US20030004383A1 - Selective para-xylene production by toluene methylation - Google Patents

Selective para-xylene production by toluene methylation Download PDF

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US20030004383A1
US20030004383A1 US10/141,159 US14115902A US2003004383A1 US 20030004383 A1 US20030004383 A1 US 20030004383A1 US 14115902 A US14115902 A US 14115902A US 2003004383 A1 US2003004383 A1 US 2003004383A1
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catalyst
crystalline material
toluene
porous crystalline
temperature
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Stephen Brown
Mark Mathias
Robert Ware
David Olson
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ExxonMobil Oil Corp
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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
    • 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
    • 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
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • 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
    • 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
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/26—After treatment, characterised by the effect to be obtained to stabilize the total catalyst structure
    • 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
    • B01J2229/42—Addition of matrix or binder particles
    • 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
    • C07C2529/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
    • 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

  • para-xylene is of particular value since it is useful in the manufacture of terephthalic acid which is an intermediate in the manufacture of synthetic fibers.
  • Equilibrium mixtures of xylene isomers either alone or in further admixture with ethylbenzene generally contain only about 24 wt. % para-xylene and separation of p-xylene from such mixtures has typically required superfractionation and multistage refrigeration steps. Such processes have involved high operation costs and resulted in only limited yields. There is therefore a continuing need to provide processes which are highly selective for the production of p-xylene.
  • U.S. Pat. Nos. 3,965,209 to Butter et al. and 4,067,920 to Kaeding teach processes for producing para-xylene in low conversion and high selectivity by reaction of toluene with methanol over a zeolite having a Constraint Index of 1-12, such as ZSM-5.
  • the zeolite is steamed at a temperature of 250-1000° C. for 0.5-100 hours to reduce the acid activity of the zeolite, as measured by its alpha activity, to less than 500 and preferably from in excess of zero to less than 20.
  • U.S. Pat. No. 4,001,346 to Chu relates to a process for the selective production of para-xylene by methylation of toluene in the presence of a catalyst comprising a crystalline aluminosilicate zeolite which has undergone prior treatment to deposit a coating of between about 15 and about 75 wt. % of coke thereon.
  • U.S. Pat. No. 4,097,543 to Haag et al. relates to a process for the selective production of para-xylene (up to about 77%) by disproportionation of toluene in the presence of a crystalline aluminosilicate catalyst which has undergone precoking to deposit a coating of at least about 2 wt. % coke thereon.
  • U.S. Pat. No. 4,380,685 to Chu relates to a process for para-selective aromatics alkylation, including the methylation of toluene, over a zeolite, such as ZSM-5, which has a constraint index of 1-12 and which has been combined with phosphorus and a metal selected from iron and cobalt.
  • Chu indicates that the catalyst can optionally be modified (without specifying the effect of the modification) by steaming at a temperature of 250-1000° C., preferably 400-700° C. for 0.5-100 hours, preferably 1-24 hours.
  • U.S. Pat. No. 4,554,394 to Forbus and Kaeding teach the use of phosphorus-treated zeolite catalysts for enhancing para-selectivity in aromatics conversion processes.
  • U.S. Pat. No. 4,623,633 to Young relates to the use of thermal shock calcination of aluminosilicates to produce up to 66% para-xylene selectivity.
  • porous crystalline materials having specific and closely defined diffusion characteristics exhibit improved selectivity for the alkylation of toluene with methanol such that the xylene product contains at least about 90% of the para-isomer at per-pass toluene conversions of at least about 15%.
  • the invention resides in a process for the selective production of para-xylene which comprises reacting toluene with methanol under alkylation conditions in the presence of a catalyst comprising a porous crystalline material having a Diffusion Parameter for 2,2-dimethylbutane of about 0.1-15 sec ⁇ 1 when measured at a temperature of 120° C. and a 2,2-dimethylbutane pressure of 60 torr (8 kPa).
  • the porous crystalline material has a Diffusion Parameter of about 0.5-10 sec ⁇ 1 .
  • the catalyst contains at least one oxide modifier and more preferably at least one oxide modifier selected from oxides of elements of Groups IIA, IIIA, IIIB, IVA, VA, VB and VIA of the Periodic Table.
  • the oxide modifier is selected from oxides of boron, magnesium, calcium, lanthanum and most preferably phosphorus.
  • the catalyst contains about 0.05 to about 20, more preferably about 0.1 to about 10 and most preferably about 0.1 to about 5, wt % of the oxide modifier based on elemental modifier.
  • the catalyst has an alpha value less than 50 and preferably less than 10.
  • the invention resides in a method for producing a catalyst for use in the selective production of para-xylene by reacting toluene with methanol, said method comprising the steps of:
  • step (b) contacting the material of step (a) with steam at a temperature of at least about 950° C. to reduce the Diffusion Parameter thereof for 2,2-dimethylbutane to about 0.1-15 sec ⁇ 1 when measured at a temperature of 120° C. and a 2,2-dimethylbutane pressure of 60 torr (8 kPa), the micropore volume of the steamed material being at least 50% of the unsteamed material.
  • said porous crystalline material used in step (a) comprises an aluminosilicate zeolite having a silica to alumina molar ratio of at least 250.
  • the present invention provides a process for alkylating toluene with methanol to selectively produce p-xylene in high yield and with a high per-pass conversion of toluene.
  • the process employs a catalyst which comprises a porous crystalline material having a Diffusion Parameter for 2,2-dimethylbutane of about 0.1-15 sec ⁇ 1 , and preferably 0.5-10 sec ⁇ 1 , when measured at a temperature of 120° C. and a 2,2-dimethylbutane pressure of 60 torr (8 kPa).
  • the Diffusion Parameter of a particular porous crystalline material is defined as D/r 2 ⁇ 10 6 , wherein D is the diffusion coefficient (cm 2 /sec) and r is the crystal radius (cm).
  • the required diffusion parameters can be derived from sorption measurements provided the assumption is made that the plane sheet model describes the diffusion process.
  • Q/Q ⁇ where Q ⁇ is the equilibrium sorbate loading
  • t is the time (sec) required to reach the sorbate loading Q.
  • the porous crystalline material employed in the process of the invention is preferably a medium-pore size aluminosilicate zeolite.
  • Medium pore zeolites are generally defined as those having a pore size of about 5 to about 7 Angstroms, such that the zeolite freely sorbs molecules such as n-hexane, 3-methylpentane, benzene and p-xylene.
  • Another common definition for medium pore zeolites involves the Constraint Index test which is described in U.S. Pat. No. 4,016,218, which is incorporated herein by reference.
  • medium pore zeolites have a Constraint Index of about 1-12, as measured on the zeolite alone without the introduction of oxide modifiers and prior to any steaming to adjust the diffusivity of the catalyst.
  • SAPOs silicoaluminophosphates
  • Suitable medium pore zeolites include ZSM-5, ZSM-11, ZSM-12, ZSM-22, ZSM-23, ZSM-35, ZSM48, and MCM-22, with ZSM-5 and ZSM-11 being particularly preferred.
  • Zeolite ZSM-5 and the conventional preparation thereof are described in U.S. Pat. No. 3,702,886, the disclosure of which is incorporated herein by reference.
  • Zeolite ZSM-11 and the conventional preparation thereof are described in U.S. Pat. No. 3,709,979, the disclosure of which is incorporated herein by reference.
  • Zeolite ZSM-12 and the conventional preparation thereof are described in U.S. Pat. No. 3,832,449, the disclosure of which is incorporated herein by reference.
  • Zeolite ZSM-23 and the conventional preparation thereof are described in U.S. Pat. No. 4,076,842, the disclosure of which is incorporated herein by reference.
  • Zeolite ZSM-35 and the conventional preparation thereof are described in U.S. Pat. No.
  • the zeolite employed in the process of the invention is ZSM-5 having a silica to alumina molar ratio of at least 250, as measured prior to any treament of the zeolite to adjust its diffusivity.
  • the medium pore zeolites described above are preferred for the process of the invention since the size and shape of their pores favor the production of p-xylene over the other xylene isomers.
  • conventional forms of these zeolites have Diffusion Parameter values in excess of the 0.1-15 sec ⁇ 1 range required for the process of the invention.
  • the required diffusivity for the present catalyst can be achieved by severely steaming the catalyst so as to effect a controlled reduction in the micropore volume of the catalyst to not less than 50%, and preferably 50-90%, of that of the unsteamed catalyst. Reduction in micropore volume is derived by measuring the n-hexane adsorption capacity of the catalyst, before and after steaming, at 90° C. and 75 torr n-hexane pressure.
  • Steaming of the porous crystalline material is effected at a temperature of at least about 950° C., preferably about 950 to about 1075° C., and most preferably about 1000 to about 1050° C. for about 10 minutes to about 10 hours, preferably from 30 minutes to 5 hours.
  • the porous crystalline material prior to steaming, with at least one oxide modifier, preferably selected from oxides of the elements of Groups IIA, IIIA, IIIB, IVA, VA, VB and VIA of the Periodic Table (IUPAC version).
  • said at least one oxide modifier is selected from oxides of boron, magnesium, calcium, lanthanum and most preferably phosphorus.
  • the total amount of oxide modifier present in the catalyst may be between about 0.05 and about 20 wt. %, and preferably is between about 0.1 and about 10 wt. %, based on the weight of the final catalyst.
  • modifier includes phosphorus
  • incorporation of modifier in the catalyst of the invention is conveniently achieved by the methods described in U.S. Pat. Nos. 4,356,338, 5,110,776, 5,231,064 and 5,348,643, the entire disclosures of which are incorporated herein by reference.
  • Treatment with phosphorus-containing compounds can readily be accomplished by contacting the porous crystalline material, either alone or in combination with a binder or matrix material, with a solution of an appropriate phosphorus compound, followed by drying and calcining to convert the phosphorus to its oxide form.
  • Contact with the phosphorus-containing compound is generally conducted at a temperature of about 25° C. and about 125° C. for a time between about 15 minutes and about 20 hours.
  • the concentration of the phosphorus in the contact mixture may be between about 0.01 and about 30 wt. %.
  • the porous crystalline material may be dried and calcined to convert the phosphorus to an oxide form. Calcination can be carried out in an inert atmosphere or in the presence of oxygen, for example, in air at a temperature of about 150 to 750° C., preferably about 300 to 500° C., for at least 1 hour, preferably 3-5 hours.
  • Representative phosphorus-containing compounds which may be used to incorporate a phosphorus oxide modifier into the catalyst of the invention include derivatives of groups represented by PX 3 , RPX 2 , R 2 PX, R 3 P, X 3 PO, (XO) 3 PO, (XO) 3 P, R 3 P ⁇ O, R 3 P ⁇ S, RPO 2 , RPS 2 , RP(O)(OX) 2 , RP(S)(SX) 2 , R 2 P(O)OX, R 2 P(S)SX, RP(OX) 2 , RP(SX) 2 , ROP(OX) 2 , RSP(SX) 2 , (RS) 2 PSP(SR) 2 , and (RO) 2 POP(OR) 2 , where R is an alkyl or aryl, such as phenyl radical, and X is hydrogen, R, or halide.
  • R is an alkyl or aryl, such as phenyl radical
  • X
  • These compounds include primary, RPH 2 , secondary, R 2 PH, and tertiary, R 3 P, phosphines such as butyl phosphine, the tertiary phosphine oxides, R 3 PO, such as tributyl phosphine oxide, the tertiary phosphine sulfides, R 3 PS, the primary, RP(O)(OX) 2 , and secondary, R 2 P(O)OX, phosphonic acids such as benzene phosphonic acid, the corresponding sulfur derivatives such as RP(S)(SX) 2 and R 2 P(S)SX, the esters of the phosphonic acids such as dialkyl phosphonate, (RO) 2 P(O)H, dialkyl alkyl phosphonates, (RO) 2 P(O)R, and alkyl dialkylphosphinates, (RO)P(O)R 2 ; phosphinous acids, R 2 POX, such
  • Corresponding sulfur derivatives may also be employed including (RS) 2 P(S)H, (RS) 2 P(S)R, (RS)P(S)R 2 , R 2 PSX, (RS)P(SX) 2 , (RS) 2 PSX, (RS) 3 P, (RS)PR 2 , and (RS) 2 PR.
  • phosphite esters include trimethylphosphite, triethylphosphite, diisopropylphosphite, butylphosphite, and pyrophosphites such as tetraethylpyrophosphite.
  • the alkyl groups in the mentioned compounds preferably contain one to four carbon atoms.
  • Suitable phosphorus-containing compounds include ammonium hydrogen phosphate, the phosphorus halides such as phosphorus trichloride, bromide, and iodide, alkyl phosphorodichloridites, (RO)PCI 2 , dialkylphosphorochloridites, (RO) 2 PCI, dialkylphosphinochloroidites, R 2 PCI, alkyl alkylphosphonochloridates, (RO)(R)P(O)CI, dialkyl phosphinochloridates, R 2 P(O)CI, and RP(O)CI 2 .
  • Applicable corresponding sulfur derivatives include (RS)PCI 2 , (RS) 2 PCI, (RS)(R)P(S)CI, and R 2 P(S)CI.
  • Particular phosphorus-containing compounds include ammonium phosphate, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, diphenyl phosphine chloride, trimethylphosphite, phosphorus trichloride, phosphoric acid, phenyl phosphine oxychloride, trimethylphosphate, diphenyl phosphinous acid, diphenyl phosphinic acid, diethylchlorothiophosphate, methyl acid phosphate, and other alcohol-P 2 O 5 reaction products.
  • Representative boron-containing compounds which may be used to incorporate a boron oxide modifier into the catalyst of the invention include boric acid, trimethylborate, boron oxide, boron sulfide, boron hydride, butylboron dimethoxide, butylboric acid, dimethylboric anhydride, hexamethylborazine, phenyl boric acid, triethylborane, diborane and triphenyl boron.
  • Representative magnesium-containing compounds include magnesium acetate, magnesium nitrate, magnesium benzoate, magnesium propionate, magnesium 2-ethylhexoate, magnesium carbonate, magnesium formate, magnesium oxylate, magnesium bromide, magnesium hydride, magnesium lactate, magnesium laurate, magnesium oleate, magnesium palmitate, magnesium salicylate, magnesium stearate and magnesium sulfide.
  • Representative calcium-containing compounds include calcium acetate, calcium acetylacetonate, calcium carbonate, calcium chloride, calcium methoxide, calcium naphthenate, calcium nitrate, calcium phosphate, calcium stearate and calcium sulfate.
  • Representative lanthanum-containing compounds include lanthanum acetate, lanthanum acetylacetonate, lanthanum carbonate, lanthanum chloride, lanthanum hydroxide, lanthanum nitrate, lanthanum phosphate and lanthanum sulfate.
  • the porous crystalline material employed in the process of the invention may be combined with a variety of binder or matrix materials resistant to the temperatures and other conditions employed in the process.
  • binder or matrix materials resistant to the temperatures and other conditions employed in the process.
  • Such materials include active and inactive materials such as clays, silica and/or metal oxides such as alumina. The latter may be either naturally occurring or in the form of gelatinous precipitates or gels including mixtures of silica and metal oxides.
  • Inactive materials suitably serve as diluents to control the amount of conversion in a given process so that products can be obtained economically and orderly without employing other means for controlling the rate of reaction.
  • These materials may be incorporated into naturally occurring clays, e.g., bentonite and kaolin, to improve the crush strength of the catalyst under commercial operating conditions.
  • Said materials i.e., clays, oxides, etc., function as binders for the catalyst. It is desirable to provide a catalyst having good crush strength because in commercial use it is desirable to prevent the catalyst from breaking down into powder-like materials.
  • These clay and/or oxide binders have been employed normally only for the purpose of improving the crush strength of the catalyst.
  • Naturally occurring clays which can be composited with the porous crystalline material include the montmorillonite and kaolin family, which families include the subbentonites, and the kaolins commonly known as Dixie, McNamee, Georgia and Florida clays or others in which the main mineral constituent is halloysite, kaolinite, dickite, nacrite, or anauxite. Such clays can be used in the raw state as originally mined or initially subjected to calcination, acid treatment or chemical modification.
  • the porous crystalline material can be composited with a porous matrix material such as silica-alumina, silica-magnesia, silica-zirconia, silica-thoria, silica-beryllia, silica-titania as well as ternary compositions such as silica-alumina-thoria, silica-alumina-zirconia silica-alumina-magnesia and silica-magnesia-zirconia.
  • a porous matrix material such as silica-alumina, silica-magnesia, silica-zirconia, silica-thoria, silica-beryllia, silica-titania as well as ternary compositions such as silica-alumina-thoria, silica-alumina-zirconia silica-alumina-magnesia and silica-magnesia-zirconia.
  • porous crystalline material and inorganic oxide matrix vary widely, with the content of the former ranging from about 1 to about 90% by weight and more usually, particularly when the composite is prepared in the form of beads, in the range of about 2 to about 80 wt. % of the composite.
  • the binder material comprises silica or a kaolin clay.
  • the porous crystalline material may be combined with a binder in the form of a fluidized bed catalyst.
  • This fluidized bed catalyst may comprise clay in the binder thereof, and may be formed by a spray-drying process to form catalyst particles having a particle size of 20-200 microns.
  • the catalyst of the invention may optionally be precoked.
  • the precoking step is preferably carried out by initially utilizing the uncoked catalyst in the toluene methylation reaction, during which coke is deposited on the catalyst surface and thereafter controlled within a desired range, typically from about 1 to about 20 wt. % and preferably from about 1 to about 5 wt. %, by periodic regeneration by exposure to an oxygen-containing atmosphere at an elevated temperature.
  • One of the advantages of the catalyst described herein is its ease of regenerability.
  • the catalyst after the catalyst accumulates coke as it catalyzes the toluene methylation reaction, it can easily be regenerated by burning off a controlled amount of coke in a partial combustion atmosphere in a regenerator at temperatures in the range of from about 400 to about 700° C.
  • the coke loading on the catalyst may thereby be reduced or substantially eliminated in the regenerator.
  • the regeneration step may be controlled such that the regenerated catalyst returning to the toluene methylation reaction zone is coke-loaded at the desired level.
  • the present process may suitably be carried out in fixed, moving, or fluid catalyst beds. If it is desired to continuously control the extent of coke loading, moving or fluid bed configurations are preferred. With moving or fluid bed configurations, the extent of coke loading can be controlled by varying the severity and/or the frequency of continuous oxidative regeneration in the catalyst regenerator.
  • the process of the present invention is generally conducted at a temperature between about 500 and about 700° C., preferably between about 500 and about 600° C., a pressure of between about 1 atmosphere and 1000 psig (100 and 7000 kPa), a weight hourly space velocity of between about 0.5 and 1000, and a molar ratio of toluene to methanol (in the reactor charge) of at least about 0.2, e.g., from about 0.2 to about 20.
  • the process is preferably conducted in the presence of added hydrogen and/or added water such that the molar ratio of hydrogen and/or water to toluene+methanol in the feed is between about 0.01 and about 10.
  • toluene can be alkylated with methanol so as to produce para-xylene at a selectivity of at least about 90 wt % (based on total C 8 aromatic product) at a per-pass toluene conversion of at least about 15 wt % and a trimethylbenzene production level less than 1 wt %.
  • FIG. 1 is a graph of Diffusion Parameter against para-xylene yield and para-xylene selectivity for the catalyst of Examples 10-14;
  • FIGS. 2 and 3 are graphs of steaming temperature against n-hexane sorption capacity and Diffusion Parameter respectively for the catalysts of Example 15.
  • micropore volume (n-hexane) measurements were made on a computer controlled (Vista/Fortran) duPont 951 Thermalgravimetric analyzer. Isotherms were measured at 90° C. and adsorption values taken at 75 torr n-hexane. The diffusion measurements were made on a TA Instruments 2950 Thermalgravimetric Analyzer equipped with a Thermal Analysis 2000 controller, a gas switching accessory and an automatic sample changer. Diffusion measurements were made at 120° C. and 60 torr 2,2-dimethylbutane. Data were plotted as uptake versus square root of time.
  • Example Example Example 2 3 4 5 Temp, ° C. 600.0 600.0 600.0 600.0 Pressure, psig 40.5 42.8 40.3 43.2 WHSV 4.0 4.0 4.0 4.0 Time on Stream, hr 4.8 20.6 5.1 5.0 Product Distribution (wt %) C5- 1.42 0.73 0.99 1.44 MeOH 0.02 0.17 0.21 1.85 BENZENE 0.25 0.13 0.20 0.27 TOLUENE 61.82 62.41 66.27 81.63 EB 0.06 0.06 0.06 0.04 P-XYL 30.38 32.21 30.52 14.26 M-XYL 3.17 2.00 0.68 0.13 O-XYL 1.37 0.94 0.33 0.11 ETOL 0.30 0.33 0.31 0.14 TMBENZENE 1.05 0.92 0.37 0.08 C10+ 0.15 0.10 0.04 0.04 100.00 100.00 100.00 Performance Data Toluene Conv.
  • a second composite catalyst containing 4.5 wt % phosphorus and 10 wt. % of a 450:1 SiO 2 /Al 2 O 3 ZSM-5 in a binder comprising silica-alumina and clay was divided into four samples which were steamed for 0.75 hours, one atmosphere steam at 950° C. (Example 6), 975° C. (Example 7), 1000° C. (Example 8), and 1025° C. (Example 9).
  • the effect of steaming temperature on the n-hexane sorption capacity (Q) and Diffusion Parameter (D/r 2 ⁇ 10 6 ) of these catalysts is summarized in Table 3 below.
  • Example Example Example 6 7 8 9 Temp, ° C. 600.0 600.0 600 600 Pressure, psig 44.3 43.1 45.3 42.0 WHSV 4.0 4.0 4.0 4.0 Time on Stream, hr 6.3 5.9 5.9 5.9 Product distribution, wt % C5- 1.70 1.68 1.69 1.57 MeOH 1.16 0.35 1.15 2.43 BENZENE 0.24 0.20 0.24 0.22 TOLUENE 65.17 67.30 73.76 83.83 EB 0.06 0.05 0.05 0.03 P-XYL 29.99 28.55 22.09 11.50 M-XYL 1.16 0.72 0.34 0.13 O-XYL 0.52 0.35 0.21 0.11 ETOL 0.31 0.28 0.21 0.11 TMBENZENE 0.63 0.46 0.27 0.07 C10+ 0.06 0.05 0.00 0.00 100.00 100.00 100.00 98.43 Performance Data Toluene Conv.
  • ZSM-5 crystals were prepared according to the method set forth in Example 33 of the Butter et al U.S. Pat. No. 3,965,209.
  • the ZSM-5 had a silica to alumina molar ratio of about 70 to 1 and was combined with an alumina binder in a ratio of 65 weight % zeolite and 35 weight % binder.
  • the bound, phosphorus-free catalyst had an n-hexane sorption capacity, Q, of 74.4 mg/g and a Diffusion Parameter for 2,2-dimethylbutane of 740 sec ⁇ 1 .
  • the catalyst was steamed at 950° C. for 65 hours at atmospheric pressure (100 kPa) in 100% steam which reduced its n-hexane sorption capacity, Q, to 32.4 mg/g, or 44% of the initial capacity, and its Diffusion Parameter for 2,2-dimethylbutane to 1.72 sec ⁇ 1 .
  • the steamed catalyst was then subjected to catalytic testing in the same manner as Examples 1-9.
  • a series of fluid bed catalysts were produced containing about 4 wt % phosphorus and 25 wt. % of a 450:1 SiO 2 /Al 2 O 3 ZSM-5 in a binder comprising kaolin clay.
  • the catalysts were steamed for 0.75 hours at varying temperatures between 1025 and 1060° C. and were used to effect the alkylation of toluene with methanol in a bench-scale fluid bed reactor in the absence of cofed hydrogen. Details of the test and the results obtained are summarized in Table 6 and FIG. 1.
  • a series of three catalysts similar to those of Examples 10-14 (25 wt % ZSM-5 of 450:1 silica/alumina ratio, 75 wt % clay binder with additional 4 wt % phosphorus) was prepared by doping respectively with calcium (2000 ppmw added), magnesium (5000 ppmw added), and both calcium and magnesium (2000 ppmw Ca/5000 ppmw Mg added). Slurries were prepared by mixing together components in the following order: ZSM-5 slurry, phosphoric acid, calcium/magnesium (from nitrate salts), and clay. Catalysts were spray dried and then air calcined at 540° C. for 3 hours.
  • the catalyst contained about 4 wt % phosphorus and 25 wt. % of ZSM-5 in a binder comprising kaolin clay and was steamed for 45 minutes at >1000° C. before being used to effect the alkylation of toluene with methanol in a fixed bed microunit.
  • Example 17 18 Catalyst Properties Phosphorus, wt % 2.8 0 D/r 2 , sec ⁇ 1 ( ⁇ 10 6 ) 2.54 36.28 Q, (n-C6) mg/g 8.1 8.8 Parent Q, mg/g 8.4 10.6 Feed Composition, wt % MeOH 12.82 13.15 Toluene 75.61 75.61 H2O 11.57 11.24 TOTAL 100 100 Reaction Conditions Feed Toluene/Methanol (mol/mol) 2.05 2.00 Feed H2O/HC (mol/mol) 0.53 0.51 Reactor Temp, F.
  • a base catalyst particle was prepared by spray-drying a mixture of ZSM-5 having a silica-alumina molar ratio of 450:1, kaolin clay and silica. After rotary calcination at 650° C. (1200° F.), the final composition of the catalyst was 40 wt % ZSM-5, 30 wt % kaolin and 30 wt % silica.
  • the calcined catalyst was divided into three samples, which were impregnated by the incipient wetness techniques with solutions containing boron (Example 19), magnesium (Example 20) and lanthanum (Example 21) respectively and having the following compositions: a) boron-containing solution 20 gm boric acid 800 gm distilled water 8 gm 30 wt % ammonium hydroxide b) magnesium-containing 20 gm magnesium nitrate hexahydrate solution 240 gm distilled water c) lanthanum-containing 20 gm lanthanum nitrate hexahydrate solution 80 gm distilled water.

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Abstract

There is provided a process for the selective production of para-xylene which comprises reacting toluene with methanol in the presence of a catalyst comprising a porous crystalline material having a Diffusion Parameter for 2,2 dimethylbutane of about 0.1-15 sec−1 when measured at a temperature of 120° C. and a 2,2 dimethylbutane pressure of 60 torr (8 kPa). The porous crystalline material is preferably a medium-pore zeolite, particularly ZSM-5, which has been severely steamed at a temperature of at least 950° C. The porous crystalline material is preferably combined with at least one oxide modifier, preferably including phosphorus, to control reduction of the micropore volume of the material during the steaming step.

Description

  • There is provided a process for the selective production of para-xylene by catalytic methylation of toluene in the presence of a solid catalyst. There is also provided a method for preparing a catalyst which is particularly suited for this reaction. [0001]
  • Of the xylene isomers, para-xylene is of particular value since it is useful in the manufacture of terephthalic acid which is an intermediate in the manufacture of synthetic fibers. Equilibrium mixtures of xylene isomers either alone or in further admixture with ethylbenzene generally contain only about 24 wt. % para-xylene and separation of p-xylene from such mixtures has typically required superfractionation and multistage refrigeration steps. Such processes have involved high operation costs and resulted in only limited yields. There is therefore a continuing need to provide processes which are highly selective for the production of p-xylene. [0002]
  • One known method for producing xylenes involves the alkylation of toluene with methanol over a solid acid catalyst. Thus the alkylation of toluene with methanol over cation-exchanged zeolite Y has been described by Yashima et al. in the Journal of Catalysis 16, 273-280 (1970). These workers reported selective production of para-xylene over the approximate temperature range of 200 to 275° C., with the maximum yield of para-xylene in the mixture of xylenes, i.e. about 50% of the xylene product mixture, being observed at 225° C. Higher temperatures were reported to result in an increase in the yield of meta-xylene and a decrease in production of para and ortho-xylenes. [0003]
  • U.S. Pat. Nos. 3,965,209 to Butter et al. and 4,067,920 to Kaeding teach processes for producing para-xylene in low conversion and high selectivity by reaction of toluene with methanol over a zeolite having a Constraint Index of 1-12, such as ZSM-5. In Butter et al the zeolite is steamed at a temperature of 250-1000° C. for 0.5-100 hours to reduce the acid activity of the zeolite, as measured by its alpha activity, to less than 500 and preferably from in excess of zero to less than 20. [0004]
  • U.S. Pat. No. 4,001,346 to Chu relates to a process for the selective production of para-xylene by methylation of toluene in the presence of a catalyst comprising a crystalline aluminosilicate zeolite which has undergone prior treatment to deposit a coating of between about 15 and about 75 wt. % of coke thereon. [0005]
  • U.S. Pat. No. 4,097,543 to Haag et al. relates to a process for the selective production of para-xylene (up to about 77%) by disproportionation of toluene in the presence of a crystalline aluminosilicate catalyst which has undergone precoking to deposit a coating of at least about 2 wt. % coke thereon. [0006]
  • U.S. Pat. No. 4,380,685 to Chu relates to a process for para-selective aromatics alkylation, including the methylation of toluene, over a zeolite, such as ZSM-5, which has a constraint index of 1-12 and which has been combined with phosphorus and a metal selected from iron and cobalt. Chu indicates that the catalyst can optionally be modified (without specifying the effect of the modification) by steaming at a temperature of 250-1000° C., preferably 400-700° C. for 0.5-100 hours, preferably 1-24 hours. [0007]
  • U.S. Pat. No. 4,554,394 to Forbus and Kaeding teach the use of phosphorus-treated zeolite catalysts for enhancing para-selectivity in aromatics conversion processes. U.S. Pat. No. 4,623,633 to Young relates to the use of thermal shock calcination of aluminosilicates to produce up to 66% para-xylene selectivity. [0008]
  • The use of phosphorus modified ZSM-5 fluid bed catalysts as additive catalysts to improve the olefin yield in fluid catalytic cracking (FCC) is described in U.S. Pat. No. 5,389,232 to Adewuyi et al. and in U.S. Pat. No. 5,472,594 to Tsang et al. [0009]
  • According to the invention, it has now been found that certain porous crystalline materials having specific and closely defined diffusion characteristics, such as can be obtained by unusually severe steaming of ZSM-5 containing an oxide modifier, exhibit improved selectivity for the alkylation of toluene with methanol such that the xylene product contains at least about 90% of the para-isomer at per-pass toluene conversions of at least about 15%. [0010]
  • In one aspect, the invention resides in a process for the selective production of para-xylene which comprises reacting toluene with methanol under alkylation conditions in the presence of a catalyst comprising a porous crystalline material having a Diffusion Parameter for 2,2-dimethylbutane of about 0.1-15 sec[0011] −1 when measured at a temperature of 120° C. and a 2,2-dimethylbutane pressure of 60 torr (8 kPa).
  • Preferably, the porous crystalline material has a Diffusion Parameter of about 0.5-10 sec[0012] −1.
  • Preferably, the catalyst contains at least one oxide modifier and more preferably at least one oxide modifier selected from oxides of elements of Groups IIA, IIIA, IIIB, IVA, VA, VB and VIA of the Periodic Table. Most preferably the oxide modifier is selected from oxides of boron, magnesium, calcium, lanthanum and most preferably phosphorus. [0013]
  • Preferably, the catalyst contains about 0.05 to about 20, more preferably about 0.1 to about 10 and most preferably about 0.1 to about 5, wt % of the oxide modifier based on elemental modifier. [0014]
  • Preferably, the catalyst has an alpha value less than 50 and preferably less than 10. [0015]
  • In a further aspect, the invention resides in a method for producing a catalyst for use in the selective production of para-xylene by reacting toluene with methanol, said method comprising the steps of: [0016]
  • (a) starting with a porous crystalline material having a Diffusion Parameter for 2,2-dimethylbutane in excess of 15 sec[0017] −1 when measured at a temperature of 120° C. and a 2,2-dimethylbutane pressure of 60 torr (8 kPa); and
  • (b) contacting the material of step (a) with steam at a temperature of at least about 950° C. to reduce the Diffusion Parameter thereof for 2,2-dimethylbutane to about 0.1-15 sec[0018] −1 when measured at a temperature of 120° C. and a 2,2-dimethylbutane pressure of 60 torr (8 kPa), the micropore volume of the steamed material being at least 50% of the unsteamed material.
  • Preferably, said porous crystalline material used in step (a) comprises an aluminosilicate zeolite having a silica to alumina molar ratio of at least 250. [0019]
  • The present invention provides a process for alkylating toluene with methanol to selectively produce p-xylene in high yield and with a high per-pass conversion of toluene. The process employs a catalyst which comprises a porous crystalline material having a Diffusion Parameter for 2,2-dimethylbutane of about 0.1-15 sec[0020] −1, and preferably 0.5-10 sec−1, when measured at a temperature of 120° C. and a 2,2-dimethylbutane pressure of 60 torr (8 kPa).
  • As used herein, the Diffusion Parameter of a particular porous crystalline material is defined as D/r[0021] 2×106, wherein D is the diffusion coefficient (cm2/sec) and r is the crystal radius (cm). The required diffusion parameters can be derived from sorption measurements provided the assumption is made that the plane sheet model describes the diffusion process. Thus for a given sorbate loading Q, the value Q/Q∞, where Q∞ is the equilibrium sorbate loading, is mathematically related to (Dt/r2)½ where t is the time (sec) required to reach the sorbate loading Q. Graphical solutions for the plane sheet model are given by J. Crank in “The Mathematics of Diffusion”, Oxford University Press, Ely House, London, 1967.
  • The porous crystalline material employed in the process of the invention is preferably a medium-pore size aluminosilicate zeolite. Medium pore zeolites are generally defined as those having a pore size of about 5 to about 7 Angstroms, such that the zeolite freely sorbs molecules such as n-hexane, 3-methylpentane, benzene and p-xylene. Another common definition for medium pore zeolites involves the Constraint Index test which is described in U.S. Pat. No. 4,016,218, which is incorporated herein by reference. In this case, medium pore zeolites have a Constraint Index of about 1-12, as measured on the zeolite alone without the introduction of oxide modifiers and prior to any steaming to adjust the diffusivity of the catalyst. In addition to the medium-pore size aluminosilicate zeolites, other medium pore acidic metallosilicates, such as silicoaluminophosphates (SAPOs), can be used in the process of the invention. [0022]
  • Particular examples of suitable medium pore zeolites include ZSM-5, ZSM-11, ZSM-12, ZSM-22, ZSM-23, ZSM-35, ZSM48, and MCM-22, with ZSM-5 and ZSM-11 being particularly preferred. [0023]
  • Zeolite ZSM-5 and the conventional preparation thereof are described in U.S. Pat. No. 3,702,886, the disclosure of which is incorporated herein by reference. Zeolite ZSM-11 and the conventional preparation thereof are described in U.S. Pat. No. 3,709,979, the disclosure of which is incorporated herein by reference. Zeolite ZSM-12 and the conventional preparation thereof are described in U.S. Pat. No. 3,832,449, the disclosure of which is incorporated herein by reference. Zeolite ZSM-23 and the conventional preparation thereof are described in U.S. Pat. No. 4,076,842, the disclosure of which is incorporated herein by reference. Zeolite ZSM-35 and the conventional preparation thereof are described in U.S. Pat. No. 4,016,245, the disclosure of which is incorporated herein by reference. ZSM-48 and the conventional preparation thereof is taught by U.S. Pat. No. 4,375,573, the disclosure of which is incorporated herein by reference. MCM-22 is disclosed in U.S. Pat. No. 5,304,698 to Husain; U.S. Pat. No. 5,250,277 to Kresge et al.; U.S. Pat. No. 5,095,167 to Christensen; and U.S. Pat. No. 5,043,503 to Del Rossi et al., the disclosure of which patents are incorporated by reference. [0024]
  • Preferably, the zeolite employed in the process of the invention is ZSM-5 having a silica to alumina molar ratio of at least 250, as measured prior to any treament of the zeolite to adjust its diffusivity. [0025]
  • The medium pore zeolites described above are preferred for the process of the invention since the size and shape of their pores favor the production of p-xylene over the other xylene isomers. However, conventional forms of these zeolites have Diffusion Parameter values in excess of the 0.1-15 sec[0026] −1 range required for the process of the invention. The required diffusivity for the present catalyst can be achieved by severely steaming the catalyst so as to effect a controlled reduction in the micropore volume of the catalyst to not less than 50%, and preferably 50-90%, of that of the unsteamed catalyst. Reduction in micropore volume is derived by measuring the n-hexane adsorption capacity of the catalyst, before and after steaming, at 90° C. and 75 torr n-hexane pressure.
  • Steaming of the porous crystalline material is effected at a temperature of at least about 950° C., preferably about 950 to about 1075° C., and most preferably about 1000 to about 1050° C. for about 10 minutes to about 10 hours, preferably from 30 minutes to 5 hours. [0027]
  • To effect the desired controlled reduction in diffusivity and micropore volume, it may be desirable to combine the porous crystalline material, prior to steaming, with at least one oxide modifier, preferably selected from oxides of the elements of Groups IIA, IIIA, IIIB, IVA, VA, VB and VIA of the Periodic Table (IUPAC version). Most preferably, said at least one oxide modifier is selected from oxides of boron, magnesium, calcium, lanthanum and most preferably phosphorus. In some cases, it may be desirable to combine the porous crystalline material with more than one oxide modifier, for example a combination of phosphorus with calcium and/or magnesium, since in this way it may be possible to reduce the steaming severity needed to achieve a target diffusivity value. The total amount of oxide modifier present in the catalyst, as measured on an elemental basis, may be between about 0.05 and about 20 wt. %, and preferably is between about 0.1 and about 10 wt. %, based on the weight of the final catalyst. [0028]
  • Where the modifier includes phosphorus, incorporation of modifier in the catalyst of the invention is conveniently achieved by the methods described in U.S. Pat. Nos. 4,356,338, 5,110,776, 5,231,064 and 5,348,643, the entire disclosures of which are incorporated herein by reference. Treatment with phosphorus-containing compounds can readily be accomplished by contacting the porous crystalline material, either alone or in combination with a binder or matrix material, with a solution of an appropriate phosphorus compound, followed by drying and calcining to convert the phosphorus to its oxide form. Contact with the phosphorus-containing compound is generally conducted at a temperature of about 25° C. and about 125° C. for a time between about 15 minutes and about 20 hours. The concentration of the phosphorus in the contact mixture may be between about 0.01 and about 30 wt. %. [0029]
  • After contacting with the phosphorus-containing compound, the porous crystalline material may be dried and calcined to convert the phosphorus to an oxide form. Calcination can be carried out in an inert atmosphere or in the presence of oxygen, for example, in air at a temperature of about 150 to 750° C., preferably about 300 to 500° C., for at least 1 hour, preferably 3-5 hours. [0030]
  • Similar techniques known in the art can be used to incorporate other modifying oxides into the catalyst of the invention. [0031]
  • Representative phosphorus-containing compounds which may be used to incorporate a phosphorus oxide modifier into the catalyst of the invention include derivatives of groups represented by PX[0032] 3, RPX2, R2PX, R3P, X3PO, (XO)3PO, (XO)3P, R3P═O, R3P═S, RPO2, RPS2, RP(O)(OX)2, RP(S)(SX)2, R2P(O)OX, R2P(S)SX, RP(OX)2, RP(SX)2, ROP(OX)2, RSP(SX)2, (RS)2PSP(SR)2, and (RO)2POP(OR)2, where R is an alkyl or aryl, such as phenyl radical, and X is hydrogen, R, or halide. These compounds include primary, RPH2, secondary, R2PH, and tertiary, R3P, phosphines such as butyl phosphine, the tertiary phosphine oxides, R3PO, such as tributyl phosphine oxide, the tertiary phosphine sulfides, R3PS, the primary, RP(O)(OX)2, and secondary, R2P(O)OX, phosphonic acids such as benzene phosphonic acid, the corresponding sulfur derivatives such as RP(S)(SX)2 and R2P(S)SX, the esters of the phosphonic acids such as dialkyl phosphonate, (RO)2P(O)H, dialkyl alkyl phosphonates, (RO)2P(O)R, and alkyl dialkylphosphinates, (RO)P(O)R2; phosphinous acids, R2POX, such as diethylphosphinous acid, primary, (RO)P(OX)2, secondary, (RO)2POX, and tertiary, (RO)3P, phosphites, and esters thereof such as the monopropyl ester, alkyl dialkylphosphinites, (RO)PR2, and dialkyl alkyphosphinite, (RO)2PR, esters. Corresponding sulfur derivatives may also be employed including (RS)2P(S)H, (RS)2P(S)R, (RS)P(S)R2, R2PSX, (RS)P(SX)2, (RS)2PSX, (RS)3P, (RS)PR2, and (RS)2PR. Examples of phosphite esters include trimethylphosphite, triethylphosphite, diisopropylphosphite, butylphosphite, and pyrophosphites such as tetraethylpyrophosphite. The alkyl groups in the mentioned compounds preferably contain one to four carbon atoms.
  • Other suitable phosphorus-containing compounds include ammonium hydrogen phosphate, the phosphorus halides such as phosphorus trichloride, bromide, and iodide, alkyl phosphorodichloridites, (RO)PCI[0033] 2, dialkylphosphorochloridites, (RO)2PCI, dialkylphosphinochloroidites, R2PCI, alkyl alkylphosphonochloridates, (RO)(R)P(O)CI, dialkyl phosphinochloridates, R2P(O)CI, and RP(O)CI2. Applicable corresponding sulfur derivatives include (RS)PCI2, (RS)2PCI, (RS)(R)P(S)CI, and R2P(S)CI.
  • Particular phosphorus-containing compounds include ammonium phosphate, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, diphenyl phosphine chloride, trimethylphosphite, phosphorus trichloride, phosphoric acid, phenyl phosphine oxychloride, trimethylphosphate, diphenyl phosphinous acid, diphenyl phosphinic acid, diethylchlorothiophosphate, methyl acid phosphate, and other alcohol-P[0034] 2O5 reaction products.
  • Representative boron-containing compounds which may be used to incorporate a boron oxide modifier into the catalyst of the invention include boric acid, trimethylborate, boron oxide, boron sulfide, boron hydride, butylboron dimethoxide, butylboric acid, dimethylboric anhydride, hexamethylborazine, phenyl boric acid, triethylborane, diborane and triphenyl boron. [0035]
  • Representative magnesium-containing compounds include magnesium acetate, magnesium nitrate, magnesium benzoate, magnesium propionate, magnesium 2-ethylhexoate, magnesium carbonate, magnesium formate, magnesium oxylate, magnesium bromide, magnesium hydride, magnesium lactate, magnesium laurate, magnesium oleate, magnesium palmitate, magnesium salicylate, magnesium stearate and magnesium sulfide. [0036]
  • Representative calcium-containing compounds include calcium acetate, calcium acetylacetonate, calcium carbonate, calcium chloride, calcium methoxide, calcium naphthenate, calcium nitrate, calcium phosphate, calcium stearate and calcium sulfate. [0037]
  • Representative lanthanum-containing compounds include lanthanum acetate, lanthanum acetylacetonate, lanthanum carbonate, lanthanum chloride, lanthanum hydroxide, lanthanum nitrate, lanthanum phosphate and lanthanum sulfate. [0038]
  • The porous crystalline material employed in the process of the invention may be combined with a variety of binder or matrix materials resistant to the temperatures and other conditions employed in the process. Such materials include active and inactive materials such as clays, silica and/or metal oxides such as alumina. The latter may be either naturally occurring or in the form of gelatinous precipitates or gels including mixtures of silica and metal oxides. Use of a material which is active, tends to change the conversion and/or selectivity of the catalyst and hence is generally not preferred. Inactive materials suitably serve as diluents to control the amount of conversion in a given process so that products can be obtained economically and orderly without employing other means for controlling the rate of reaction. These materials may be incorporated into naturally occurring clays, e.g., bentonite and kaolin, to improve the crush strength of the catalyst under commercial operating conditions. Said materials, i.e., clays, oxides, etc., function as binders for the catalyst. It is desirable to provide a catalyst having good crush strength because in commercial use it is desirable to prevent the catalyst from breaking down into powder-like materials. These clay and/or oxide binders have been employed normally only for the purpose of improving the crush strength of the catalyst. [0039]
  • Naturally occurring clays which can be composited with the porous crystalline material include the montmorillonite and kaolin family, which families include the subbentonites, and the kaolins commonly known as Dixie, McNamee, Georgia and Florida clays or others in which the main mineral constituent is halloysite, kaolinite, dickite, nacrite, or anauxite. Such clays can be used in the raw state as originally mined or initially subjected to calcination, acid treatment or chemical modification. [0040]
  • In addition to the foregoing materials, the porous crystalline material can be composited with a porous matrix material such as silica-alumina, silica-magnesia, silica-zirconia, silica-thoria, silica-beryllia, silica-titania as well as ternary compositions such as silica-alumina-thoria, silica-alumina-zirconia silica-alumina-magnesia and silica-magnesia-zirconia. [0041]
  • The relative proportions of porous crystalline material and inorganic oxide matrix vary widely, with the content of the former ranging from about 1 to about 90% by weight and more usually, particularly when the composite is prepared in the form of beads, in the range of about 2 to about 80 wt. % of the composite. [0042]
  • Preferably, the binder material comprises silica or a kaolin clay. [0043]
  • Procedures for preparing silica-bound zeolites, such as ZSM-5, are described in U.S. Pat. Nos. 4,582,815; 5,053,374; and 5,182,242. A particular procedure for binding ZSM-5 with a silica binder involves an extrusion process. [0044]
  • The porous crystalline material may be combined with a binder in the form of a fluidized bed catalyst. This fluidized bed catalyst may comprise clay in the binder thereof, and may be formed by a spray-drying process to form catalyst particles having a particle size of 20-200 microns. [0045]
  • The catalyst of the invention may optionally be precoked. The precoking step is preferably carried out by initially utilizing the uncoked catalyst in the toluene methylation reaction, during which coke is deposited on the catalyst surface and thereafter controlled within a desired range, typically from about 1 to about 20 wt. % and preferably from about 1 to about 5 wt. %, by periodic regeneration by exposure to an oxygen-containing atmosphere at an elevated temperature. [0046]
  • One of the advantages of the catalyst described herein is its ease of regenerability. Thus, after the catalyst accumulates coke as it catalyzes the toluene methylation reaction, it can easily be regenerated by burning off a controlled amount of coke in a partial combustion atmosphere in a regenerator at temperatures in the range of from about 400 to about 700° C. The coke loading on the catalyst may thereby be reduced or substantially eliminated in the regenerator. If it is desired to maintain a given degree of coke loading, the regeneration step may be controlled such that the regenerated catalyst returning to the toluene methylation reaction zone is coke-loaded at the desired level. [0047]
  • The present process may suitably be carried out in fixed, moving, or fluid catalyst beds. If it is desired to continuously control the extent of coke loading, moving or fluid bed configurations are preferred. With moving or fluid bed configurations, the extent of coke loading can be controlled by varying the severity and/or the frequency of continuous oxidative regeneration in the catalyst regenerator. [0048]
  • The process of the present invention is generally conducted at a temperature between about 500 and about 700° C., preferably between about 500 and about 600° C., a pressure of between about 1 atmosphere and 1000 psig (100 and 7000 kPa), a weight hourly space velocity of between about 0.5 and 1000, and a molar ratio of toluene to methanol (in the reactor charge) of at least about 0.2, e.g., from about 0.2 to about 20. The process is preferably conducted in the presence of added hydrogen and/or added water such that the molar ratio of hydrogen and/or water to toluene+methanol in the feed is between about 0.01 and about 10. [0049]
  • Using the process of the invention, toluene can be alkylated with methanol so as to produce para-xylene at a selectivity of at least about 90 wt % (based on total C[0050] 8 aromatic product) at a per-pass toluene conversion of at least about 15 wt % and a trimethylbenzene production level less than 1 wt %.
    •
  • The invention will now be more particularly described in the following Examples and the accompanying drawing, in which: [0051]
  • FIG. 1 is a graph of Diffusion Parameter against para-xylene yield and para-xylene selectivity for the catalyst of Examples 10-14; and [0052]
  • FIGS. 2 and 3 are graphs of steaming temperature against n-hexane sorption capacity and Diffusion Parameter respectively for the catalysts of Example 15.[0053]
  • In the Examples, micropore volume (n-hexane) measurements were made on a computer controlled (Vista/Fortran) duPont 951 Thermalgravimetric analyzer. Isotherms were measured at 90° C. and adsorption values taken at 75 torr n-hexane. The diffusion measurements were made on a TA Instruments 2950 Thermalgravimetric Analyzer equipped with a Thermal Analysis 2000 controller, a gas switching accessory and an automatic sample changer. Diffusion measurements were made at 120° C. and 60 torr 2,2-dimethylbutane. Data were plotted as uptake versus square root of time. Fixed bed catalytic testing was conducted using a {fraction (3/8)}″ (1 cm) outside diameter, down-flow reactor using a two gram catalyst sample. The product distribution was analyzed with an on-line Varian 3700 GC ([0054] Supelcowax 10 capillary column, 30 m in length, 0.32 mm internal diameter, and 0.5 μm film thickness).
    • EXAMPLES 1-5
  • Five samples of a composite catalyst containing 2.9 wt. % phosphorus and 10 wt % of a 450:1 SiO[0055] 2/Al2O3 ZSM-5 in a binder comprising silica-alumina and clay were steamed for 0.75 hours, one atmosphere steam at 975° C. (Example 1), 1000° C. (Example 2), 1025° C. (Example 3), 1050° C. (Example 4) and 1075° C. (Example 5). The effect of steaming temperature on the n-hexane sorption capacity (Q) compared to that of the unsteamed catalyst (10.7 mg/g) and on the Diffusion Parameter (D/r2×106) is summarized in Table 1 below.
  • Samples of the five steamed catalysts were then used in toluene methylation tests on a feed comprising toluene, methanol and water such that toluene/MeOH molar ratio=2 and H[0056] 2O/HC molar ratio=2 (where HC=toluene+methanol). The tests were conducted at 600° C., 40 psig (380 kPa) and HC WHSV=4 in the presence of hydrogen such that H2/HC molar ratio=2. The results of Examples 2-5 are summarised in Table 2.
    TABLE 1
    % retention of D/r2
    Steaming initial sorption sec−1
    Catalyst ID Temp (° C.) Q(n-C6, mg/g) capacity (×106)
    Ex. 1  975 10.3  96 21.2
    Ex. 2 1000 9.7 91 16.4
    Ex. 3 1025 9.1 85 10.2
    Ex. 4 1050 8.4 79  3.2
    Ex. 5 1075 6.5 61  0.3
  • [0057]
    TABLE 2
    Example Example Example Example
    2 3 4 5
    Temp, ° C. 600.0 600.0 600.0 600.0
    Pressure, psig 40.5 42.8 40.3 43.2
    WHSV 4.0 4.0 4.0 4.0
    Time on Stream, hr 4.8 20.6 5.1 5.0
    Product Distribution
    (wt %)
    C5- 1.42 0.73 0.99 1.44
    MeOH 0.02 0.17 0.21 1.85
    BENZENE 0.25 0.13 0.20 0.27
    TOLUENE 61.82 62.41 66.27 81.63
    EB 0.06 0.06 0.06 0.04
    P-XYL 30.38 32.21 30.52 14.26
    M-XYL 3.17 2.00 0.68 0.13
    O-XYL 1.37 0.94 0.33 0.11
    ETOL 0.30 0.33 0.31 0.14
    TMBENZENE 1.05 0.92 0.37 0.08
    C10+ 0.15 0.10 0.04 0.04
    100.00 100.00 100.00 100.00
    Performance Data
    Toluene Conv. % 33.21 32.56 28.39 11.80
    MeOH Conv. % 99.71 97.76 97.76 75.12
    MeOH Utilization, 62.08 63.72 57.53 34.26
    mol %
    p-Xylene Selectivity, % 86.99 91.64 96.80 98.35
    Xylene Yield on 37.73 37.98 34.07 15.67
    Toluene, wt %
    p-Xylene Yield on Tol, 32.8 34.8 33.0 15.4
    wt %
    Xylenes/Aromatic 95.1 95.8 97.0 96.2
    Product, wt %
  • From Table 2 it will be seen, with the catalyst of Examples 1-5, steaming at a temperature in excess of 1000° C. was necessary to reduce the D/r2 value below 15 and with the Example 2 catalyst (steamed at 1000° C. to a D/r2 value of 16.4), the p-selectivity of the catalyst was below 87%. As the steaming temperature increased above 1000° C. to 1075° C., the para-xylene selectivity increased but with the catalyst steamed at 1075° C. this was accompanied by a significant decrease in the para-xylene yield and the methanol utilization (moles of xylene produced/moles of methanol converted). [0058]
    • EXAMPLES 6-9
  • A second composite catalyst containing 4.5 wt % phosphorus and 10 wt. % of a 450:1 SiO[0059] 2/Al2O3 ZSM-5 in a binder comprising silica-alumina and clay was divided into four samples which were steamed for 0.75 hours, one atmosphere steam at 950° C. (Example 6), 975° C. (Example 7), 1000° C. (Example 8), and 1025° C. (Example 9). The effect of steaming temperature on the n-hexane sorption capacity (Q) and Diffusion Parameter (D/r2×106) of these catalysts is summarized in Table 3 below.
  • Samples of the four steamed catalysts were then used in toluene methylation tests conducted as in Examples 2-5 with the HC WHSV=4. The results of Examples 6-9 are summarised in Table 4. [0060]
    TABLE 3
    Steaming Q(n-C6, % retention of initial D/r2
    Catalyst ID Temp (° C.) mg/g) sorption capacity sec−1(×106)
    Unsteamed 12.7  21.7 
    Sample
    Ex. 6  950 9.4 74 6.3
    Ex. 7  975 7.2 57 5.3
    Ex. 8 1000 7.9 62  1.92
    Ex. 9 1025 7.0 55  0.84
  • [0061]
    TABLE 4
    Example Example Example Example
    6 7 8 9
    Temp, ° C. 600.0 600.0 600 600
    Pressure, psig 44.3 43.1 45.3 42.0
    WHSV 4.0 4.0 4.0 4.0
    Time on Stream, hr 6.3 5.9 5.9 5.9
    Product distribution,
    wt %
    C5- 1.70 1.68 1.69 1.57
    MeOH 1.16 0.35 1.15 2.43
    BENZENE 0.24 0.20 0.24 0.22
    TOLUENE 65.17 67.30 73.76 83.83
    EB 0.06 0.05 0.05 0.03
    P-XYL 29.99 28.55 22.09 11.50
    M-XYL 1.16 0.72 0.34 0.13
    O-XYL 0.52 0.35 0.21 0.11
    ETOL 0.31 0.28 0.21 0.11
    TMBENZENE 0.63 0.46 0.27 0.07
    C10+ 0.06 0.05 0.00 0.00
    100.00 100.00 100.00 98.43
    Performance Data
    Toluene Conv. % 29.73 27.44 20.47 9.62
    MeOH Conv. % 97.81 95.17 84.14 66.42
    MeOH Utilization, 59.02 59.02 49.02 32.20
    mol %
    p-Xylene Selectivity, % 94.70 96.38 97.58 97.95
    Xylene Yield on Tol, 34.14 31.93 24.40 12.66
    wt %
    p-Xylene Yield on Tol, 32.3 30.8 23.8 12.4
    wt %
    Xylenes/Aromatic 96.1 96.6 96.7 96.5
    Product, wt %
    • COMPARATIVE EXAMPLE A
  • ZSM-5 crystals were prepared according to the method set forth in Example 33 of the Butter et al U.S. Pat. No. 3,965,209. The ZSM-5 had a silica to alumina molar ratio of about 70 to 1 and was combined with an alumina binder in a ratio of 65 weight % zeolite and 35 weight % binder. [0062]
  • The bound, phosphorus-free catalyst had an n-hexane sorption capacity, Q, of 74.4 mg/g and a Diffusion Parameter for 2,2-dimethylbutane of 740 sec[0063] −1. The catalyst was steamed at 950° C. for 65 hours at atmospheric pressure (100 kPa) in 100% steam which reduced its n-hexane sorption capacity, Q, to 32.4 mg/g, or 44% of the initial capacity, and its Diffusion Parameter for 2,2-dimethylbutane to 1.72 sec−1. The steamed catalyst was then subjected to catalytic testing in the same manner as Examples 1-9. In particular, experiments were conducted at 600° C., 40 psig (380 kPa), H2/HC=2, H2O/HC=2, WHSV=4 with a toluene/MeOH=2 feed. The results are summarized in Table 5, which provides data for an average analysis of three samples taken at 28.53, 33.32 and 37.22 hours on stream.
    TABLE 5
    Temp, ° C. 600
    Pressure, psig 39.63
    WHSV 4.00
    Time on Stream, hr 33.0
    Product Distribution, wt %
    C5- 0.36
    DME 0.09
    MeOH 1.35
    BENZENE 0.19
    TOLUENE 71.91
    EB 0.05
    P-XYL 21.40
    M-XYL 1.91
    O-XYL 1.18
    ETOL 0.17
    TMBENZENE 1.29
    C10+ 0.09
    100.00
    Performance Data
    Toluene Conv. % 22.30
    MeOH Conv. % 80.74
    MeOH Utilization, mol % 53.79
    p-Xylene Selectivity, % 87.37
    Xylene Yield on Toluene, wt % 26.47
    p-Xylene Yield on Toluene, wt % 23.1
    Xylenes/Aromatic Product, wt % 93.2
  • The data in Table 5 show that in Comparative Example A, although the toluene conversion was 22.30%, the para-selectivity was only 87.37%, the methanol conversion was only 80.74% and the wt % xylenes based on the total aromatic product was only 93.2. Furthermore, the yield of the unwanted by-product, trimethylbenzene, was 1.29 wt. %. [0064]
    • EXAMPLES 10-14
  • A series of fluid bed catalysts were produced containing about 4 wt % phosphorus and 25 wt. % of a 450:1 SiO[0065] 2/Al2O3 ZSM-5 in a binder comprising kaolin clay. The catalysts were steamed for 0.75 hours at varying temperatures between 1025 and 1060° C. and were used to effect the alkylation of toluene with methanol in a bench-scale fluid bed reactor in the absence of cofed hydrogen. Details of the test and the results obtained are summarized in Table 6 and FIG. 1. It will be seen that, as the Diffusion Parameter of the catalyst decreased with increasing steaming severity, the para-xylene selectivity increased generally linearly whereas the para-xylene yield increased to a maximum at a D/r2 value of 1-2×10−6 sec−1 before decreasing again.
    TABLE 6
    Example No. 10 11 12 13 14
    Catalyst Properties
    Phosphorus, wt % 3.9 3.8 4.1 4.1 3.8
    Steaming Temp, C 1025 1031 1033 1033 1060
    D/r2, sec-1 (×106) 1.14 0.71 2.81 6.5 0.45
    Q, (n-C6) mg/g 19.7 19 14.1 14.2 17.8
    Parent Q, mg/g 21.6 21.6 17.1 20.7 21.9
    Reaction Conditions
    Feed Toluene/Methanol (mol/mol) 2.08 2.03 1.93 2.06 2.17
    Feed H2O/HC (mol/mol) 0.47 0.46 0.63 0.63 0.51
    Reactor Temp, F 1105 1107 1113 1108 1110
    Reactor P, psig 20.6 20.7 20.8 21.7 20.7
    HC WHSV 1.71 1.75 1.75 1.72 1.71
    Time On Stream, Hrs 10 10 10 10 2
    Feed Composition, wt %
    MeOH 12.81 13.12 13.20 12.50 12.26
    Toluene 76.76 76.53 73.19 73.93 76.51
    H2O 10.43 10.35 13.61 13.57 11.23
    Product Composition, wt %
    C5- 1.46 1.65 1.67 1.52 2.41
    MeOH 0.01 0.03 0.09 0.01 0.29
    Benzene 0.40 0.31 0.33 0.34 0.32
    Toluene 54.60 55.89 50.81 52.41 62.16
    EB 0.05 0.05 0.05 0.05 0.04
    p-Xylene 22.15 21.68 21.72 19.85 15.70
    m-Xylene 1.87 1.16 2.33 2.94 0.42
    o-Xylene 0.78 0.50 1.00 1.25 0.20
    Styrene 0.02 0.02 0.02 0.02 0.02
    E-Toluene 0.25 0.25 0.23 0.23 0.20
    TMBenzene 0.52 0.48 0.70 0.72 0.24
    C10+ 0.28 0.34 0.31 0.30 0.39
    H2O 17.61 17.64 20.74 20.36 17.61
    Performance Data
    Toluene Conv, % 28.9 27.0 30.6 29.1 18.8
    MeOH Conv, % 99.9 99.8 99.3 99.9 97.6
    MeOH Utilization, mol % 58.5 53.8 57.7 58.1 41.1
    p-Xylene Selectivity, % 89.3 92.9 86.7 82.6 96.2
    Xylene Yield on Tol, wt % 32.3 30.5 34.2 32.5 21.3
    p-Xylene Yield on Tol, wt % 28.9 28.3 29.7 26.8 20.5
    Xylenes/Aromatic Products, wt % 95.7 95.3 95.0 94.8 94.8
    • EXAMPLE 15
  • A series of three catalysts similar to those of Examples 10-14 (25 wt % ZSM-5 of 450:1 silica/alumina ratio, 75 wt % clay binder with additional 4 wt % phosphorus) was prepared by doping respectively with calcium (2000 ppmw added), magnesium (5000 ppmw added), and both calcium and magnesium (2000 ppmw Ca/5000 ppmw Mg added). Slurries were prepared by mixing together components in the following order: ZSM-5 slurry, phosphoric acid, calcium/magnesium (from nitrate salts), and clay. Catalysts were spray dried and then air calcined at 540° C. for 3 hours. Three samples of each catalyst were then steamed for 45 minutes in 1 atmosphere steam at 950° C., 1000° C., and 1050° C., respectively. The n-hexane sorption capacity and the Diffusion Parameter of the catalysts are plotted against steaming temperature in FIGS. 2 and 3. The presence of magnesium (and calcium to a lesser extent) decreases the steaming temperature required to produce a catalyst with a given Diffusion Parameter. These data show that combinations of oxide modifiers can effectively be used to produce the desired catalyst. [0066]
    • EXAMPLE 16
  • A comparison was made between a catalyst similar to those used in Examples 10-14, in which the initial zeolite had a silica/alumina molar ratio of 450, and a catalyst produced from ZSM-5 having an initial silica/alumina molar ratio of 26. In each case the catalyst contained about 4 wt % phosphorus and 25 wt. % of ZSM-5 in a binder comprising kaolin clay and was steamed for 45 minutes at >1000° C. before being used to effect the alkylation of toluene with methanol in a fixed bed microunit. The results are summarized in Table 7 from which it will be seen that the 26:1 material had significantly lower activity (as indicated by the lower WHSV necessary to achieve comparable toluene conversion), lower para-selectivity and lower methanol utilization than the 450:1 material. [0067]
    TABLE 7
    Catalyst Properties
    Percent ZSM-5 25 25
    Si:Al Ratio 450 26
    Steaming Temperature, ° C. 1051 1016
    Reaction Conditions
    Temperature, ° C. 600 585
    Pressure, psig 40 40
    WHSV 8.0 2.50
    Tol/MeOH (mol/mol) 2.0 2.00
    H2/HC (mol/mol) 2.0 2.00
    H2O/HC (mol/mol) 2.0 2.00
    Time on Stream, hr 14.30 6.00
    Product composition, wt %
    C5- 0.05 2.12
    DME 0.00 0.00
    MeOH 0.40 0.32
    BENZENE 0.13 0.23
    TOLUENE 64.42 65.83
    EB 0.06 0.05
    P-XYLENE 32.66 27.82
    M-XYLENE 0.94 1.81
    O-XYLENE 0.42 0.75
    ETHYL TOLUENE 0.33 0.25
    TMBENZENE 0.56 0.76
    C10+ 0.04 0.06
    Performance Data
    Toluene Conv., % 30.68 29.16
    MeOH Conv., % 94.30 95.43
    MeOH Utilization, mol % 67.37 59.46
    p-Xylene Selectivity, % 96.02 91.58
    Xylene Yield on Tol, wt % 36.61 32.69
    p-Xylene Yield on Tol, wt % 35.2 29.9
    Xylenes/Aromatic Products, wt % 96.8 95.7
    • EXAMPLES 17 AND 18
  • Two composite catalysts were produced containing 10 wt % of 450:1 SiO[0068] 2/Al2O3 ZSM-5 in a kaolin clay matrix which in one case also contained 2.8 wt % phosphorus (Example 17) and the other case did not contain phosphorus (Example 18). Each catalyst was steamed at 1010° C. for 0.75 hour and was then used to effect the alkylation of toluene with methanol in a bench-scale fluid bed reactor containing 80 grams of catalyst. The properties of the steamed catalysts and the results of the toluene alkylation tests are shown in Table 8 below.
  • From Table 8 it will be seen that the Diffusion Parameter, D/r[0069] 2 of the phosphorus-free catalyst of Example 18 remained high after steaming. In addition, it will be seen that the para-xylene selectivity and yield of the phosphorus containing catalyst of Example 17 were significantly higher than those of the phosphorus-free catalyst of Example 18.
    TABLE 8
    Example 17 18
    Catalyst Properties
    Phosphorus, wt % 2.8 0
    D/r2, sec−1 (×106) 2.54 36.28
    Q, (n-C6) mg/g 8.1 8.8
    Parent Q, mg/g 8.4 10.6
    Feed Composition, wt %
    MeOH 12.82 13.15
    Toluene 75.61 75.61
    H2O 11.57 11.24
    TOTAL 100 100
    Reaction Conditions
    Feed Toluene/Methanol (mol/mol) 2.05 2.00
    Feed H2O/HC (mol/mol) 0.53 0.51
    Reactor Temp, F. 1107 1108
    Reactor Pressure, psig 19 21.6
    HC WHSV 1.72 1.74
    Time On Stream, Hrs 6 6
    Product Composition, wt %
    C5- 1.66 1.53
    MeOH 0.34 0.33
    Benzene 0.26 0.31
    Toluene 55.09 54.33
    EB 0.04 0.03
    p-Xylene 20.08 15.94
    m-Xylene 1.57 4.83
    o-Xylene 0.72 2.3
    Styrene 0.02 0.01
    E-Toluene 0.23 0.17
    TMBenzene 0.61 1.49
    C10+ 0.29 0.25
    H2O 19.09 18.48
    TOTAL 100 100
    Performance Data
    Toluene Conv, % 27.1 28.1
    MeOH Conv, % 97.3 97.5
    MeOH Utilization, mol % 54.1 54.3
    p-Xylene Selectivity, % 89.8 69.1
    Xylene Yield on Tol, wt % 29.6 30.5
    p-Xylene Yield on Tol, wt % 26.6 21.1
    Xylenes/Aromatic Products, wt % 94.9 92.2
    • EXAMPLES 19-21
  • A base catalyst particle was prepared by spray-drying a mixture of ZSM-5 having a silica-alumina molar ratio of 450:1, kaolin clay and silica. After rotary calcination at 650° C. (1200° F.), the final composition of the catalyst was 40 wt % ZSM-5, 30 wt % kaolin and 30 wt % silica. The calcined catalyst was divided into three samples, which were impregnated by the incipient wetness techniques with solutions containing boron (Example 19), magnesium (Example 20) and lanthanum (Example 21) respectively and having the following compositions: [0070]
    a) boron-containing solution  20 gm boric acid
    800 gm distilled water
     8 gm 30 wt % ammonium hydroxide
    b) magnesium-containing  20 gm magnesium nitrate hexahydrate
    solution 240 gm distilled water
    c) lanthanum-containing  20 gm lanthanum nitrate hexahydrate
    solution  80 gm distilled water.
  • In each case, impregnation was conducted by incipient wetness by adding 0.79 gm of the appropriate solution to a catalyst sample, after which the sample was dried at 150° C. for 2 hours and then air calcined at 550° C. for 4 hours to convert the ammonium and nitrate salts to oxides. The oxide-modified catalysts were then heated in 1 atmosphere steam at 1000° C. Table 9 lists the oxide loading on each catalyst on an elemental basis and the n-hexane adsorption capacity (Q in mg/g) and Diffusion Parameter (D/r[0071] 2×106 sec−1) of the unsteamed and steamed catalysts.
    TABLE 9
    Oxide Loading Q (n-C6, mg/g) D/r2 sec−1 (×106)
    Unsteamed
    Catalyst
    Example 19 0.2 wt % boron 52.6 17  
    Example 20 0.5 wt % magnesium 42.7 24.2 
    Example 21 4.9 wt % lanthanum 39.8 19.9 
    Steamed
    Catalyst
    Example 19 0.2 wt % boron 32.7 2.6
    Example 20 0.5 wt % magnesium 37.3 9.4
    Example 21 4.9 wt % lanthanum 31.1 1.4
  • The steamed catalysts of Examples 19 and 21 were then tested in the alkylation of toluene with methanol under the conditions and with the results listed in Table 10. [0072]
    TABLE 10
    Example 19 21
    Reaction Conditions
    Temperature, C. 592 592
    Pressure, psia 16 16
    WHSV 3 4
    Time on stream, minutes 402 6
    Product Composition, wt %
    C5- 2.33 2.47
    Methanol 0.59 3.18
    Benzene 0.07 0.04
    Toluene 64.6 67.54
    Ethylbenzene 0.06 0.06
    P-xylene 28.05 23.02
    M-xylene 1.81 1.47
    O-xylene 0.75 0.61
    Ethyltoluene 0.31 0.30
    Thmethylbenzene 1.08 0.78
    C10+ 0.34 0.52
    Performance Data
    % of total xylenes
    Para 91.6 91.71
    Meta 5.90 5.85
    Ortho 2.46 2.44
    Total xylenes, wt % 30.61 25.10
    Xylenes/total aromatic product 94.46 93.81
    Toluene conversion 30.2 25.9
    Methanol conversion 96.3 79.9
    Methanol utilization 60 60

Claims (20)

What is claimed is:
1. A process for the selective production of para-xylene which comprises reacting toluene with methanol under alkylation conditions in the presence of a catalyst comprising a porous crystalline material having a Diffusion Parameter for 2,2 dimethylbutane of about 0.1-15 sec−1 when measured at a temperature of 120° C. and a 2,2 dimethylbutane pressure of 60 torr (8 kPa).
2. The process of claim 1, wherein said Diffusion Parameter of said porous crystalline material is about 0.5-10 sec−1.
3. The process of claim 1, wherein said porous crystalline material has undergone prior treatment with steam at a temperature of at least 950° C. to adjust the Diffusion Parameter of said material to about 0.1-15 sec−1.
4. The process of claim 3, wherein said porous crystalline material has undergone prior treatment with steam at a temperature of at least 1000° C. for between about 10 minutes and about 100 hours.
5. The process of claim 4, wherein the steaming reduces the pore volume of the catalyst to not less than 50% of that of the unsteamed catalyst.
6. The process of claim 1, wherein the catalyst contains at least one oxide modifier selected from oxides of elements of Groups IIA, IIIA, IIIB, IVA, IVB, VA and VIA of the Periodic Table.
7. The process of claim 1, wherein the catalyst contains at least one oxide modifier selected from oxides of boron, magnesium, calcium, lanthanum and phosphorus.
8. The process of claim 1, wherein the catalyst contains about 0.05 to about 20 wt % of the oxide modifier based on the elemental modifier.
9. The process of claim 1, wherein the catalyst contains about 0.1 to about 10 wt % of the oxide modifier based on the elemental modifier.
10. The process of claim 1, wherein the catalyst has an average particle size of about 20 to 200 microns
11. The process of claim 1, wherein the porous crystalline material is an aluminosilicate zeolite.
12. The process of claim 11, wherein said zeolite is ZSM-5 or ZSM-11.
13. The process of claim 1, wherein said alkylation conditions include a temperature between about 500 and 700° C., a pressure of between about 1 atmosphere and 1000 psig (100 and 7000 kPa), a weight hourly space velocity between about 0.5 and about 1000 and a molar ratio of toluene to methanol of at least about 0.2.
14. The process of claim 1, wherein said alkylation is conducted in the presence of added hydrogen and/or water such that the molar ratio of hydrogen and/or water to toluene+methanol in the feed is about 0.01 to about 10.
15. A method for producing a catalyst for use in the selective production of para-xylene by reacting toluene with methanol, said method comprising the steps of:
(a) starting with a porous crystalline material having a Diffusion Parameter for 2,2-dimethylbutane in excess of 15 sec−1 when measured at a temperature of 120° C. and a 2,2-dimethylbutane pressure of 60 torr (8 kPa); and
(b) contacting the material of step (a) with steam at a temperature of at least about 950° C. to reduce the Diffusion Parameter thereof for 2,2-dimethylbutane to about 0.1-15 sec−1 when measured at a temperature of 120° C. and a 2,2-dimethylbutane pressure of 60 torr (8 kPa), the micropore volume of the steamed material being at least 50% of the unsteamed material.
16. The method of claim 15, wherein the porous crystalline material is combined with a source of at least one oxide modifier selected from oxides of elements of Groups IIA, IIIA, IIIB, IVA, VA, VB and VIA of the Periodic Table prior to step (b).
17. The method of claim 15, wherein the porous crystalline material is combined with a source of at least one oxide modifier selected from oxides of boron, magnesium, calcium, lanthanum and phosphorus prior to step (b).
18. The method of claim 15, wherein the porous crystalline material used in step (a) is an aluminosilicate zeolite having a Constraint Index of about 1 to 12.
19. The method of claim 18, wherein the zeolite has a silica to alumina molar ratio of at least 250.
20. The method of claim 15, wherein step (b) is conducted at a temperature of at least 1000° C. for about 10 minutes to about 100 hours.
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Publication number Priority date Publication date Assignee Title
EP1478462A2 (en) * 2002-02-28 2004-11-24 ExxonMobil Chemical Patents Inc. Molecular sieve compositions, catalyst thereof, their making and use in conversion processes
US20050239635A1 (en) * 2004-04-23 2005-10-27 Ghosh Ashim K Method of modifying zeolite catalyst
US20050240070A1 (en) * 2004-04-23 2005-10-27 Ghosh Ashim K Zeolite catalyst and method
US20070032690A1 (en) * 2005-08-03 2007-02-08 Ghosh Ashim K Zeolite catalyst and method of preparing and use of zeolite catalyst
US20080033067A1 (en) * 2002-11-14 2008-02-07 Ou John D Y Para-Xylene Production Process Employing In-Situ Catalyst Selectivation
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US10099973B2 (en) 2014-06-04 2018-10-16 Dalian Institute Of Chemical Physics, Chinese Academy Of Sciences Method for preparing p-xylene and co-producing propylene with high selectivity
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Families Citing this family (74)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU2003247572A1 (en) * 2002-06-19 2004-01-06 Exxonmobil Chemical Patents Inc. Manufacture of xylenes from reformate
US7119239B2 (en) * 2002-06-19 2006-10-10 Exxonmobil Chemical Patents Inc. Manufacture of xylenes using reformate
US7074739B2 (en) * 2002-11-19 2006-07-11 Exxonmobil Chemical Patents Inc. Multi-component molecular sieve catalyst compositions and their use in aromatics reactions
US7084318B2 (en) * 2003-08-01 2006-08-01 Saudi Basic Industries Corporation Toluene methylation process
US7060864B2 (en) * 2003-09-30 2006-06-13 Saudi Basic Industries Corporation Toluene methylation process
US7060644B2 (en) * 2004-01-08 2006-06-13 Saudi Basic Industries Corporation Aromatic alkylation catalyst and method
US6943131B1 (en) * 2004-03-02 2005-09-13 Saudi Basic Industries Corporation Selective zeolite catalyst modification
US7105713B2 (en) * 2004-06-09 2006-09-12 Saudi Basic Industries Corporation Preparation of alkyl-aromatic products
US7304194B2 (en) * 2005-05-05 2007-12-04 Saudi Basic Industries Corporation Hydrothermal treatment of phosphorus-modified zeolite catalysts
KR100598988B1 (en) * 2005-05-18 2006-07-12 주식회사 하이닉스반도체 Overlay vernier and method of manufacturing the semiconductor device
CN100340486C (en) * 2005-11-16 2007-10-03 汕头大学 Method for preparing pure finely porous molecular sieve psosessing even distribution of acid strength
US7662737B2 (en) * 2005-12-22 2010-02-16 Saudi Basic Industries Corporation Bound phosphorus-modified zeolite catalyst, method of preparing and method of using thereof
CN101437611B (en) * 2006-05-08 2015-04-22 埃克森美孚化学专利公司 Improved catalyst composition
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KR101948358B1 (en) * 2011-08-03 2019-02-14 토탈 리서치 앤드 테크놀로지 펠루이 Use of a catalyst comprising a phosphorus modified zeolite in an alcohol dehydration process
US9006506B2 (en) 2011-10-07 2015-04-14 Exxonmobil Chemical Patents Inc. Alkylation process
EP2768609A1 (en) 2011-10-17 2014-08-27 ExxonMobil Research and Engineering Company Process for producing phosphorus modified zeolite catalysts
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CN105814009B (en) 2013-12-20 2021-11-12 埃克森美孚研究工程公司 Catalyst for selective conversion of oxygenates to aromatics
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Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4380685A (en) * 1980-05-19 1983-04-19 Mobil Oil Corporation Shape selective reactions with zeolite catalysts modified with iron and/or cobalt
US4491678A (en) * 1982-10-19 1985-01-01 Idemitsu Kosan Company Limited Process for the production of para-xylene

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EP1478462A2 (en) * 2002-02-28 2004-11-24 ExxonMobil Chemical Patents Inc. Molecular sieve compositions, catalyst thereof, their making and use in conversion processes
US20080033067A1 (en) * 2002-11-14 2008-02-07 Ou John D Y Para-Xylene Production Process Employing In-Situ Catalyst Selectivation
US7902414B2 (en) * 2002-11-14 2011-03-08 Exxonmobil Chemical Patents Inc. Para-xylene production process employing in-situ catalyst selectivation
US20080306317A1 (en) * 2004-04-23 2008-12-11 Ashim Kumar Ghosh Aromatic Alkylation with Phosphorus-modified Zeolite catalyst
EP1602406A1 (en) * 2004-04-23 2005-12-07 Sabic Americas, Inc. Method of modifying zeolite catalyst
US20050239635A1 (en) * 2004-04-23 2005-10-27 Ghosh Ashim K Method of modifying zeolite catalyst
US20050240070A1 (en) * 2004-04-23 2005-10-27 Ghosh Ashim K Zeolite catalyst and method
US20090036723A1 (en) * 2004-04-23 2009-02-05 Ashim Kumar Ghosh Method of Preparing a Xylene Product
US7713898B2 (en) 2004-04-23 2010-05-11 Saudi Basic Industries Corporation Method of making a phosphorus-modified zeolite catalyst
EP2138231A1 (en) * 2004-04-23 2009-12-30 Sabic Americas, Inc. Method of modifying zeolite catalyst
US7674942B2 (en) 2005-08-03 2010-03-09 Saudi Basic Industries Corporation Method of preparing an alkyl aromatic product with phosphorus-treated zeolite catalyst
US20080176736A1 (en) * 2005-08-03 2008-07-24 Saudi Basic Industries Corporation Phosphorus-Containing Zeolite Catalyst
US20070032690A1 (en) * 2005-08-03 2007-02-08 Ghosh Ashim K Zeolite catalyst and method of preparing and use of zeolite catalyst
US20080275280A1 (en) * 2005-08-03 2008-11-06 Ashim Kumar Ghosh Method of Preparing an Alkyl Aromatic Product with Phosphorus-Treated Zeolite Catalyst
WO2008020965A3 (en) * 2006-08-16 2008-10-16 Cymer Inc Euv optics
WO2008020965A2 (en) * 2006-08-16 2008-02-21 Cymer, Inc. Euv optics
US20090253949A1 (en) * 2008-04-02 2009-10-08 Saudi Basic Industries Corporation Pretreatment of a phosphorus-modified zeolite catalyst for a toluene methylation process
KR101635651B1 (en) * 2008-04-02 2016-07-01 사우디 베이식 인더스트리즈 코포레이션 Pretreatment of a phosphorus-modified zeolite catalyst for an aromatic alkylation
US8115041B2 (en) * 2008-04-02 2012-02-14 Saudi Basic Industries Corporation Pretreatment of a phosphorus-modified zeolite catalyst for an aromatic alkylation process
KR20100136992A (en) * 2008-04-02 2010-12-29 사우디 베이식 인더스트리즈 코포레이션 Pretreatment of a phosphorus-modified zeolite catalyst for an aromatic alkylation
US8436222B2 (en) 2008-04-02 2013-05-07 Saudi Basic Industries Corporation Pretreatment of a phosphorus-modified zeolite catalyst for an aromatic alkylation process
US20100113850A1 (en) * 2008-11-03 2010-05-06 Ashim Kumar Ghosh Stable Shape-Selective Catalyst for Aromatic Alkylation and Methods of Using and Preparing
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
US20100144514A1 (en) * 2008-12-09 2010-06-10 Nicholas Christopher P Process for Making Catalyst for Olefin Upgrading
US20100144513A1 (en) * 2008-12-09 2010-06-10 Nicholas Christopher P Catalyst for Olefin Upgrading
US8062987B2 (en) 2009-10-05 2011-11-22 Saudi Basic Industries Corporation Phosphorus-containing zeolite catalysts and their method of preparation
US20110082025A1 (en) * 2009-10-05 2011-04-07 Ashim Kumar Ghosh Phosphorus-Containing Zeolite Catalysts and Their Method of Preparation
US20140256537A1 (en) * 2011-05-22 2014-09-11 Fina Technology, Inc. Addition of a Base to Enhance Product Yield in Alkylation Reactions
WO2013009399A1 (en) * 2011-07-11 2013-01-17 Exxonmobil Chemical Patents Inc. Alkylation of benzene and/or toluene with methanol
US20130150640A1 (en) * 2011-12-08 2013-06-13 Gtc Technology Us, Llc Production of xylenes by methylation of aromatic compounds
US9278342B2 (en) 2012-07-02 2016-03-08 Saudi Basic Industries Corporation Method of modifying a phosphorus-containing zeolite catalyst
CN102872903A (en) * 2012-10-12 2013-01-16 常州大学 Preparation method of in-process shape-selective catalyst for para-xylene synthesis
US10099973B2 (en) 2014-06-04 2018-10-16 Dalian Institute Of Chemical Physics, Chinese Academy Of Sciences Method for preparing p-xylene and co-producing propylene with high selectivity
WO2016032636A1 (en) * 2014-08-26 2016-03-03 Exxonmobil Chemical Patents Inc. Treatment of off-gas in the production of para-xylene by the methylation of toluene and/or benzene
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US11498062B2 (en) * 2016-09-30 2022-11-15 Regents Of The University Of Minnesota Phosphorus-containing solid catalysts and reactions catalyzed thereby, including synthesis of p-xylene
CN111712478A (en) * 2018-02-20 2020-09-25 环球油品有限责任公司 Method and apparatus for methylating toluene and benzene in an aromatics complex

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