improvements are needed.
DETAILED DESCRIPTION
[0008] It has been found that increased selectivity for para-isomers of dialkylated aromatic products can be obtained over ZSM-5-type zeolite catalysts after treating with a fluoride-containing compound. As used herein, the expression "ZSM-5-type" is meant to refer to those zeolites that are isostructurally the same as ZSM-5 zeolites. Additionally, the expressions "ZSM-5" and "ZSM-5-type" may also be used herein interchangeably to encompass one another and should not be construed in any limiting sense.
[0009] The ZSM-5 zeolite and its preparation is described in U.S. Patent No. 3,702,886, which is herein incorporated by reference. In the present invention, the ZSM-5 zeolite may include those having a silica/alumina molar ratio of from 25 or more prior to modification, more particularly a silica/alumina molar ratio of from about 25 to about 1000 prior to modification.
[0010] Although specific reference is made to the use of the modified catalyst in toluene methylation, for which the modified zeolite is particularly well suited, it will be apparent to those skilled in the art that the catalyst may have application for use in other types of reactions, such as transalkylation and other aromatic alkylation reactions. In particular, the catalyst of the invention may have application to such reactions to provide increased selectivity for para-isomer in mixed dialkylated aromatic products.
[0011] As used herein, catalytic activity for toluene methylation can be expressed as the % moles of toluene converted with respect to the moles of toluene fed and can be defined as: Mole% Toluene Conversion = (T; - T0/ T x 100 (2) where, Tj is the number of moles of toluene fed and T0 is the number of moles toluene unreacted. As used herein, selectivity for total xylenes may be expressed as: Mole% Total Xylene Selectivity = (Xtχ/Ti-T0) x 100 (3) where, Xtx is the number of moles of total (o-, m- or p-) xylenes in the product. As used herein, selectivity for p-xylene may be expressed as: Mole% p-Xylene Selectivity = (Xp/Xtχ) x 100 • (4) where, Xp is the number of moles of p-xylene. [0012] The fluorided-zeolite catalyst may be made by incorporating fluoride in zeolite by vapor phase fluoridation or liquid impregnation. See A.K. Ghosh and R.A. Kydd, Fluorine-Promoted Catalysts, Catal. Rev.-Sci. Eng., 1985, pp. 539-589 Vol. 27(4), which is herein incorporated by reference. In vapor phase fluoridation, the zeolite is maintained in contact with vapors of a fluoride-containing compound at a temperature between 100 °C and 500 °C. Impregnation is carried out by saturating the zeolite with a solution containing an appropriate amount of fluoride-containing compound and then evaporating the liquid. The fluoride-containing compound may include F2, HF, BF3, NH4F, NH4BF4, CF4, CHF3, CH2F2, CF3COOH, CF3OH, CF3OCF3, CF3CH2OH, SF6, SO2F2, SOF2 or NH4SiF6. One or more different fluoride-containing compounds may be used to treat the zeolite catalyst, either simultaneously, as a single mixture or sequentially. The amount of fluoride used may provide a fluoride content of the treated catalyst of from 0.05 wt% F or more as measured by using ASTM E-442 (Oxygen Flask Combustion and Ion-Selective Electrode) method.
[0013] The starting zeolite may be an NH - or H-fdrm ZSM-5 zeolite, which may be in the form of a powder or any other form. The zeolite catalyst may be prepared by treating a slurry of the zeolite with an aqueous solution of the fluoride-containing compound. All liquid in the zeolite slurry with the fluoride containing compound may be evaporated at a temperature between room temperature to about 70 °C, although higher temperatures may be used. The slurry may also be stirred or agitated during this step to ensure uniform treatment. The slurry may be heated until all liquids are evaporated.
[0014] The fluoride-modified zeolite catalyst may be used unbound or be bound with a binder. Examples of suitable binders include such materials as alumina, clay, and silica. Those techniques used for preparing the bound catalyst are well known in the art. The catalyst, bound or unbound, may be calcined at a temperature between 400 °C and 570 °C in an environment containing oxygen, typically air. [0015] The resulting fluoride-treated ZSM-5 zeolite catalyst may show a slight decrease in both BET surface area (SA) and total pore volume (PN), as measured by Ν2 adsorption, compared to the same untreated ZSM-5 zeolite catalyst. The fluoride treated catalyst may have a BET surface area of 350 m2/g or less, more particularly 330 m2/g or less, and still more particularly 300 m2/g or less, and may have a pore volume of about 0.25 ml/g or less.
[0016] The modified catalyst may be contacted with an appropriate feed under alkylation reaction conditions to carry out aromatic alkylation. Examples of alkylation reactions for which the invention has application include toluene alkylation with an alkylating agent such as methanol. Other alkylation reactions may include transalkylation, such as gas phase toluene disproportionation in the presence of hydrogen to produce benzene and mixed xylenes.
[0017[ The reactor pressure for toluene methylation or other aromatic alkylation may vary, but typically ranges from about 10 to about 1000 psig. [0018] The reaction may be carried in a variety of different reactors that are commonly used for carrying out aromatic alkylation reactions. Single or multiple reactors in series and/or parallel are suitable for carrying out the toluene methylation or other aromatic alkylation reactions.
[0019] In particular, the modified catalyst is useful in toluene methylation for preparing a xylene product from a feed of toluene and methanol that has increased selectivity for p-xylene. In such reactions, water may be introduced with the feed in an amount of at least 0.1 moles water per mole of toluene/methanol feed, as described in US. Patent Application Serial No. 10/675,780, filed September 30, 2003, which is herein incorporated by reference. A hydrogen cofeed is also used. The hydrogen may be used in an amount of at least 1.0 mole per mole of toluene/methanol feed. [0020] The fluoride-treated zeolite catalyst may exhibit at least a 50% increase in selectivity for para-isomers in aromatic alkylation reactions compared to the same zeolite catalyst without such treatment under similar aromatic alkylation reaction conditions. When ZSM-5-type zeolite catalysts modified in accordance with the invention are used in toluene methylation, a mixed xylene product having a p-xylene content of 50%, 60%, 70% or more by total moles of xylene may be obtained. [0021] The following examples further illustrate the invention. EXAMPLES CATALYST PREPARATION Catalyst A-D
[0022] To form each catalyst, a slurry of HZSM-5 zeolite powder having a SiO2/Ai2θ3 mole ratio of about 280 in deionized water was prepared in a beaker. The beaker was placed on a hot plate and the zeolite suspension was stirred using a magnetic stir bar. Hydrofluoric acid (40% in water) was slowly added to the slurry. In certain cases, the HF solution was further diluted by adding water prior to adding to the zeolite slurry. The temperature of the zeolite suspension (or slurry) was maintained at <70°C. All liquid was evaporated at a temperature below 70 °C. The zeolite was then dried at about 90 °C at least for 4 hours and then was calcined in air at approximately 510 °C for 10 hrs. The HF treated and calcined zeolite was then pressed to form pellets and was crushed and sized using 20 and 40 mesh screens. [0023] A series of catalysts A-D were prepared using the above technique by varying the amount of hydrofluoric acid with respect to the amount of starting HZSM- 5 powder. The amount of zeolite, water (to form slurry), aqueous HF and additional water (to dilute HF further, if any) are shown Table 1. The BET surface area and total pore volume (measured by N2 adsorption) for catalysts A-D are presented in Table 1 below. Comparative Catalyst E
[0024] A non-modified HZSM-5 zeolite catalyst (Catalyst E) was also tested. The starting material was an NH4-ZSM-5 zeolite powder having a SiO2/Al2O3 mole ratio of 280. The zeolite powder was calcined at 530 °C under air for 10 hr and then pressed and sized using 20 and 40 mesh screens for use in a reactor for toluene methylation reaction. BET surface area and total pore volume (measured by N2 adsorption) for catalyst E are presented in Table 1 below. Comparative Catalyst F
[0025] A H2SO4 treated NH4-ZSM-5 zeolite catalyst (Catalyst F) was also tested. The starting material was an NH4-ZSM-5 zeolite powder having a SiO2/Al2O3 mole ratio of 280. A zeolite slurry was made by adding 25.33 g of the zeolite and 50 ml water. The slurry was heated and continuously stirred. 10.41 g of H2SO4 (95-98%) was added to the zeolite slurry when its temperature was about 90 °C. All liquid was evaporated by heating the slurry at 90-100 °C. The acid modified zeolite was dried at 90 °C and then calcined at a temperature between 500 and 530 °C under air for 10 hr. The calcined zeolite was then pressed and sized using 20 and 40 mesh screens for use in a reactor for toluene methylation reaction. BET surface area and total pore volume (measured by N2 adsorption) for catalyst F are presented in Table 1 below.
TABLE 1 Catalyst Acid Treatment Wt% F SA, m2/g PV, ml/g Zeolite, g Water3, ml Acid", g Water0, ml A 4.02 47 1.24 0 <0.037 329.0 0.243 B 8.00 191 2.43 191 0.047 298.3 0.230 C 5.06 10 2.01 0 0.088 312.7 0.233 D 5.02 10 4.00 0 0.206 279.6 0.232 E None 375.0 0.244 F 25.33 50 10.41d 0 368.4 0.249
"Amount of water added to make zeolite slurry; Unless stated otherwise acid is 40% HF (in water); °Amount of water added to 40% HF to further dilute prior to adding to zeolite slurry; dH2S04 (95-98%).
EXAMPLES 1-7
[0026] The catalysts A-E, as referenced in Table 1 and prepared as described above, were used in toluene methylation reactions. The reactions were each carried out in a fixed bed, continuous flow type reactor. In each case, the catalyst used was dried by slowly raising the catalyst bed temperature (about 5 °C/min) to 200 °C under hydrogen (H2) flow for at least one hour. A premixed toluene and methanol feed (molar ratio 2/1) was added to the reactor at 200 °C and the catalyst bed inlet temperature was increased to about 500 °C. The liquid hourly space velocity (LHSN) based on toluene/methanol feed was maintained at about 31 hr" and cofeed of H2 gas was fed and maintained to provide a H2/HC molar ratio of about 0.1. Water was added to the hydrocarbon (HC) feed and was vaporized prior to introduction into the reactor. The H2O/HC molar ratio was about 0.65 and the reactor pressure was about 20 psig. The following results were obtained, as presented in Table 2 below. Table 2. Catalysts for Toluene Methylation
EXAMPLES 1 2 4 5 6 7 Catalyst ID A B C D E F Catalytic Performance Test Catalyst Bed Inlet Temp/°C 500 503 503 506 500 504 Reactor Inlet Pressure, psig 21 23 21 22 23 22 LHSVa 31 31 31 31 30 30 Cofeed H20, mole/mole HC 0.65 0.65 0.65 0.65 0.66 0.66 Feed Cofeed H2, mole/mole HC 0.11 0.11 0.11 0.11 0.11 0.11 Feed Product Distribution, wt%b
C5- 1.34 2.21 1.48 3.34 1.71 3.34
Dimethylether 0.00 0.01 0.01 0.01 0.00 0
Methanol 0.00 0.44 0.37 0.01 0.53 0.48
Benzene 0.00 0 0.00 0 0.46 0.41
Toluene 62.21 65.37 66.42 65.00 61.44 64.16
EthylBenzene 0.00 0 0.00 0.07 0.00 0
Para-Xylene (PX) 18.12 21.66 20.26 20.61 10.00 9.33
Meta-Xylene (MX) 10.00 6.23 5.56 5.37 16.01 13.63
Ortho-Xylene (OX) 4.57 3.13 2.91 2.71 6.44 5.52
EthylToluene 0.27 0.31 0.33 0.33 0.78 1.03
TrimethylBenzene 3.07 0.26 2.34 2.18 2.40 1.92
C10+ 0.41 0.38 0.33 0.36 0.23 0.20
Toluene Conv., mole% 33.41 29.7 29.05 29.45 33.37 30.03
Total Xylenes Selectivity, % 89.72 97.02 90.56 90.67 89.33 88.81
PX in Total Xylenes, % 55.42 69.84 70.52 71.84 30.82 35.02
"Based on toluene and methanol feed. Excluding H20 and normalized to 100%.
[0027] The fluoride-modified HZSM-5 zeolite showed an increase in p-xylene selectivity. For example, fluoride-modified HZSM-5 Catalysts A, B, C and D showed a 55%, 70%, 71% and 72% p-xylene content, respectively, in total xylenes compared to 31% p-xylene for non-modified ZSM-5 Catalyst E, when used in toluene methylation under the same reaction conditions. This represents at least a 50% increase in selectivity for para-isomers in aromatic alkylation reactions for the fluoride-treated catalyst compared to the same zeolite catalyst without such treatment under similar aromatic alkylation reaction conditions. As shown, increases in selectivity for para-isomers by as much as 80%, 100% or more compared to the same zeolite catalyst without such treatment used under similar aromatic alkylation reaction conditions can be obtained.
[0028] The sulfuric acid-modified Catalyst F did not show a significant increase in p-xylene selectivity, as compared to the non-modified Catalyst E [0029] Structurally, the fluoride-modified zeolite showed a reduction in BET surface area, while the total pore volume remained generally unchanged compared to the non-modified zeolite. The BET surface area of non-fluorided ZSM-5 catalyst (E) is 375 m2/g, and that of fluorided ZSM-5 catalyst (D) 280 m2/g. [0030] While the invention has been shown in only some of its forms, it should be apparent to those skilled in the art that it is not so limited, but is susceptible to various changes and modifications without departing from the scope of the invention. Accordingly, it is appropriate that the appended claims be construed broadly and in a manner consistent with the scope of the invention.

Claims

CLAIMSWe claim:
1. A method of modifying a ZSM-5-type zeolite catalyst to increase selectivity of the catalyst for para-isomers in aromatic alkylation reactions, the method comprising contacting a ZSM-5-type zeolite catalyst with a fluoride-containing compound.
2. The method of claim 1, wherein the zeolite is contacted with a fluoride- containing compound through at least one of vapor phase fluoridation and liquid impregnation.
3. The method of claim 1 , wherein the fluoride-containing compound is selected from a group consisting of F2, HF, BF3, NH4F, NH4BF4, CF4, CHF3, CH2F23 CF3COOH, CF3OH, CF3OCF3, CF3CH2OH, SF6, SO2F2, SOF2 and NH4SiF6.
4. The method of claim 1, wherein the fluoride -treated zeolite catalyst exhibits at least a 50% increase in selectivity for para-isomers in aromatic alkylation reactions compared to the same zeolite catalyst without such treatment under similar aromatic alkylation reaction conditions.
5. The method of claim 1 , wherein the ZSM-5-type zeolite catalyst has a silica to alumina ratio of from 25 to 1000.
6. The method of claim 1 , wherein the fluoride-treated zeolite catalyst has a BET surface area that is at least 10% less than that of the same zeolite catalyst without such treatment.
7. The method of claim 1 , wherein the fluoride-treated zeolite catalyst has a BET surface area of 350 m2/g or less.
8. The method of claim 1, wherein the fluoride-treated zeolite provides at least 50% para-xylene selectivity of mixed-xylenes when used in toluene methylation reactions.
9. The method of claim 1 , wherein the fluoride-treated zeolite catalyst contains at least 0.05 wt% F as measured by ASTM E-442.
10. A catalyst for use in aromatic alkylation comprising a fluoride-containing ZSM-5-type zeolite catalyst.
11. The catalyst of claim 10, wherein the zeolite catalyst contains at least 0.05 wt% F as measured by ASTM E-442.
12. The catalyst of claim 10, wherein the zeolite catalyst has a BET surface area of 350 m2/g or less.
13. The catalyst of claim 12, wherein the zeolite catalyst has a pore volume of about 25ml/g or less.
14. The catalyst of claim 10, wherein the zeolite catalyst provides at least 50% para-xylene selectivity of mixed-xylenes when used in toluene methylation reactions.
15. A method of preparing an alkyl aromatic product comprising: providing a fluoride-treated ZSM-5-type zeolite catalyst within a reactor; and contacting the catalyst with an aromatic hydrocarbon and an alkylating agent under reaction conditions suitable for aromatic alkylation to form a di-alkyl aromatic product.
16. The method of claim 15, wherein the fluoride-treated ZSM-5 zeolite catalyst is treated with a fluoride-containing compound selected from a group consisting of F2, HF, BF3, NH4F, NH4BF4, CF4, CHF3, CH2F2, CF3COOH, CF3OH, CF3OCF3, CF3CH2OH, SF6, SO2F2, SOF2 andNH4SiF6.
17. The method of claim 16, wherein the fluoride-containing compound is hydrofluoric acid (HF).
18. The method of claim 15, wherein the ZSM-5-type zeolite catalyst has a silica to alumina ratio of from 25 to 1000.
19. The method of claim 15, wherein the fluoride-treated zeolite has a BET surface area that is at least 10% less than that of the same zeolite catalyst without such treatment.
20. The method of claim 15, wherein the di-alkyl aromatic product contains at least 40% para-isomers of the di-alkyl aromatic product by total mixed-di- alkyl aromatic product when used in aromatic alkylation reactions.
21. A method of preparing a xylene product comprising: providing a fluoride-treated ZSM-5-type zeolite catalyst within a reactor; and contacting the catalyst with toluene/methanol feed under reaction conditions suitable for toluene methylation to form a xylene product containing at least 50% para-xylene by total mixed xylenes.
PCT/US2005/020213 2004-06-09 2005-06-08 Fluoride-modified zeolite catalyst and method WO2005123251A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US86402104A 2004-06-09 2004-06-09
US10/864,021 2004-06-09

Publications (1)

Publication Number Publication Date
WO2005123251A1 true WO2005123251A1 (en) 2005-12-29

Family

ID=35461384

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2005/020213 WO2005123251A1 (en) 2004-06-09 2005-06-08 Fluoride-modified zeolite catalyst and method

Country Status (2)

Country Link
US (2) US7105713B2 (en)
WO (1) WO2005123251A1 (en)

Families Citing this family (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7368410B2 (en) 2005-08-03 2008-05-06 Saudi Basic Industries Corporation Zeolite catalyst and method of preparing and use of zeolite catalyst
US8846559B2 (en) 2008-11-03 2014-09-30 Saudi Basic Industries Corporation Stable shape-selective catalyst for aromatic alkylation and methods of using and preparing
US8062987B2 (en) 2009-10-05 2011-11-22 Saudi Basic Industries Corporation Phosphorus-containing zeolite catalysts and their method of preparation
US8466080B2 (en) 2010-09-15 2013-06-18 Uop Llc Catalysts, processes for preparing the catalysts, and processes for transalkylating aromatic hydrocarbon compounds
US9238599B2 (en) * 2011-12-07 2016-01-19 Exxonmobil Chemical Patents Inc. Alkylaromatic process
US9278342B2 (en) 2012-07-02 2016-03-08 Saudi Basic Industries Corporation Method of modifying a phosphorus-containing zeolite catalyst
US8969643B2 (en) 2013-05-23 2015-03-03 Saudi Basic Industries Corporation Method for conversion of aromatic hydrocarbons
US9783462B2 (en) 2013-09-10 2017-10-10 Saudi Basic Industries Corporation Toluene methylation with transalkylation of heavy aromatics
US9364815B2 (en) 2013-11-07 2016-06-14 Saudi Basic Industries Corporation Method of preparing an alumina catalyst support and catalyst for dehydrogenation reactions, and its use
US11208365B2 (en) 2016-12-20 2021-12-28 Uop Llc Processes and apparatuses for methylation of aromatics in an aromatics complex
US11130719B2 (en) 2017-12-05 2021-09-28 Uop Llc Processes and apparatuses for methylation of aromatics in an aromatics complex
CN110156040A (en) * 2018-02-12 2019-08-23 中国石油天然气股份有限公司 ZSM-5 molecular sieve and preparation method thereof
US11130720B2 (en) 2018-03-23 2021-09-28 Uop Llc Processes for methylation of aromatics in an aromatics complex
CN109180422B (en) * 2018-09-18 2021-04-06 山东东岳化工有限公司 Method for preparing tetrafluoroethylene and co-producing hexafluoropropylene by catalytic cracking of trifluoromethane
CN110013875A (en) * 2019-05-28 2019-07-16 河南师范大学 A kind of preparation method of fluorine richness molecular sieve FER
CN114073976B (en) * 2020-08-10 2023-04-07 中国科学院大连化学物理研究所 Modified ZSM-5 molecular sieve and preparation method and application thereof
CN114713209B (en) * 2021-01-06 2024-04-05 浙江蓝天环保高科技股份有限公司 Fluoride modified adsorbent and method for purifying crude hexafluoro-1,3-butadiene

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4520219A (en) * 1982-09-24 1985-05-28 Idemitsu Kosan Company Limited Process for the production of pseudocumene or durene

Family Cites Families (132)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6444A (en) * 1849-05-08 Machinery for cutting soles of boots and shoes
US681168A (en) * 1901-03-06 1901-08-20 Benjamin J Graham Acetylene-gas generator.
US3965207A (en) 1975-01-06 1976-06-22 Mobil Oil Corporation Selective production of para-xylene
CA1169038A (en) 1980-11-04 1984-06-12 Koji Sumitani Crystalline aluminosilicate zeolites and process for production thereof
US4704495A (en) 1980-12-29 1987-11-03 Mobil Oil Corporation Catalytic conversions using shape selective metallic catalysts
US5254767A (en) 1982-04-30 1993-10-19 Mobil Oil Corp. Highly siliceous porous crystalline material and its use in conversion of oxygenates
US5336478A (en) 1982-04-30 1994-08-09 Mobil Oil Corp. Highly siliceous porous crystalline material
US5248841A (en) 1982-04-30 1993-09-28 Mobil Oil Corporation Hydrocarbon conversion with ZSM-22 zeolite
US4902406A (en) 1982-04-30 1990-02-20 Mobil Oil Corporation Synthesis of zeolite ZSM-22
US5254770A (en) 1982-09-01 1993-10-19 Mobil Oil Corp. Isomerization of aromatic compounds over ZSM-22 zeolite
US4973781A (en) 1982-11-17 1990-11-27 Mobil Oil Corporation Zeolite ZSM-57 and catalysis therewith
US4914067A (en) 1983-05-02 1990-04-03 Uop Catalytic cracking catalysts and cracking process using mixed catalyst system
US4548914A (en) 1983-08-26 1985-10-22 Mobil Oil Corporation Zeolite catalysts of improved activity and para-selectivity
DE3332563A1 (en) 1983-09-09 1985-03-28 Basf Ag, 6700 Ludwigshafen METHOD FOR DESULFURING H (ARROW DOWN) 2 (ARROW DOWN) GASES
US4891197A (en) 1983-12-19 1990-01-02 Mobil Oil Corporation Silicophosphoaluminates and related crystalline oxides
US4694114A (en) 1984-01-11 1987-09-15 Mobil Oil Corporation Process for isomerizing alkyl aromatic hydrocarbons utilizing ZSM-23 zeolite and a hydrogenation/dehydrogenation metal
US4623633A (en) 1984-01-17 1986-11-18 Union Oil Company Of California Shock calcined aluminosilicate zeolites
US4758328A (en) 1984-01-17 1988-07-19 Union Oil Company Of California Shock calcined aluminosilicate zeolites
US4716135A (en) 1984-04-09 1987-12-29 Mobil Oil Corporation Organophosphorus-modified zeolites and method of preparation
US4638106A (en) 1984-07-13 1987-01-20 Exxon Research & Engineering Co. Two stage process for improving the catalyst life of zeolites in the synthesis of lower olefins from alcohols and their ether derivatives
US4912073A (en) 1984-07-16 1990-03-27 Mobil Oil Corp. Larger pore molecular sieves of controlled activity
US5047141A (en) 1984-07-16 1991-09-10 Mobil Oil Corporation Larger pore molecular sieves of controlled activity
US4873067A (en) 1984-08-21 1989-10-10 Mobil Oil Corporation Zeolite ZSM-57
IL73146A (en) 1984-10-02 1988-11-15 Yeda Res & Dev Catalysts and process for the production of hydrocarbons and substitution of hydrocarbons
US4891467A (en) 1984-10-15 1990-01-02 Amoco Corporation Selective synthesis of pseudocumene and durene
US4623530A (en) 1985-02-20 1986-11-18 United States Steel Corporation Crystalline magnesia-silica composites and process for producing same
US4721827A (en) 1985-02-20 1988-01-26 Aristech Chemical Corportion Crystalline magnesia-silica composites and process for producing same
US4727209A (en) 1985-06-11 1988-02-23 Uop Inc. Hydrocarbon alkylation processes employing a phosphorus-modified alumina composite
US4665251A (en) 1985-06-12 1987-05-12 Mobil Oil Corporation Aromatization reactions with zeolites containing phosphorus oxide
US4590321A (en) 1985-06-12 1986-05-20 Mobil Oil Corporation Aromatization reactions with zeolites containing phosphorus oxide
US4673767A (en) 1985-11-25 1987-06-16 Amoco Corporation AMS-1B crystalline borosilicate molecular sieve-based catalyst compositions and process for toluene alkylation
US4670616A (en) 1985-11-25 1987-06-02 Amoco Corporation AMS-1B crystalline borosilicate molecular sieve-based catalyst compositions and process for toluene methylation
US4695666A (en) 1985-12-09 1987-09-22 Uop Inc. Phosphorus-containing alumina catalyst for the isomerization of aromatics
US4746763A (en) 1987-04-22 1988-05-24 Uop Inc. Process for producing aromatic compounds from C2 -C6 aliphatic hydrocarbons
US4943545A (en) 1987-06-08 1990-07-24 Mobil Oil Corporation Activation of zeolites
US4761513A (en) 1987-07-01 1988-08-02 Uop Inc. Temperature control for aromatic alkylation process
FR2623423B1 (en) 1987-11-23 1990-03-30 Centre Nat Rech Scient NOVEL ZEOLITH-BASED CATALYSTS MODIFIED BY ALKALINE ELEMENTS IN METALLIC FORM, THEIR PREPARATION AND THEIR APPLICATION TO THE ALKYLATION OF ALKYL-AROMATIC DERIVATIVES
US4935574A (en) 1988-03-29 1990-06-19 E. I. Du Pont De Nemours And Company Preparation of para-xylene by toluene methylation
FR2629444B1 (en) 1988-04-01 1990-12-07 Rhone Poulenc Chimie SILICA AND GERMANIUM OXIDE ZEOLITES AND PROCESS FOR THE SYNTHESIS THEREOF
US4891930A (en) 1988-04-04 1990-01-09 Schaefer Alan W Apparatus and process for applying a cover, to a round hay bale
US4847223A (en) 1988-04-08 1989-07-11 Concordia University Superacidic catalysts for low temperature conversion of aqueous ethanol to ethylene
US4861930A (en) 1988-09-28 1989-08-29 Uop Combination process for the conversion of a C2 -C6 aliphatic hydrocarbon
GB8829923D0 (en) 1988-12-22 1989-02-15 Ici Plc Zeolites
US5178748A (en) 1988-12-22 1993-01-12 Imperial Chemical Industries Catalytic reactions using zeolites
US5124299A (en) 1989-08-02 1992-06-23 E. I. Du Pont De Nemours And Company Catalysis using blends of perfluorinated ion-exchange polymers with perfluorinated diluents
US5233102A (en) 1989-08-02 1993-08-03 E. I. Du Pont De Nemours And Company Olefin hydration
US5094995A (en) 1989-08-02 1992-03-10 E. I. Du Pont De Nemours And Company Supported perfluorinated ion-exchange polymers
US5105047A (en) 1989-08-02 1992-04-14 E. I. Du Pont De Nemours And Company Catalysis using blends of perfluorinated ion-exchange polymers with perfluorinated diluents
US5043502A (en) 1990-03-16 1991-08-27 Uop Production of xylenes from light aliphatic hydrocarbons via dehydrocyclodimerization and methylation
US5173461A (en) 1990-03-21 1992-12-22 Mobil Oil Corporation Toluene disproportionation catalyst
US5534239A (en) 1990-03-23 1996-07-09 Societe Nationale Elf Aquitaine Process for the synthesis of a silica enriched crystalline aluminosilicate having the offretite structure, the aluminosilicate obtained and its use as a catalyst for the conversion of hydrocarbons
GB9013859D0 (en) 1990-06-21 1990-08-15 Ici Plc Zeolites
GB9013916D0 (en) 1990-06-22 1990-08-15 Ici Plc Zeolites
EP0466545A1 (en) 1990-06-29 1992-01-15 Rhone-Poulenc Chimie Zeolites based on silica and oxides of tetravalent elements, method for their synthesis and their use
EP0473509A3 (en) 1990-08-29 1992-03-18 Rhone-Poulenc Chimie Method for preparation of zeolites based on silica and, possibly, oxides of tetravalent elements
US5348643A (en) 1991-03-12 1994-09-20 Mobil Oil Corp. Catalytic conversion with improved catalyst
US5456821A (en) 1991-03-12 1995-10-10 Mobil Oil Corp. Catalytic conversion with improved catalyst
US5110776A (en) 1991-03-12 1992-05-05 Mobil Oil Corp. Cracking catalysts containing phosphate treated zeolites, and method of preparing the same
US5366948A (en) 1991-03-12 1994-11-22 Mobil Oil Corp. Catalyst and catalytic conversion therewith
US5231064A (en) 1991-03-12 1993-07-27 Mobil Oil Corp. Cracking catalysts comprising phosphorus and method of preparing and using the same
US5171921A (en) 1991-04-26 1992-12-15 Arco Chemical Technology, L.P. Production of olefins
US5321183A (en) 1992-03-12 1994-06-14 Mobil Oil Corp. Process for the regioselective conversion of aromatics to para-disubstituted benzenes
US5571768A (en) 1992-03-12 1996-11-05 Mobil Oil Corporation Zeolite functionalized with organosiliceous groups
US5498814A (en) 1992-03-12 1996-03-12 Mobil Oil Corp. Regioselective methylation of toluene to para-xylene
US5475179A (en) 1992-03-12 1995-12-12 Mobil Oil Regioselective production of para-dialkyl benzenes
US5516736A (en) 1992-03-12 1996-05-14 Mobil Oil Corp. Selectivating zeolites with organosiliceous agents
EP0568913A3 (en) 1992-05-03 1995-03-22 Dalian Chemical Physics Inst Process for the conversion of methanol to light olefins and catalyst used for such process.
US5318696A (en) 1992-12-11 1994-06-07 Mobil Oil Corporation Catalytic conversion with improved catalyst catalytic cracking with a catalyst comprising a large-pore molecular sieve component and a ZSM-5 component
US5294578A (en) 1992-12-23 1994-03-15 Mobil Oil Corp. Supported acid catalysts, their preparation and use in organic compound conversion
US5365003A (en) 1993-02-25 1994-11-15 Mobil Oil Corp. Shape selective conversion of hydrocarbons over extrusion-modified molecular sieve
US5349113A (en) 1993-02-25 1994-09-20 Mobil Oil Corp. Shape selective hydrocarbon conversion over pre-selectivated, activated catalyst
CN1034223C (en) 1993-03-29 1997-03-12 中国石油化工总公司 Cracking catalyst for processing low-carbon olefines
US5378670A (en) 1993-04-16 1995-01-03 W. R. Grace & Co.-Conn. Phosphorus zeolites/molecular sieves
US5362697A (en) 1993-04-26 1994-11-08 Mobil Oil Corp. Synthetic layered MCM-56, its synthesis and use
US5430213A (en) 1993-05-06 1995-07-04 Exxon Chemical Patents Inc. Process for producing 1,4-dienes
US5698756A (en) 1993-05-28 1997-12-16 Mobil Oil Corporation Toluene alkylation with ethylene to produce para-ethyloluene
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
US5523510A (en) 1993-08-30 1996-06-04 Texaco Inc. Treated bound ferrierite zeolites for skeletal isomerization of n-olefins to iso-olefins
US5563310A (en) 1993-09-14 1996-10-08 Mobil Oil Corporation Toluene alkylation with methanol
DE69421288T2 (en) 1993-10-18 2000-02-03 Mobil Oil Corp POROUS SYNTHETIC CRYSTALLINE MATERIAL MCM-58, WHOSE SYNTHESIS AND USE
EP0655277A1 (en) 1993-11-01 1995-05-31 Csir Amorphous aluminosilicate catalyst
US5457078A (en) 1993-11-29 1995-10-10 Mobil Oil Corporation Manufacture of improved zeolite Beta catalyst
US5561095A (en) 1994-03-31 1996-10-01 Exxon Chemical Patents Inc. Supported lewis acid catalysts for hydrocarbon conversion reactions
AU2131095A (en) 1994-03-31 1995-10-23 Exxon Chemical Patents Inc. Supported lewis acid catalysts derived from superacids useful for hydrocarbon conversion reactions
AU2199695A (en) 1994-03-31 1995-10-23 Exxon Chemical Patents Inc. Supported lewis acid catalysts for hydrocarbon conversion reactions
US5576256A (en) 1994-05-23 1996-11-19 Intevep, S.A. Hydroprocessing scheme for production of premium isomerized light gasoline
US5689024A (en) 1994-06-03 1997-11-18 Mobil Oil Corporation Use of crystalline SUZ-9
US5939597A (en) * 1994-11-10 1999-08-17 Mobil Oil Corporation Fluid bed process for para-xylene production
US5646314A (en) 1994-11-16 1997-07-08 Arco Chemical Technology, L.P. Process for titanium silicalite-catalyzed epoxidation
US5573746A (en) 1995-06-06 1996-11-12 Mobil Oil Corporation Zeolite synthesis with amino acid directing agents
US6060633A (en) * 1995-10-20 2000-05-09 Chen; Frank Joung-Yei Supported Lewis acid catalysts derived from superacids useful for hydrocarbon conversion reactions
US5811613A (en) 1996-04-05 1998-09-22 Indian Petrochemicals Corporation Limited Process for the production of para-diethylbenzene
CA2204461C (en) * 1996-05-14 2006-07-04 Thomas V. Harris Process for producing an alkylated, non-oxygen-containing aromatic hydrocarbon
US6048816A (en) * 1996-10-02 2000-04-11 Mobil Oil Corporation Catalyst and process for converting methanol to hydrocarbons
EP0888817B1 (en) * 1996-11-27 2004-11-10 Idemitsu Kosan Co., Ltd. Process for producing a catalyst for cleaning exhaust gas
US5925586A (en) * 1996-12-31 1999-07-20 Exxon Chemical Patents, Inc. Phosphorus modified small pore molecular sieve catalysts, and their use in the production of light olefins
CN1059133C (en) * 1997-03-24 2000-12-06 中国石油化工总公司 Phosphorus containing molecular sieve with MFI structure
US5905051A (en) 1997-06-04 1999-05-18 Wu; An-Hsiang Hydrotreating catalyst composition and processes therefor and therewith
US5898089A (en) * 1997-07-09 1999-04-27 Phillips Petroleum Company Hydrocarbon aromatization process using a zeolite
US6034283A (en) * 1997-07-18 2000-03-07 Asahi Kasei Kogyo Kabushiki Kaisha Process for production of cyclic alcohols
US6047544A (en) * 1997-08-20 2000-04-11 Nissan Motor Co., Ltd. Engine exhaust gas purification catalyst and exhaust gas purifier
JP3741548B2 (en) * 1997-09-17 2006-02-01 中国石油化工集団公司 Pencil-type molecular sieve-containing composition and preparation method thereof
US6423879B1 (en) * 1997-10-02 2002-07-23 Exxonmobil Oil Corporation Selective para-xylene production by toluene methylation
US6211104B1 (en) * 1997-10-15 2001-04-03 China Petrochemical Corporation Catalyst for catalytic pyrolysis process for the production of light olefins and the preparation thereof
US6040257A (en) * 1997-11-07 2000-03-21 Phillips Petroleum Company Hydrocarbon conversion catalyst composition and processes therefor and therewith
WO1999028031A1 (en) * 1997-12-03 1999-06-10 Exxon Chemical Patents Inc. Catalyst comprising a zeolite partially coated with a second zeolite, its use for hydrocarbon conversion
CN1069682C (en) * 1997-12-23 2001-08-15 中国石油化工总公司 Layer-column clay catalyst for heavy-oil catalytic thermal cracking and its preparation
US6395664B1 (en) * 1998-02-19 2002-05-28 Uop Llc Process for reactivating a deactivated dehydrocyclodimerization catalyst with water
US6074975A (en) * 1998-03-03 2000-06-13 Phillips Petroleum Company Hydrocarbon conversion catalyst composition and processes therefor and therewith
US6417421B1 (en) * 1998-03-03 2002-07-09 Phillips Petroleum Company Hydrocarbon conversion catalyst composition and process therefor and therewith
US6080303A (en) * 1998-03-11 2000-06-27 Exxon Chemical Patents, Inc. Zeolite catalyst activity enhancement by aluminum phosphate and phosphorus
US5955641A (en) * 1998-03-16 1999-09-21 Chevron Chemical Company Llc Method of making dimethylnaphthalenes
US6288298B1 (en) * 1998-05-26 2001-09-11 Exxonmobil Chemical Patents Inc. Naphtha cracking utilizing new catalytic silicoaluminophosphates having an AEL structure
US6100437A (en) * 1998-07-10 2000-08-08 Albemarle Corporation Alkylation process of alkyl-benzene with olefin using a sodium-and-potassium catalyst
US6124227A (en) * 1998-08-28 2000-09-26 Phillips Petroleum Company Hydrocarbon conversion catalyst composition and processes therefor and therewith
ES2224702T3 (en) * 1998-09-28 2005-03-01 Bp Corporation North America Inc. PROCEDURE FOR THE PRODUCTION OF OLEFINS USING A PENTASIL ZAOLITA BASED CATALYST.
JP3868128B2 (en) * 1998-10-05 2007-01-17 新日本石油株式会社 Gas oil hydrodesulfurization apparatus and method
JP3871449B2 (en) * 1998-10-05 2007-01-24 新日本石油株式会社 Hydrodesulfurization method of light oil
CN1096296C (en) * 1998-11-13 2002-12-18 中国石油化工集团公司 Hydrocracking catalyst for producing middle distillate and its preparation method
US6090274A (en) * 1998-12-29 2000-07-18 Phillips Petroleum Company Hydrotreating catalyst composition and processes therefor and therewith
US6699811B1 (en) * 1999-05-05 2004-03-02 Exxon Mobil Chemical Patents Inc. Tailored zeolite bound zeolite catalyst and its use for hydrocarbon conversion
US6388156B1 (en) * 1999-05-14 2002-05-14 Exxonmobil Chemical Patents Inc. Direct selective synthesis of para-xylene by reacting an aromatic compound with a methylating agent formed from CO, Co2 and H2
JP3859940B2 (en) * 1999-08-06 2006-12-20 日産自動車株式会社 Exhaust gas purification catalyst and method for producing the same
US6187982B1 (en) * 1999-10-15 2001-02-13 Mobil Oil Corporation Process for converting dienes and oxygenates to para-xylene and light olefins
US6726834B2 (en) * 1999-10-22 2004-04-27 Intevep, S.A. Process for catalytic cracking of a hydrocarbon feed with a MFI aluminisilcate composition
EP1116775A1 (en) * 2000-01-12 2001-07-18 Akzo Nobel N.V. Catalyst composition with high efficiency for the production of light olefins
US6773694B1 (en) * 1999-12-22 2004-08-10 Uop Llc Process for synthesizing molecular sieves
JP3489048B2 (en) * 2000-02-01 2004-01-19 日産自動車株式会社 Exhaust gas purification catalyst
US6506954B1 (en) * 2000-04-11 2003-01-14 Exxon Mobil Chemical Patents, Inc. Process for producing chemicals from oxygenate
JP3904802B2 (en) * 2000-04-26 2007-04-11 日産自動車株式会社 Exhaust gas purification catalyst and method for producing the same
DE60122243T2 (en) * 2000-06-28 2007-06-28 Ict Co. Ltd. purifying catalyst
TWI240716B (en) * 2000-07-10 2005-10-01 Bp Corp North America Inc Pressure swing adsorption process for separating paraxylene and ethylbenzene from mixed C8 aromatics

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4520219A (en) * 1982-09-24 1985-05-28 Idemitsu Kosan Company Limited Process for the production of pseudocumene or durene

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
GHOSH ET AL: "An infrared study of the effect HF treatment on the acidity of ZSM-5.", ZEOLITES., vol. 10, 1990, pages 766 - 771, XP002988566 *

Also Published As

Publication number Publication date
US20060189477A1 (en) 2006-08-24
US7446069B2 (en) 2008-11-04
US20050277795A1 (en) 2005-12-15
US7105713B2 (en) 2006-09-12

Similar Documents

Publication Publication Date Title
US7105713B2 (en) Preparation of alkyl-aromatic products
US7279608B2 (en) Toluene methylation process with increased methanol selectivity
US7560608B2 (en) Method of preparing a xylene product
EP1725329B1 (en) Selective zeolite catalyst modification
US7576026B2 (en) Method of hydrothermal treatment of phosphorus-modified zeolite catalyts
EP2498907B1 (en) Phosphorus-containing zeolite catalysts and their method of preparation
US20080176736A1 (en) Phosphorus-Containing Zeolite Catalyst
KR20080019012A (en) Zeolite catalyst and method
KR101287257B1 (en) Toluene methylation process
EP2509934A2 (en) Aromatic alkylation process

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BW BY BZ CA CH CN CO CR CU CZ DE DK DM DZ EC EE EG ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KM KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NA NG NI NO NZ OM PG PH PL PT RO RU SC SD SE SG SK SL SM SY TJ TM TN TR TT TZ UA UG US UZ VC VN YU ZA ZM ZW

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): BW GH GM KE LS MW MZ NA SD SL SZ TZ UG ZM ZW AM AZ BY KG KZ MD RU TJ TM AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LT LU MC NL PL PT RO SE SI SK TR BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG

121 Ep: the epo has been informed by wipo that ep was designated in this application
NENP Non-entry into the national phase

Ref country code: DE

WWW Wipo information: withdrawn in national office

Country of ref document: DE

122 Ep: pct application non-entry in european phase