WO2000074847A1 - Accroissement de la selectivite d'un catalyseur - Google Patents

Accroissement de la selectivite d'un catalyseur Download PDF

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Publication number
WO2000074847A1
WO2000074847A1 PCT/US2000/013003 US0013003W WO0074847A1 WO 2000074847 A1 WO2000074847 A1 WO 2000074847A1 US 0013003 W US0013003 W US 0013003W WO 0074847 A1 WO0074847 A1 WO 0074847A1
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Prior art keywords
zeolite
agent
component
toluene
para
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PCT/US2000/013003
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English (en)
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WO2000074847A8 (fr
Inventor
John Ou
Youchang Xie
Xiangyun Long
Xiawan Yang
Lili Guan
Bieying Zhao
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Exxon Chemical Patents Inc.
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Priority claimed from US09/312,104 external-priority patent/US6388156B1/en
Priority claimed from US09/327,241 external-priority patent/US6613708B1/en
Application filed by Exxon Chemical Patents Inc. filed Critical Exxon Chemical Patents Inc.
Priority to BR0011679-3A priority Critical patent/BR0011679A/pt
Priority to CA002371225A priority patent/CA2371225A1/fr
Priority to EP00935926A priority patent/EP1189697A1/fr
Priority to MXPA01012623A priority patent/MXPA01012623A/es
Priority to AU51312/00A priority patent/AU5131200A/en
Publication of WO2000074847A1 publication Critical patent/WO2000074847A1/fr
Publication of WO2000074847A8 publication Critical patent/WO2000074847A8/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/82—Phosphates
    • B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
    • B01J29/85—Silicoaluminophosphates [SAPO compounds]
    • 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
    • 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
    • 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
    • B01J29/405—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 containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
    • 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
    • B01J37/082—Decomposition and pyrolysis
    • B01J37/086—Decomposition of an organometallic compound, a metal complex or a metal salt of a carboxylic acid
    • 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
    • B01J2229/12—After treatment, characterised by the effect to be obtained to alter the outside of the crystallites, e.g. selectivation
    • 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
    • B01J2229/32—Reaction with silicon compounds, e.g. TEOS, siliconfluoride
    • 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
    • B01J2229/34—Reaction with organic or organometallic compounds
    • 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
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • B01J37/0203—Impregnation the impregnation liquid containing organic compounds

Definitions

  • the present invention relates to methods for modifying zeolite catalysts and catalysts so modified, and more particularly relates, in one embodiment, to methods for modifying zeolite catalysts to make them more selective to the synthesis of para-substituted dialkylbenzenes relative to other dialkylbenzene isomers, as well as useful in other reactions, and catalysts so modified.
  • para-xylene is of particular value as a large volume chemical intermediate in a number of applications being useful in the manufacture of terephthalates which are intermediates for the manufacture of polyethylene terephthalate (PET).
  • One source of feedstocks for manufacturing PX is by disproportionation of toluene into xylenes.
  • One of the disadvantages of this process is that large quantities of benzene are also produced.
  • Another source of feedstocks used to obtain PX involves the isomerization of a feedstream that contains non-equilibrium quantities of mixed ortho- and meta-xylene isomers (OX and MX, respectively) and is lean with respect to PX content.
  • a disadvantage of this process is that the separation of the PX from the other isomers is expensive.
  • Zeolites are known to catalyze the reaction of toluene with other reactants to make xylenes.
  • Some zeolites are silicate based materials which are comprised of a silica lattice and, optionally, alumina combined with exchangeable cations such as alkali or alkaline earth metal ions.
  • the term "zeolites" includes materials containing silica and optionally alumina, it is recognized that the silica and alumina portions may be replaced in whole or in part with other oxides.
  • germanium oxide, tin oxide, phosphorus oxide, and mixtures thereof can replace the silica portion.
  • Boron oxide, iron oxide, gallium oxide, indium oxide, and mixtures thereof can replace the alumina portion.
  • zeolite shall mean not only materials containing silicon and, optionally, aluminum atoms in the crystalline lattice structure thereof, but also materials which contain suitable replacement atoms for such silicon and aluminum, such as gallosilicates, borosilicates, ferrosilicates, and the like.
  • Aluminophosphate zeolites are made of alternating AIO 4 and PO 4 tetrahedra. Aluminophosphate-based materials have lower acidity compared to aluminosilicates. The lower acidity eliminates many side reactions, raises reactants' utilization, and extends catalyst life.
  • Aluminophosphate-based zeolites are often abbreviated as ALPO. Substitution of silicon for P and/or a P-AI pair produces silicoaluminophosphate zeolites, abbreviated as SAPO.
  • alkylaromatic compounds can be synthesized by reacting an aromatic compound such as toluene with a mixture of carbon dioxide (CO 2 ), and carbon monoxide (CO) and hydrogen (H 2 ) (synthesis gas) at alkylation conditions in the presence of a catalyst system, which comprises (1) a composite of oxides of zinc, copper, chromium, and/or cadmium; and (2) an aluminosilicate material, either crystalline or amorphous, such as zeolites or clays; as disclosed in U.S. Pat. Nos. 4,487,984 and 4,665,238.
  • a catalyst system which comprises (1) a composite of oxides of zinc, copper, chromium, and/or cadmium; and (2) an aluminosilicate material, either crystalline or amorphous, such as zeolites or clays; as disclosed in U.S. Pat. Nos. 4,487,984 and 4,665,238.
  • Such catalyst systems are not capable of producing greater than equilibrium concentrations of para- xylene (PX) in the xylene-fraction product.
  • the xylene-fraction product contains a mixture of xylene isomers at or near the equilibrium concentration, i.e., 24% PX, 54% MX, and 22% OX.
  • the lack of para- xylene selectivity in alkylation of toluene with syngas can be caused by (1 ) the acidic sites on the sur ace outside the zeolite channels, and/or (2) the channel structure not being able to differentiate para-xylene from its isomers.
  • zeolites can be modified to enhance their molecular-sieving or shape-selective capability. Such modification treatments are usually called zeolite selectivation.
  • Selectivated zeolites can more accurately differentiate molecules on the basis of molecular dimension or steric characteristics than the unselectivated precursors. For example, silanized ZSM-5 zeolites adsorbed PX much more preferentially over MX than untreated ZSM-5. It is believed that the deposition of silicon oxide onto zeolite surfaces from the silanization treatment has (1 ) passivated the active sites on the external surface of zeolite crystals, and (2) narrowed zeolitic pores to facilitate the passage of the smaller PX molecules and prevent the bigger MX and OX molecules from entering or exiting the pores.
  • para-alkyl selectivation refers to modifying a catalyst or catalytic reaction system so that it preferentially forms more para-substituted dialkylbenzenes than the expected equilibrium proportions relative to the other isomers.
  • Zeolite selectivation can be accomplished using many techniques. Reports of using compounds of silicon, phosphorous, boron, antimony, coke, magnesium, etc. for selectivation have been documented.
  • a method for modifying catalysts involving contacting first component, such as crystalline or amorphous aluminosilicates, substituted aluminosilicates, substituted silicates, crystalline or amorphous aluminophosphates, zeolite-bound zeolites, substituted aluminophosphates, and mixtures thereof with an agent which may be compounds of elements selected from Groups 1 through 16, and mixtures thereof.
  • first component such as crystalline or amorphous aluminosilicates, substituted aluminosilicates, substituted silicates, crystalline or amorphous aluminophosphates, zeolite-bound zeolites, substituted aluminophosphates, and mixtures thereof.
  • catalysts particularly zeolite catalysts
  • organometaUic compounds in such a way to enhance selectivity to para-substituted alkyl benzenes in the synthesis of alkyl benzenes. It will be appreciated that the modified catalysts of this invention will find utility in catalyzing other reactions.
  • the improvement in para-substituted selectivity is achieved by treating the catalysts with proper chemical compounds of elements selected from Groups 1-16, and mixtures thereof, to (1 ) inhibit the external acidic sites to minimize aromatic alkylation on the non-para positions, and/or the isomerization of the para-substituted compounds, and/or (2) impose more restrictions on the channel structure to facilitate the formation and transport of para-substituted aromatic compounds, in one non-limiting explanation of the mechanism of the invention. It must be understood that such treatment may be performed on aluminophosphate catalyst reaction systems of this invention, but that some aluminophosphate catalyst reaction systems do not require this para- substituted selectivation treatment to be effective at para-substituent selectivation.
  • the catalytic reaction systems suitable for this invention include (1 ) a first component of one or more than one silicate-based materials, including but not necessarily limited to, crystalline or amorphous aluminosilicates, substituted aluminosilicates, substituted silicates, zeolite- bound zeolites, and/or crystalline or amorphous aluminophosphates, and/or substituted aluminophosphates and mixtures thereof, and, optionally (2) a second component of one or more than one of the metals or oxides of the metals selected from Groups 1 , 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 , 12, 13, 14, 15, and 16 (new IUPAC notation, e.g.
  • the first and second components may be chemically mixed, physically mixed, and combinations thereof, as will be described.
  • the composition of the proposed catalyst reaction systems may range from 95 wt.% silicate-based material or aluminophosphate-based material first component/5 wt.% metals or metal oxides second component, if present, to 5 wt.% silicate-based material or aluminophosphate-based material first component/95 wt.% metals or metal oxides second component, if present.
  • the selectivation techniques of this invention may be practiced before or after the silicate-based materials or aluminophosphate-based materials are mixed with or combined chemically or physically with metals or metal oxides, if used. That is, in some embodiments, the silicate-based materials and aluminophosphate-based materials may be selectivated before combination with metals or metal oxides. In other embodiments, silicate-based materials and aluminophosphate-based materials may be selectivated after combination with metals or metal oxides. The former process might be termed "pre- selectivation", while the latter process may be termed "post-selectivation".
  • zeolite materials such as silicate-based zeolites such as faujasites, morden ⁇ tes, pentasils, etc.
  • Zeolite materials suitable for this invention include silicate-based zeolites and amorphous compounds.
  • Silicate-based zeolites are made of alternating SiO 2 and MO x tetrahedra, where in the formula M is an element selected from the Groups 1 through 16 of the Periodic Table (new IUPAC). These types of zeolites have 8-, 10-, or 12-membered oxygen ring channels. Silicate-based materials are generally acidic.
  • the more preferred zeolites of this invention include 10- and 12-membered ring zeolites, such as ZSM-5, ZSM-11 , ZSM-22, ZSM-48, ZSM-57, etc.
  • silicate-based materials have one-dimensional channel structures, which are capable of generating higher-than-equilibrium PX selectivity. These materials may optionally be para-substituent selectivated. Other silicate-based materials having two- or three- dimensional channel structures are preferably para- substituent selectivated or modified to be more selective through the use of certain chemical compounds, as will be described, such as organometaUic compounds and compounds of elements selected from Groups 1-16.
  • the selectivation of the zeolite materials including the silicate-based materials can be accomplished using compounds including, but not necessarily limited to silicon, phosphorus, boron, antimony, magnesium compounds, coke, and the like, and mixtures thereof.
  • silicate-based materials suitable for the second component include zeolite bound zeolites as described in WO 97/45387.
  • Zeolite bound zeolite catalysts useful in the present invention concern first crystals of an acidic intermediate pore size first zeolite and a binder comprising second crystals of a second zeolite.
  • the zeolite bound zeolite catalyst suitable for use in the present process does not contain significant amounts of non-zeolitic binders.
  • the first zeolite used in the zeolite bound zeolite catalyst is an intermediate pore size zeolite.
  • Intermediate pore size zeolites have a pore size from about 5 to about 7 A and include, for example, AEL, MFI, MEL, MFS, MEI, MTW, EUO, MTT, HEU, FER, and TON structure type zeolites. These zeolites are described in Atlas of Zeolite Structure Types, eds. W. H. Meier and D. H. Olson, Butterworth-Heineman, Third Edition, 1992.
  • Examples of specific intermediate pore size zeolites include, but are not limited to, ZSM-5, ZSM-11 , ZSM-12, ZSM-22, ZSM-23, ZSM-34, ZSM-35, ZSM-38, ZSM-48, ZSM-50, and ZSM-57.
  • Preferred first zeolites are galliumsilicate zeolites having an MFI structure and aluminosilicate zeolites having an MFR structure.
  • the second zeolite will usually have an intermediate pore size and have less activity than the first zeolite.
  • the second zeolite will be substantially non-acidic and will have the same structure type as the first zeolite.
  • the preferred second zeolites are aluminosilicate zeolites having a silica to alumina mole ratio greater than 100 such as low acidity ZSM-5. If the second zeolite is an aluminosilicate zeolite, the second zeolite will generally have a silica to alumina mole ratio greater than 200:1 , e.g., 500:1 ; 1 ,000:1 , etc., and in some applications will contain no more than trace amounts of alumina.
  • the second zeolite can also be silicalite, i.e., a MFI type substantially free of alumina, or silicalite 2, a MEL type substantially free of alumina.
  • the second zeolite is usually present in the zeolite bound zeolite catalyst in an amount in the range of from about 10% to 60% by weight based on the weight of the first zeolite and, more preferably, from about 20% to about 50% by weight.
  • the second zeolite crystals preferably have a smaller size than the first zeolite crystals and more preferably will have an average particle size from about 0.1 to about 0.5 microns.
  • the second zeolite crystals, in addition to binding the first zeolite particles and maximizing the performance of the catalyst will preferably intergrow and form an overgrowth which coats or partially coats the first zeolite crystals.
  • the crystals will be resistant to attrition.
  • the zeolite bound zeolite catalyst suitable for the process of the present invention is preferably prepared by a three step procedure. The first step involves the synthesis of the first zeolite crystals prior to converting it to the zeolite bound zeolite catalyst.
  • a silica-bound aluminosilicate zeolite can be prepared preferably by mixing a mixture comp ⁇ sing the aluminosilicate crystals, a silica gel or sol, water and optionally an extrusion aid and, optionally, the metal component until a homogeneous composition in the form of an extrudable paste develops.
  • the final step is the conversion of the silica present in the silica-bound catalyst to a second zeolite which serves to bind the first zeolite crystals together.
  • aluminophosphate-based materials may be used in conjunction with metal oxides for aromatic alkylation with syngas.
  • Aluminophosphate-based materials usually have lower acidity compared to silicate-based materials.
  • the lower acidity eliminates many side reactions, raises reactants' utilization, and extends catalyst life.
  • Further catalytic reaction systems suitable for this invention include aluminophosphate-based materials and amorphous compounds.
  • Aluminophosphate-based materials are made of alternating AIO 4 and PO 4 tetrahedra. Members of this family have 8- (e.g. AIPO 4 -12, -17, -21 , -25, - 34, -42, etc.), 10- (e.g. AIPO 4 -11 , 41 , etc.), or 12- (AIPO -5, -31 , etc.) membered oxygen ring channels. Although AIPO 4 s are neutral, substitution of Al and/or P by cations with lower charge introduces a negative charge in the framework, which is countered by cations imparting acidity.
  • substitution of silicon for P and/or a P-AI pair turns the neutral binary composition (i.e. Al, P) into a series of acidic-ternary- composition (Si, Al, P) based SAPO molecular sieves, such as SAPO-5, -
  • Acidic ternary compositions can also be created by substituting divalent metal ions for aluminum, generating the MeAPO materials.
  • Me is a metal ion which can be selected from the group consisting of, but not limited to, Mg, Co, Fe, Zn and the like. Acidic materials such as MgAPO (magnesium substituted), CoAPO
  • substitution can also create acidic quaternary-composition based materials such as the MeAPSO series, including FeAPSO (Fe, Al, P, and Si), MgAPSO (Mg, Al, P, Si), MnAPSO, CoAPSO, ZnAPSO (Zn, Al, P, Si), etc.
  • Some preferred aluminophosphate-based materials of this invention include 10- and 12-membered ring molecular sieves (SAPO-11 , -31 , -41 ; MeAPO-11 , -31 , -41 ; MeAPSO-11 , -31 , 41 ; EIAPO-11 , -31 , -41 ; EIAPSO-11 , -31 , -41 , etc.) which already have significant shape selectivity due to their narrow channel structure.
  • SAPO-11 , -31 , -41 10- and 12-membered ring molecular sieves
  • MeAPO-11 , -31 , -41 MeAPSO-11 , -31 , 41 ;
  • EIAPO-11 , -31 , -41 EIAPSO-11 , -31 , -41 , etc.
  • aluminophosphates may be para-alkyl selectivated or modified to be more selective through the use of certain chemical compounds, as will be described, such as organometaUic compounds and compounds of elements selected from Groups 1-16.
  • the para-alkyl selectivation of the zeolite materials including the aluminophosphate-based materials can be accomplished using compounds including, but not necessarily limited to silicon, phosphorus, boron, antimony, magnesium compounds, coke, and the like, and mixtures thereof.
  • the preparation of the catalytic reaction systems can be accomplished with several techniques known to those skilled in the art. Some examples are given below.
  • Para-selectivation involves the treatment of the above mentioned catalytic reaction system materials with proper chemical compounds of elements selected from Groups 1-16, and mixtures thereof.
  • the composition of the selectivated catalyst may range from 1 wt.% of the seiectivating elements/99 wt.% of the first component to 99 wt.% of the selectivating elements/1 wt.% of the first component.
  • selectiveating elements is meant the elemental portion of the elemental form or elemental oxide form of the seiectivating chemical compounds.
  • Some para-substituent selectivation treatments are known, e.g. using silicon compounds. Other compounds that may be used include, but are not limited to compounds of phosphorus, boron, antimony, magnesium, and the like, and coke, and the like.
  • Para-substituent selectivation treatments of the mate ⁇ als of the above catalytic reaction systems can be carried out either prior to the selective formation of PX (ex situ) or during the PX formation (in situ), to use PX formation as a non- limiting example.
  • the seiectivating agents are added with the feed to the reactor containing a catalytic reaction system.
  • the technique for seiectivating the materials according to the method of this invention is based on the consideration that by depositing on a silicate-based material or aluminophosphate-based material one or more than one of the organometaUic compounds which are too bulky to enter the channels (or other seiectivating agent), one should be able to modify only the external surface and regions around channel mouth.
  • the fact that the selectivation agent does not enter the channels preserves the active sites inside the channels. Since the channel active sites account for more the majority of the total active sites, their remaining active prevents any significant loss of reactivity or conversion.
  • One type of the bulky organometaUic compounds suitable for seiectivating 10-member-ring zeolites, such the ZSM family (e.g. ZSM-5, - 11 , -22, -48, etc.), mordenite, etc., is the salts of large organic anions and metallic cations.
  • the organic anions can be selected from molecules containing carboxylic and/or phenolic functional groups, including but not limited to phthalate, ethylenediaminetetraacetic acid (EDTA), vitamin B-5, trihydroxy benzoic acid, pyrogallate, salicylate, sulfosalicylate, citrate, naphthalene dicarboxylate, anthradiolate, camphorate, and others.
  • the metallic cations can be selected from the element(s) of Groups 1 , 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 , 12, 13, 14, 15, and 16 (new IUPAC notation).
  • Other compounds for seiectivating the silicate-based and aluminophosphate- based materials include, but are not necessarily limited to silicon, phosphorus, boron, antimony, magnesium compounds, coke, and the like, and mixtures thereof.
  • Selectivation of silicate-based materials and aluminophosphate- based materials with the above-mentioned organometaUic salts can be accomplished by various means. For example, one can use impregnation of a solution of an organometaUic salt onto a silicate-based material or aluminophosphate-based material. Either water or any suitable organic solvent can be used. Addition of non-metallic salts and/or adjustments of pH to facilitate the treatment are optional. Heat will be provided to drive off the solvent, leaving behind a material coated homogeneously with the organometaUic salt.
  • Drying and calcination of the coated zeolite or aluminophosphate-based material at appropriate temperatures will turn the salt into metal oxide form or elemental metal form (agent derivative).
  • a dry-mix technique which involves mixing directly a zeolite in the form of powder or particles with an organometaUic salt also in the form of powder or particles without the use of any solvent.
  • the mixture will then be subjected to heat treatment, which facilitates the dispersion of the salt over the material and eventually turns the salt into elemental form or metal oxide form (agent derivative).
  • the catalytic reaction systems can be prepared by adding solutions of elemental metal salts either in series to or as a mixture with the fine powder or particles such as extrudates, spheres, etc. of the unselectivated silicate-based materials having one dimensional channel structures, or optionally ex situ selectivated silicate-based materials, unselectivated aluminophosphate-based materials, or optionally ex situ selectivated aluminophosphate-based materials, until incipient wetness is reached.
  • the solvent water or other solvents
  • the solvent can be evacuated under heat or vacuum using typical equipment such as a rotary evaporator.
  • the final product is dried, calcined, and pelletized, if necessary.
  • solutions of metal salts and the ex situ selectivated fine powder or particles such as extrudates, spheres, etc. of silicate-based and aluminophosphate-based materials are thoroughly mixed.
  • a dilute basic solution e.g. ammonia, sodium carbonate, potassium hydroxide, etc.
  • the precipitate is filtered and washed thoroughly with water.
  • the final product is dried, calcined, and pelletized, if necessary.
  • the catalytic reaction systems can also be prepared using physical mixing. Finely divided powders of metal(s) or metal oxide(s), or powders of metal(s) or metal oxide(s) supported on any inert materials, are mixed thoroughly with finely divided powder of the ex situ selectivated silicate- based materials, unselectivated aluminophosphate-based materials, or optionally ex situ selectivated aluminophosphate-based materials in a blending machine or a grinding mortar. The mixture is optionally pelletized before use.
  • an extrudable paste may be formed.
  • the resulting paste can be molded, e.g. extruded, and cut into small strands which can then be dried and calcined.
  • the catalytic reaction system can also be prepared by mixing physically the particles of silicate-based material or aluminophosphate- based materials components and the particles of the metal and/or metal oxide second components, if present.
  • the same metals and/or metal oxides can also be used alone or together to selectivate catalytic reaction systems and thus simultaneously catalyze syngas and/or other reactions.
  • the catalytic reaction system can also be formed by packing the first and the second components, if present, in a stacked-bed manner with some of the first component in front of the physical or chemical mixture of the first and second components.
  • the catalyst reaction systems Prior to exposing the catalysts to the feed components of toluene and/or benzene, H 2 , CO, and/or CO 2 and/or methanol, the catalyst reaction systems can optionally be activated under a reducing environment (e.g. 1-80% H 2 in N 2 ) at 150-500°C, and 1-200 atm (1.01 x 10 5 - 2.03 x 10 7 Pa) for 2-48 hours.
  • a reducing environment e.g. 1-80% H 2 in N 2
  • 1-200 atm (1.01 x 10 5 - 2.03 x 10 7 Pa
  • the average crystal size of the crystals in the silicate-based material or aluminophosphate-based materials is preferably from above
  • micron 0.1 micron to about 100 microns, more preferably from about 1 micron to about 100 microns.
  • crystal size may be determined directly by taking a suitable scanning electron microscope (SEM) picture of a representative sample of the crystals.
  • SEM scanning electron microscope
  • the catalysts of this invention may be used in a methylation process which can be carried out as a batch type, semi-continuous or continuous operation utilizing a fixed or moving bed catalyst system. Multiple injection of the methylating agent may be employed.
  • the methylating agent includes CO, CO 2 and H 2 and/or CH 3 OH and derivatives thereof.
  • the methylating agent reacts with benzene to form toluene.
  • Toluene reacts with the methylating agent to form a xylene, preferably PX in this invention.
  • Toluene and/or benzene and the methylating agent(s) are usually premixed and fed together into the reaction vessel to maintain the desired ratio between them with no local concentration of either reactant to disrupt reaction kinetics.
  • the catalytic reaction systems of this invention have the capability of preventing or reducing the side reactions of the methylating agents with themselves, and in particular that the para- substituent selectivated catalytic reaction systems function to catalyze more than one reaction, that is, that a syngas reaction is catalyzed to form methylating agents which react with benzene and/or toluene to produce PX, e.g.
  • a syngas reaction is catalyzed to form methylating agents which react with benzene and/or toluene to produce PX, e.g.
  • the methylating agent is produced on a local, molecular scale, its concentrations are very low (as contrasted with feeding a methylating agent as a co-reactant).
  • the catalyst activity decrease is less than 0.5% toluene and/or benzene conversion per day, preferably less than 0.1%
  • the feed mixtures can be co-fed into a reactor containing one of the above mentioned catalytic reaction systems.
  • the catalytic reaction system and reactants can be heated to reaction temperatures separately or together. Reaction can be carried out at a temperature from about 100-700°C, preferably from about 200-600°C; at a pressure from about 1-300 atm (1.01 x 10 5 -3.04 x 10 7
  • composition of the feed i.e. the mole ratio of H 2 /CO(and/or CO 2 )/aromatic can be from of about 0.01-10/0.01- 10/0.01-10, preferably from about 0.1-10/0.1-10/0.1-10.
  • typical methylating agents include or are formed from, but are not necessarily limited to hydrogen together with carbon monoxide and/or carbon monoxide, and/or methanol, but also dimethylether, methylchloride, methylbromide, and dimethylsulfide.
  • the toluene can be pure, or in a mixture with benzene.
  • the benzene may alkylate to toluene, and/or ultimately to PX, with or without recycle.
  • the presence of benzene may also enhance heat and/or selectivity control.
  • Unextracted toluene which is a mixture of toluene and similar boiling range olefins and paraffins, is preferred in one embodiment.
  • premium extracted toluene essentially pure toluene
  • extracted aromatics essentially a relatively pure mixture of toluene and benzene
  • Unextracted toluene and benzene which contains toluene, benzene, and olefins and paraffins that boil in a similar range to that of toluene or benzene, may also be employed.
  • the feed may contain one or more paraffins and/or olefins having at least 4 carbon atoms; the catalytic reaction systems have the dual function to crack the paraffins and/or olefins and methylate benzene or toluene to selectively produce PX.
  • some of the catalytic reaction systems of this invention may be multifunctional in some embodiments, catalyzing a reaction or reactions of CO, H 2 , and/or CO 2 and/or methanol to produce a methylating agent, catalyzing the selective methylation of toluene and/or benzene to produce PX, and catalyzing the cracking of paraffins and olefins into relatively lighter products.
  • the PX method is capable of producing mixtures of xylenes where PX comprises at least 30 wt.% of the mixture, preferably at least 36 wt.%, and most preferably at least 48 wt.%.
  • the method of this invention is also capable of converting at least 5 wt.% of the aromatic compound to a mixture of xylenes, preferably greater than 15 wt.%.
  • This example illustrates the lack of para-selectivity from an untreated ZSM-5 for toluene methylation with methanol.
  • the ZSM-5 zeolite had a SiO 2 /AI 2 O 3 ratio of 38. It was tested at the conditions of
  • This example illustrates the loss of zeolite activity or conversion from conventional selectivation techniques that use compounds which are small enough to enter the zeolite channels.
  • Toluene methylation results on this double-treated zeolite showed a toluene conversion of 18% and a PX concentration in the xylene-fraction product of 90%. Comparing Example II to Example I, it is apparent that an increase of PX selectivity from 24% to 90% lowered the conversion from 46% to 18%.
  • This example illustrates the use of bulky organometaUic salts for zeolite selectivation.
  • An aqueous solution of lanthanum nitrate was prepared by dissolving 18.0 gram of La(NO 3 ) 3 -6H 2 O in 80.0 cc of water. 60 cc of 25% ammonia solution was added to the lanthanum solution with stirring. The addition was completed in a period of 10 minutes. The precipitate of La(OH) 3 was filtered and suspended into 300 cc of water.
  • EDTA ethylenediaminetetraacetic acid
  • the La-treated zeolite was tested for toluene methylation with methanol at the same conditions as that in Examples I and II. Test results indicated a toluene conversion of 38% and a PX selectivity of 81 %.
  • This example illustrates the use of another bulky organometaUic salt for zeolite selectivation.
  • An aqueous solution of Mg(NO 3 ) 2 was prepared by mixing 128.35 g of Mg(NO 3 ) 2 -6H 2 O in 300 cc water. 60 cc of 25% ammonia solution was added to the Mg(NO 3 ) 2 solution with stirring in a 10 minutes period. The Mg(OH) 2 precipitate was filtered and suspended in 500 cc water. 66.36 g phthalic acid was deeded to the suspension with stirring and heating to obtain a clear solution, which was boiled and concentrated to 300 cc. It was cooled to room temperature and filtered to obtain a Mg-phthalate filtrate having a concentration of 0.017g Mg per cc of filtrate.
  • the catalyst comprises (1 ) Cr and Zn mixed metal oxides; and (2) H-ZSM- 5 zeolite with a SiO 2 /AI 2 O 3 molar ratio of 30 (obtained from PQ
  • the Cr and Zn mixed metal oxides were prepared by co-precipitation of Cr(NO 3 ) 3 and Zn(NO 3 ) 2 with NH OH. 7.22 grams of Cr(NO 3 ) 3 and 13.41 grams of Zn(NO 3 ) 2 were dissolved in 100 ml distilled water separately. The two solutions were then mixed together. NH 4 OH was slowly added into the mixed solution with stirring until the pH value of the solution reached about 8. The precipitate was filtered and recovered. This precipitate was dried at a temperature of 120°C for 12 hours, and then calcined in air at 500°C for 6 hours. These Cr/Zn mixed metal oxides were ground into powders.
  • the catalytic reaction system was prepared by physically mixing powders of a composition of 50% (w/w) Cr/Zn mixed metal oxides and 50% (w/w) H-ZSM-5 zeolite. Powders of 2.0 grams of Cr/Zn mixed metal oxides and 2.0 grams of H-ZSM-5 zeolite were mixed thoroughly in a grinding mortar. The mixed catalytic reaction system powders were pelletized and screened to 8-12 mesh (0.89-0.73 cm) particles.
  • This example shows that the synthesis of xylenes with syngas alkylation of toluene can be achieved in a catalytic process as disclosed in a prior process. However, this example indicates that this process cannot achieve high para-xylene selectivity when the aluminosilicate component in the catalytic reaction system is not modified for shape selectivity.
  • the catalytic reaction system was prepared as in Example V. The catalyst was reduced at 350°C under 5% H 2 (balanced with 95% N 2 ) for 16 hours at 1 atm prior to reaction.
  • the catalytic reaction system was evaluated with co-feed of syngas (CO and H 2 ) and toluene with a composition of H 2 /CO/toluene of 2/1/0.5 (molar ratio), a temperature of about 450°C, and a pressure of about 18 atm (i.e., 250 psig, 2.53 x 10 7 Pa).
  • the WHSV Weight Hourly Space Velocity
  • Test results are given in Table 1. Similar to prior art reported, the selectivity of para-xylene in xylenes is about 25%, which is close to equilibrium, with toluene conversion of 28.6% and xylene selectivity of 71.1 %.
  • ZSM-5 zeolite with magnesium oxide as the seiectivating agent 11.68 grams of magnesium hydroxide was mixed with distilled water. To the solution was added 20.44 grams of ammonium nitrate and 33.54 grams of phthalic acid in sequence. The mixture was heated to obtain a clear solution, which was cooled to room temperature before use. 14.80 grams of the solution was mixed with 7.77 grams of a ZSM-5 zeolite (SiO 2 /AIO 2 of 50). The mixture was heated to evaporate the water solvent. The remaining solid was dried at 120°C for 12 hours and calcined at 500°C for 8 hours with air purge. The para-alkyl selectivated ZSM-5 zeolite contained approximately 9 wt.% of magnesium oxide. INVENTIVE EXAMPLE VIII
  • the catalytic reaction system comprises (1 ) Mn and Zn mixed metal oxides, and (2) MgO modified H-ZSM-5 zeolite with a SiO 2 /AIO 2 of 38.
  • the same preparation procedures as that given in Example VII were used.
  • the Mn and Zn mixed metal oxides were prepared by co-precipitation of Mn(NO 3 ) 2 and Zn(NO 3 ) 2 with NH 4 OH. 4.14 grams of Mn(NO 3 ) 2 and 13.44 grams of Zn(NO 3 ) 2 were dissolved in 100 ml distilled water separately. The two solutions were then mixed together.
  • the catalytic reaction system was prepared by physically mixing powders of a composition of 50% (w/w) Mn/Zn mixed metal oxides and 50% (w/w) MgO modified H-ZSM-5 zeolite. Powders of 2.0 grams of Mn/Zn mixed metal oxides and 2.0 grams of MgO modified H-ZSM-5 zeolite were mixed thoroughly in a grinding mortar. The mixed catalytic reaction system powders were pelletized and screened to 8-12 mesh (0.89-0.73 cm) particles.
  • This example illustrates that metal oxides other than Cr/Zn mixed metal oxides are also suitable as one of the components in the catalytic reaction system used in the xylenes synthesis with syngas alkylation of toluene.
  • this example demonstrates that high para-xylene selectivity can be obtained when the aluminosilicate component in the catalytic reaction system is modified for shape selectivity.
  • the catalytic reaction system was prepared as in Example VIII. The catalytic reaction system was reduced at 350°C under 5% H 2 (balanced with 95% N 2 ) for 16 hours at 1 atm prior to reaction.
  • Example VI The reaction was conducted under similar conditions to those in Example VI. Test results are given in Table 2.
  • the para-xylene selectivity in xylenes is about 76.0% with toluene conversion of 10.9% and xylene selectivity of 85.4%.
  • the para-xylene selectivity is significantly enhanced when the aluminosilicate component is modified for shape selectivity.
  • the catalytic reaction system used in this example was comprised of a composition of (1 ) 50% (w/w) Cr, Zn, and Mg mixed metal oxides, and (2) 50% (w/w) MgO modified H-ZSM-5 zeolite with a SiO 2 /AIO 2 of 38.
  • the Cr, Zn, and Mg mixed metal oxides were prepared in a similar method as described in Example V with co- precipitation of Cr(NO 3 ) 3 , Zn(NO 3 ) 2 , and Mg(NO 3 ) 2 with NH 4 OH.
  • the magnesium oxide-modified ZSM zeolite was prepared as described in Example VIII.
  • the catalytic reaction system was prepared by physical mixing as described in Example V.
  • the catalytic reaction system was reduced at 350°C under 5% H 2 (balanced with 95% N 2 ) for 16 hours at 1 atm (1.01 x 10 5 Pa) prior to reaction.
  • the catalytic reaction system was evaluated with co-feed of syngas (CO and H 2 ) and toluene with a varied composition of H 2 /CO/toluene, a temperature from 450-490°C, and a pressure in the range of 18-28 atm (i.e. 250-390 psig, 2.53 x 10 7 -3.95 x 10 7 Pa).
  • the WHSV Weight Hourly Space Velocity
  • Table 3 Some of the test results are shown in Table 3. As shown in Table 3, a toluene conversion of 34% was achieved with a similar para-xylene selectivity when the reaction was operated at a temperature of ca. 460°C, a pressure of ca. 28 atm (390 psig.), and a WHSV of ca. 1.5 h " for toluene with respect to catalytic reaction system.
  • Feed Composition mole ratio 2/1/0.25 2/1/0.25 2/1/0.5 2/1/0.5
  • This example illustrates the problems of low methanol selectivity and fast catalytic reaction system deactivation associated with a low aromatic/methanol ratio and one-time methanol injection.
  • the catalytic reaction system was extrudates of SAPO-11 material obtained from UOP. The extrudates were ground and screened to 8-12 mesh (0.89-0.73 cm) and calcined at 550°C under air for 16 hours prior to use.
  • the catalytic reaction system was evaluated at 350°C, 25 atm (350 psig, 3.55 x 10 7 Pa), and 8 h " WHSV.
  • the feed was a mixture of toluene/methanol with a molar ratio of 3.6. Test results are given in Table 4.
  • This example demonstrates the problems of fast catalytic reaction system deactivation for MgO para-alkyl selectivated H-ZSM-5 in toluene methylation with low toluene/methanol ratio and one-time methanol injection.
  • the catalytic reaction system was MgO-para-alkyl selectivated H-ZSM-5 with a SiO 2 /AIO 2 ratio of 38.
  • the same preparation procedure as that given in Example VIII was used.
  • the catalytic reaction system was pelletized and screened to 40-60 mesh.
  • the catalytic reaction system was tested at 460°C, 1 atm, and 14 h "1 WHSV.
  • the feed was a mixture of toluene/methanol with a molar ratio of 1.0.
  • the Cr and Zn mixed metal oxides were prepared as described in Example I.
  • the magnesium oxide-modified ZSM zeolite was prepared as described in Example V.
  • the Cr/Zn mixed metal oxides were ground into powders.
  • the catalytic reaction system was prepared by physically mixing powders of a composition of (1 ) 34% (w/w) Cr and Zn mixed metal oxides, and (2) 66% MgO modified H-ZSM-5 zeolite.
  • the mixed catalytic reaction system powders were pelletized and screened to 8-12 mesh (0.89-0.73 cm) particles.
  • the catalytic reaction system was reduced at 350°C under 5% H 2 (balanced with 95% N 2 ) for 16 hours at 1 atm (1.01 x 10 5 Pa) prior to reaction.
  • the organometaUic modifier was magnesium phthalate.
  • the catalytic reaction system was evaluated with similar operation conditions as those in Example II. Test results are given in Table 7. It is seen that the catalytic reaction system had a stable activity for toluene conversion with stable PX selectivity.

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Abstract

Cette invention concerne la modification de catalyseurs par dépôt à la surface de ces catalyseurs d'un agent dérivé d'un agent du type composé organométallique. Une telle modification permet d'obtenir un catalyseur à sélectivité accrue face aux alkylbenzènes para-substitués, tels que le para-xylène (PX), par réaction d'un composé aromatique tel que le toluène et/ou le benzène, avec un agent de méthylation sélectionné parmi l'hydrogène et le monoxyde de carbone et/ou le dioxyde de carbone et/ou le méthanol. L'utilisation de ces catalyseurs à sélectivité accrue permet la récupération d'alkylbenzènes para-substitués avec une sélectivité supérieure ou égale à 80 %, largement supérieure à la concentration d'équilibre de 24 %.
PCT/US2000/013003 1999-05-14 2000-05-11 Accroissement de la selectivite d'un catalyseur WO2000074847A1 (fr)

Priority Applications (5)

Application Number Priority Date Filing Date Title
BR0011679-3A BR0011679A (pt) 1999-06-07 2000-05-11 Seletivação de catalisador
CA002371225A CA2371225A1 (fr) 1999-05-14 2000-05-11 Accroissement de la selectivite d'un catalyseur
EP00935926A EP1189697A1 (fr) 1999-05-14 2000-05-11 Accroissement de la selectivite d'un catalyseur
MXPA01012623A MXPA01012623A (es) 1999-05-14 2000-05-11 Selectivacion de catalizador.
AU51312/00A AU5131200A (en) 1999-06-07 2000-05-11 Catalyst selectivation

Applications Claiming Priority (4)

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US09/312,104 1999-05-14
US09/312,104 US6388156B1 (en) 1999-05-14 1999-05-14 Direct selective synthesis of para-xylene by reacting an aromatic compound with a methylating agent formed from CO, Co2 and H2
US09/327,241 US6613708B1 (en) 1999-06-07 1999-06-07 Catalyst selectivation
US09/327,241 1999-06-07

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WO2004043593A1 (fr) * 2002-11-14 2004-05-27 Exxonmobil Chemical Patents Inc. Procede de production de para-xylene mettant en oeuvre une methode de selection in situ d'un catalyseur
WO2006043767A1 (fr) 2004-10-18 2006-04-27 Lg Chem, Ltd. Catalyseur de craquage d'hydrocarbures mettant en oeuvre la deposition chimique en phase liquide et procede de preparation de celui-ci
CN105163851A (zh) * 2013-04-29 2015-12-16 沙特基础工业公司 石脑油转化成烯烃的催化方法

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DE102006003954A1 (de) * 2006-01-26 2007-08-02 Sick Ag Lichtgitter
CN102464540B (zh) * 2010-11-17 2016-07-06 中国石油化工股份有限公司 用于生产对位烷基化芳烃的方法

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Publication number Priority date Publication date Assignee Title
WO2004043593A1 (fr) * 2002-11-14 2004-05-27 Exxonmobil Chemical Patents Inc. Procede de production de para-xylene mettant en oeuvre une methode de selection in situ d'un catalyseur
US7902414B2 (en) 2002-11-14 2011-03-08 Exxonmobil Chemical Patents Inc. Para-xylene production process employing in-situ catalyst selectivation
WO2006043767A1 (fr) 2004-10-18 2006-04-27 Lg Chem, Ltd. Catalyseur de craquage d'hydrocarbures mettant en oeuvre la deposition chimique en phase liquide et procede de preparation de celui-ci
EP1809417A1 (fr) * 2004-10-18 2007-07-25 LG Chemical Limited Catalyseur de craquage d'hydrocarbures mettant en oeuvre la deposition chimique en phase liquide et procede de preparation de celui-ci
EP1809417A4 (fr) * 2004-10-18 2010-12-22 Lg Chemical Ltd Catalyseur de craquage d'hydrocarbures mettant en oeuvre la deposition chimique en phase liquide et procede de preparation de celui-ci
CN105163851A (zh) * 2013-04-29 2015-12-16 沙特基础工业公司 石脑油转化成烯烃的催化方法
US10099210B2 (en) 2013-04-29 2018-10-16 Saudi Basic Industries Corporation Catalytic methods for converting naphtha into olefins

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