WO1998014415A1 - Selective para-xylene production by toluene methylation - Google Patents
Selective para-xylene production by toluene methylation Download PDFInfo
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- WO1998014415A1 WO1998014415A1 PCT/US1997/018079 US9718079W WO9814415A1 WO 1998014415 A1 WO1998014415 A1 WO 1998014415A1 US 9718079 W US9718079 W US 9718079W WO 9814415 A1 WO9814415 A1 WO 9814415A1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
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- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
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- 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
- B01J29/005—Mixtures of molecular sieves comprising at least one molecular sieve which is not an aluminosilicate zeolite, e.g. from groups B01J29/03 - B01J29/049 or B01J29/82 - B01J29/89
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/061—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof containing metallic elements added to the zeolite
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- 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
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- 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
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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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/30—After treatment, characterised by the means used
- B01J2229/36—Steaming
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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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/30—After treatment, characterised by the means used
- B01J2229/40—Special temperature treatment, i.e. other than just for template removal
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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
- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/82—Phosphates
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- C07C2527/14—Phosphorus; Compounds thereof
- C07C2527/16—Phosphorus; Compounds thereof containing oxygen
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- 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
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- 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.
- One known method for producing xylenes involves the alkylation of toluene with methanol over a solid acid catalyst.
- U.S. Patent 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. Patent 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. Patent 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. Patent 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. Patent 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. Patent 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 " - 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, IMA, NIB, 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 x10 ⁇ , 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/C where Q propane 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. Patent 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-
- Zeolite ZSM-5 and the conventional preparation thereof are described in U.S. Patent 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. Patent 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. Patent 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. Patent 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. Patent 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 HA, 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.
- incorporation of modifier in the catalyst of the invention is conveniently achieved by the methods described in U.S. Patent 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.
- R is an alkyl or aryl, such as phenyl radical
- X is hydrogen
- These compounds include primary, RPH 2 , secondary, R 2 PH, 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, 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
- 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 , dialkylphosphoro- chloridites, (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 .
- Applicable corresponding sulfur derivatives include (RS)PCI 2 ,
- 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 O5 reaction products.
- 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.
- 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.
- 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.
- 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.
- 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.
- the binder material comprises silica or a kaolin clay. Procedures for preparing silica-bound zeolites, such as ZSM-5, are described in U.S. Patent 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.
- 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%.
- Figure 1 is a graph of Diffusion Parameter against para-xylene yield and para-xylene selectivity for the catalyst of Examples 10-14;
- Figures 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.
- a second composite catalyst containing 4.5 wt% phosphorus and 10 wt.% of a 450:1 SiO 2 /AI 2 O3 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/ xlO 6 ) of these catalysts is summarized in Table 3 below.
- ZSM-5 crystals were prepared according to the method set forth in Example 33 of the Butter et al U.S. Patent 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
- 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 32.4mg/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 /AI 2 O3 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 Figure 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.
- 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.
- 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.
- 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 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.
- 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
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
Claims
Priority Applications (8)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US09/341,008 US6423879B1 (en) | 1997-10-02 | 1997-10-02 | Selective para-xylene production by toluene methylation |
DE69734206T DE69734206T2 (en) | 1996-10-02 | 1997-10-02 | SELECTIVE PREPARATION OF P-XYLOL BY METHYLATION OF TOLUOL |
BR9712484-2A BR9712484A (en) | 1996-10-02 | 1997-10-02 | Selective production of paraxylene by toluene methylation |
AU48954/97A AU718083B2 (en) | 1996-10-02 | 1997-10-02 | Selective para-xylene production by toluene methylation |
NZ334123A NZ334123A (en) | 1996-10-02 | 1997-10-02 | Process for producing para-xylene by reacting toulene with methanol using a porous crystalline catalyst like aluminosilicate zeolite (ZSM-5 or ZSM-11) |
CA002267915A CA2267915C (en) | 1996-10-02 | 1997-10-02 | Selective para-xylene production by toluene methylation |
EP97911629A EP0935591B1 (en) | 1996-10-02 | 1997-10-02 | Selective para-xylene production by toluene methylation |
JP51696698A JP4077518B2 (en) | 1996-10-02 | 1997-10-02 | Selective production of para-xylene by methylation of toluene |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US72527796A | 1996-10-02 | 1996-10-02 | |
US08/725,277 | 1996-10-02 |
Related Child Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US09/341,008 A-371-Of-International US6423879B1 (en) | 1997-10-02 | 1997-10-02 | Selective para-xylene production by toluene methylation |
US10/141,159 Division US6504072B1 (en) | 1999-11-15 | 2002-05-08 | Selective para-xylene production by toluene methylation |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1998014415A1 true WO1998014415A1 (en) | 1998-04-09 |
Family
ID=24913880
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US1997/018079 WO1998014415A1 (en) | 1996-10-02 | 1997-10-02 | Selective para-xylene production by toluene methylation |
Country Status (20)
Country | Link |
---|---|
EP (1) | EP0935591B1 (en) |
JP (1) | JP4077518B2 (en) |
KR (1) | KR100569657B1 (en) |
CN (1) | CN1088694C (en) |
AR (1) | AR010997A1 (en) |
AU (1) | AU718083B2 (en) |
BR (1) | BR9712484A (en) |
CA (1) | CA2267915C (en) |
DE (1) | DE69734206T2 (en) |
ES (1) | ES2244994T3 (en) |
ID (1) | ID21235A (en) |
IN (1) | IN207438B (en) |
MX (1) | MX207687B (en) |
MY (1) | MY122348A (en) |
NZ (1) | NZ334123A (en) |
RU (1) | RU2179964C2 (en) |
TR (1) | TR199900717T2 (en) |
TW (1) | TW375602B (en) |
WO (1) | WO1998014415A1 (en) |
ZA (1) | ZA978671B (en) |
Cited By (17)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5994603A (en) * | 1996-05-29 | 1999-11-30 | Exxon Chemical Patents Inc. | Methylation of toluene to para-xylene |
EP1073614A1 (en) * | 1998-04-06 | 2001-02-07 | Mobil Oil Corporation | Catalyst and process for converting methanol to hydrocarbons |
JP2002544247A (en) * | 1999-05-14 | 2002-12-24 | エクソンモービル・ケミカル・パテンツ・インク | Direct and selective synthesis of para-xylene |
US6613708B1 (en) | 1999-06-07 | 2003-09-02 | Exxonmobil Chemical Patents Inc. | Catalyst selectivation |
WO2004000767A1 (en) * | 2002-06-19 | 2003-12-31 | Exxonmobil Chemical Patents Inc. | Manufacture of xylenes from reformate |
WO2004043593A1 (en) * | 2002-11-14 | 2004-05-27 | Exxonmobil Chemical Patents Inc. | Para-xylene production process employing in-situ catalyst selectivation |
WO2004074219A2 (en) | 2003-02-18 | 2004-09-02 | Johnson Matthey Public Limited Company | Process for producing para-xylene |
WO2005018806A1 (en) * | 2003-08-15 | 2005-03-03 | Exxonmobil Chemical Patents Inc. | Boron selectivation of molecular sieve catalysts and use thereof in hydrocarbon conversion |
WO2005033071A2 (en) | 2003-09-30 | 2005-04-14 | Saudi Basic Industries Corporation | Toluene methylation process |
US7119239B2 (en) | 2002-06-19 | 2006-10-10 | Exxonmobil Chemical Patents Inc. | Manufacture of xylenes using reformate |
US7176339B2 (en) | 2002-06-19 | 2007-02-13 | Exxonmobil Chemical Patents Inc. | Manufacture of xylenes using reformate |
US7238636B2 (en) | 2003-07-23 | 2007-07-03 | Exxonmobil Chemical Patents Inc. | High temperature calcination of selectivated molecular sieve catalysts for activity and diffusional modification |
US7799962B2 (en) | 2003-12-31 | 2010-09-21 | Exxonmobil Chemical Patents Inc. | Process for aromatic alkylation |
CN102395544A (en) * | 2009-04-14 | 2012-03-28 | 埃克森美孚化学专利公司 | Process for the purification of paraxylene |
CN103638963A (en) * | 2013-12-06 | 2014-03-19 | 陕西煤化工技术工程中心有限公司 | P-xylene fluid catalyst prepared by performing alkylation of methylbenzene methyl alcohol and preparation method thereof |
WO2014120422A1 (en) * | 2013-01-31 | 2014-08-07 | Exxonmobile Chemical Patents, Inc. | Production of para-xylene |
EP3433223A4 (en) * | 2016-03-25 | 2019-12-25 | ExxonMobil Chemical Patents Inc. | Catalyst and process for the production of para-xylene |
Families Citing this family (20)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7399727B2 (en) * | 2004-04-23 | 2008-07-15 | Saudi Basic Industries Corporation | Zeolite catalyst and method |
JP4965798B2 (en) * | 2004-07-30 | 2012-07-04 | サウジ ベイシック インダストリーズ コーポレイション | Methylation of toluene |
CN101172252B (en) * | 2006-11-01 | 2010-05-12 | 中国石油化工股份有限公司 | Reforming catalyst and application in high selectivity production of para-xylene of the same |
US8115041B2 (en) * | 2008-04-02 | 2012-02-14 | Saudi Basic Industries Corporation | Pretreatment of a phosphorus-modified zeolite catalyst for an aromatic alkylation process |
CN101306974B (en) * | 2008-06-12 | 2011-03-30 | 江苏工业学院 | Process for catalytically synthesizing p-xylene |
US8344197B2 (en) * | 2009-10-21 | 2013-01-01 | Exxonmobil Chemical Patents Inc. | Production of para-xylene by the methylation of benzene and/or toluene |
TWI495511B (en) * | 2011-07-27 | 2015-08-11 | Exxonmobil Chem Patents Inc | Fluid bed reactor with staged baffles |
KR102049289B1 (en) * | 2011-12-08 | 2019-11-27 | 쥐티씨 테크놀로지 유에스,엘엘씨 | Production of xylenes by methylation of aromatic compounds |
US9156749B2 (en) * | 2012-05-31 | 2015-10-13 | Exxonmobil Chemical Patents Inc. | Styrene removal in paraxylene recovery process |
CN103664488B (en) * | 2012-09-05 | 2015-09-09 | 中国石油化工股份有限公司 | Remove the aromatic hydrocarbons methanol alkylation method of oxygenatedchemicals impurity |
CN103113182B (en) * | 2013-01-22 | 2015-01-07 | 上海华谊(集团)公司 | Method for synthesizing paraxylene from toluene and methanol in shape-selective alkylating mode |
CN104096589A (en) * | 2013-04-02 | 2014-10-15 | 上海华谊(集团)公司 | Toluene and methanol shape-selective alkylation catalyst and method thereof |
JP2017523157A (en) * | 2014-06-30 | 2017-08-17 | エクソンモービル・ケミカル・パテンツ・インク | Method for producing para-xylene |
CN106458788B (en) * | 2014-06-30 | 2019-11-26 | 埃克森美孚化学专利公司 | The method for preparing dimethylbenzene |
JP6743173B2 (en) * | 2016-03-25 | 2020-08-19 | エクソンモービル・ケミカル・パテンツ・インク | Catalysts and processes for the production of paraxylene |
JP6899430B2 (en) * | 2016-10-06 | 2021-07-07 | エクソンモービル・ケミカル・パテンツ・インク | Process of methylating aromatic hydrocarbons |
CN110023271B (en) * | 2016-10-06 | 2022-08-19 | 埃克森美孚化学专利公司 | Process for the selectivation of catalysts for the production of para-xylene by the methylation of benzene and/or toluene |
CN106669818B (en) * | 2016-12-27 | 2019-08-30 | 西安元创化工科技股份有限公司 | It is a kind of to be alkylated preparation to the preparation method and applications of methyl-ethyl benzene catalyst |
CN108786906B (en) * | 2017-04-27 | 2020-08-07 | 中国科学院大连化学物理研究所 | In-situ preparation method of catalyst for co-production of p-xylene and low-carbon olefin from toluene prepared from benzene and methanol |
CN108786904B (en) * | 2017-04-27 | 2020-08-11 | 中国科学院大连化学物理研究所 | In-situ preparation method of catalyst for preparing low-carbon olefin and co-producing p-xylene |
Citations (2)
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 |
-
1997
- 1997-09-26 ZA ZA978671A patent/ZA978671B/en unknown
- 1997-09-30 AR ARP970104502A patent/AR010997A1/en unknown
- 1997-10-01 IN IN2186CH1997 patent/IN207438B/en unknown
- 1997-10-01 MY MYPI97004583A patent/MY122348A/en unknown
- 1997-10-01 TW TW86114279A patent/TW375602B/en not_active IP Right Cessation
- 1997-10-02 JP JP51696698A patent/JP4077518B2/en not_active Expired - Fee Related
- 1997-10-02 BR BR9712484-2A patent/BR9712484A/en not_active IP Right Cessation
- 1997-10-02 WO PCT/US1997/018079 patent/WO1998014415A1/en active IP Right Grant
- 1997-10-02 NZ NZ334123A patent/NZ334123A/en unknown
- 1997-10-02 AU AU48954/97A patent/AU718083B2/en not_active Ceased
- 1997-10-02 ID IDW990145A patent/ID21235A/en unknown
- 1997-10-02 KR KR1019997002588A patent/KR100569657B1/en not_active IP Right Cessation
- 1997-10-02 EP EP97911629A patent/EP0935591B1/en not_active Expired - Lifetime
- 1997-10-02 DE DE69734206T patent/DE69734206T2/en not_active Expired - Lifetime
- 1997-10-02 CA CA002267915A patent/CA2267915C/en not_active Expired - Fee Related
- 1997-10-02 RU RU99109016/04A patent/RU2179964C2/en not_active IP Right Cessation
- 1997-10-02 CN CN97198340A patent/CN1088694C/en not_active Expired - Fee Related
- 1997-10-02 ES ES97911629T patent/ES2244994T3/en not_active Expired - Lifetime
- 1997-10-02 TR TR1999/00717T patent/TR199900717T2/en unknown
-
1999
- 1999-03-25 MX MX9902863A patent/MX207687B/en not_active IP Right Cessation
Patent Citations (2)
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 |
Non-Patent Citations (1)
Title |
---|
See also references of EP0935591A4 * |
Cited By (32)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5994603A (en) * | 1996-05-29 | 1999-11-30 | Exxon Chemical Patents Inc. | Methylation of toluene to para-xylene |
EP1073614A1 (en) * | 1998-04-06 | 2001-02-07 | Mobil Oil Corporation | Catalyst and process for converting methanol to hydrocarbons |
EP1073614A4 (en) * | 1998-04-06 | 2002-06-05 | Exxonmobil Oil Corp | Catalyst and process for converting methanol to hydrocarbons |
JP2002544247A (en) * | 1999-05-14 | 2002-12-24 | エクソンモービル・ケミカル・パテンツ・インク | Direct and selective synthesis of para-xylene |
US6613708B1 (en) | 1999-06-07 | 2003-09-02 | Exxonmobil Chemical Patents Inc. | Catalyst selectivation |
US7119239B2 (en) | 2002-06-19 | 2006-10-10 | Exxonmobil Chemical Patents Inc. | Manufacture of xylenes using reformate |
US7655823B2 (en) | 2002-06-19 | 2010-02-02 | Exxonmobil Chemical Patents Inc. | Manufacture of xylenes from reformate |
US7396967B2 (en) | 2002-06-19 | 2008-07-08 | Exxonmobil Chemical Patents Inc. | Manufacture of xylenes using reformate |
WO2004000767A1 (en) * | 2002-06-19 | 2003-12-31 | Exxonmobil Chemical Patents Inc. | Manufacture of xylenes from reformate |
US7176339B2 (en) | 2002-06-19 | 2007-02-13 | Exxonmobil Chemical Patents Inc. | Manufacture of xylenes using reformate |
WO2004043593A1 (en) * | 2002-11-14 | 2004-05-27 | Exxonmobil Chemical Patents Inc. | 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 |
WO2004074219A2 (en) | 2003-02-18 | 2004-09-02 | Johnson Matthey Public Limited Company | Process for producing para-xylene |
WO2004074219A3 (en) * | 2003-02-18 | 2004-10-14 | Johnson Matthey Plc | Process for producing para-xylene |
US7321072B2 (en) | 2003-02-18 | 2008-01-22 | Johnson Matthey Plc | Process for producing paraxylene by methylating toluene with methanol at a low contacting time |
US7238636B2 (en) | 2003-07-23 | 2007-07-03 | Exxonmobil Chemical Patents Inc. | High temperature calcination of selectivated molecular sieve catalysts for activity and diffusional modification |
US7326818B2 (en) | 2003-08-15 | 2008-02-05 | Exxonmobil Chemical Patents Inc. | Selectivation of molecular sieve catalysts and use therof in hydrocarbon conversion |
WO2005018806A1 (en) * | 2003-08-15 | 2005-03-03 | Exxonmobil Chemical Patents Inc. | Boron selectivation of molecular sieve catalysts and use thereof in hydrocarbon conversion |
EP1675808A2 (en) * | 2003-09-30 | 2006-07-05 | Saudi Basic Industries Corporation | Toluene methylation process |
WO2005033071A2 (en) | 2003-09-30 | 2005-04-14 | Saudi Basic Industries Corporation | Toluene methylation process |
EP1675808A4 (en) * | 2003-09-30 | 2010-03-24 | Saudi Basic Ind Corp | Toluene methylation process |
US7799962B2 (en) | 2003-12-31 | 2010-09-21 | Exxonmobil Chemical Patents Inc. | Process for aromatic alkylation |
US8252967B2 (en) | 2009-04-14 | 2012-08-28 | Exxonmobil Chemical Patents Inc. | Process for the purification of paraxylene |
CN102395544A (en) * | 2009-04-14 | 2012-03-28 | 埃克森美孚化学专利公司 | Process for the purification of paraxylene |
US8507744B2 (en) | 2009-04-14 | 2013-08-13 | Exxonmobil Chemical Patents Inc. | Process for the purification of paraxylene |
CN102395544B (en) * | 2009-04-14 | 2014-08-27 | 埃克森美孚化学专利公司 | Process for the purification of paraxylene |
US8981171B2 (en) | 2009-04-14 | 2015-03-17 | Exxonmobil Chemical Patents Inc. | Process for the purification of paraxylene |
WO2014120422A1 (en) * | 2013-01-31 | 2014-08-07 | Exxonmobile Chemical Patents, Inc. | Production of para-xylene |
KR101935708B1 (en) | 2013-01-31 | 2019-01-04 | 엑손모빌 케미칼 패턴츠 인코포레이티드 | Production of para-xylene |
CN103638963A (en) * | 2013-12-06 | 2014-03-19 | 陕西煤化工技术工程中心有限公司 | P-xylene fluid catalyst prepared by performing alkylation of methylbenzene methyl alcohol and preparation method thereof |
EP3433223A4 (en) * | 2016-03-25 | 2019-12-25 | ExxonMobil Chemical Patents Inc. | Catalyst and process for the production of para-xylene |
US10647633B2 (en) | 2016-03-25 | 2020-05-12 | Exxonmobil Chemical Patents Inc. | Catalyst and process for the production of para-xylene |
Also Published As
Publication number | Publication date |
---|---|
AU718083B2 (en) | 2000-04-06 |
CA2267915A1 (en) | 1998-04-09 |
TR199900717T2 (en) | 1999-07-21 |
AR010997A1 (en) | 2000-08-02 |
EP0935591B1 (en) | 2005-09-14 |
EP0935591A1 (en) | 1999-08-18 |
DE69734206T2 (en) | 2006-07-06 |
BR9712484A (en) | 2000-01-11 |
DE69734206D1 (en) | 2005-10-20 |
MY122348A (en) | 2006-04-29 |
ES2244994T3 (en) | 2005-12-16 |
ZA978671B (en) | 1999-03-26 |
MX207687B (en) | 2002-05-06 |
JP4077518B2 (en) | 2008-04-16 |
TW375602B (en) | 1999-12-01 |
AU4895497A (en) | 1998-04-24 |
CN1088694C (en) | 2002-08-07 |
KR20000048645A (en) | 2000-07-25 |
JP2001524069A (en) | 2001-11-27 |
EP0935591A4 (en) | 2001-04-18 |
NZ334123A (en) | 1999-11-29 |
IN207438B (en) | 2007-06-29 |
CN1231653A (en) | 1999-10-13 |
KR100569657B1 (en) | 2006-04-11 |
MX9902863A (en) | 1999-08-31 |
RU2179964C2 (en) | 2002-02-27 |
CA2267915C (en) | 2008-04-01 |
ID21235A (en) | 1999-05-06 |
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