WO2016140900A1 - High meso-surface area pentasil zeolite for use in xylene conversion - Google Patents

High meso-surface area pentasil zeolite for use in xylene conversion Download PDF

Info

Publication number
WO2016140900A1
WO2016140900A1 PCT/US2016/020007 US2016020007W WO2016140900A1 WO 2016140900 A1 WO2016140900 A1 WO 2016140900A1 US 2016020007 W US2016020007 W US 2016020007W WO 2016140900 A1 WO2016140900 A1 WO 2016140900A1
Authority
WO
WIPO (PCT)
Prior art keywords
xylene
mole ratio
value
zeolite
para
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/US2016/020007
Other languages
French (fr)
Inventor
Gregory B. KUZMANICH
Jaime G. Moscoso
Deng-Yang Jan
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Honeywell UOP LLC
Original Assignee
UOP LLC
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by UOP LLC filed Critical UOP LLC
Publication of WO2016140900A1 publication Critical patent/WO2016140900A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/22—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by isomerisation
    • C07C5/27—Rearrangement of carbon atoms in the hydrocarbon skeleton
    • C07C5/2729—Changing the branching point of an open chain or the point of substitution on a ring
    • C07C5/2732—Catalytic processes
    • C07C5/2737—Catalytic processes with crystalline alumino-silicates, e.g. molecular sieves
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/40—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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/64—Pore diameter
    • B01J35/643—Pore diameter less than 2 nm
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/64—Pore diameter
    • B01J35/647—2-50 nm
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/70—Catalysts, in general, characterised by their form or physical properties characterised by their crystalline properties, e.g. semi-crystalline
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/70—Catalysts, in general, characterised by their form or physical properties characterised by their crystalline properties, e.g. semi-crystalline
    • B01J35/77—Compounds characterised by their crystallite size
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
    • C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
    • C01B39/36—Pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/22—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by isomerisation
    • C07C5/27—Rearrangement of carbon atoms in the hydrocarbon skeleton
    • C07C5/2702—Catalytic processes not covered by C07C5/2732 - C07C5/31; Catalytic processes covered by both C07C5/2732 and C07C5/277 simultaneously
    • C07C5/2708—Catalytic processes not covered by C07C5/2732 - C07C5/31; Catalytic processes covered by both C07C5/2732 and C07C5/277 simultaneously with crystalline alumino-silicates, e.g. molecular sieves
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/22—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by isomerisation
    • C07C5/27—Rearrangement of carbon atoms in the hydrocarbon skeleton
    • C07C5/2767—Changing the number of side-chains
    • C07C5/277—Catalytic processes
    • C07C5/2775—Catalytic processes with crystalline alumino-silicates, e.g. molecular sieves
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C7/00—Purification; Separation; Use of additives
    • C07C7/005—Processes comprising at least two steps in series
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C7/00—Purification; Separation; Use of additives
    • C07C7/12—Purification; Separation; Use of additives by adsorption, i.e. purification or separation of hydrocarbons with the aid of solids, e.g. with ion-exchangers
    • 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
    • B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
    • B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
    • 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
    • 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
    • B01J2235/00—Indexing scheme associated with group B01J35/00, related to the analysis techniques used to determine the catalysts form or properties
    • B01J2235/15—X-ray diffraction
    • 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
    • B01J2235/00—Indexing scheme associated with group B01J35/00, related to the analysis techniques used to determine the catalysts form or properties
    • B01J2235/30—Scanning electron microscopy; Transmission electron microscopy
    • 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
    • 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
    • C07C2529/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups C07C2529/08 - C07C2529/65
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Definitions

  • the present invention relates to the use of a new family of aluminosilicate zeolites, having a designation of UZM-54.
  • UZM-54 is characterized by unique x-ray diffraction patterns, high meso-surface area and low Si/Al ratio compositions.
  • aromatics complexes are designed to maximize the yield of benzene and para-xylene.
  • Benzene is a versatile petrochemical building block used in many different products based on its derivation including ethylbenzene, cumene, and cyclohexane.
  • Para- xylene is also an important building block, which is used almost exclusively for the production of polyester fibers, resins, and films formed via terephthalic acid or dimethyl terephthalate intermediates.
  • an aromatics complex may be configured in many different ways depending on the desired products, available feedstocks, and investment capital available. A wide range of options permits flexibility in varying the product slate balance of benzene and para-xylene to meet downstream processing requirements.
  • U.S. Pat. No. 3,996,305 to Berger discloses a fractionation scheme primarily directed to trans alkylation of toluene and Cg alkylaromatics in order to produce benzene and xylene.
  • the trans alkylation process is also combined with an aromatics extraction process.
  • the fractionation scheme includes a single column with two streams entering and with three streams exiting the column for integrated economic benefits.
  • U.S. Pat. No. 4,341,914 to Berger discloses a transalkylation process with recycle of Cg alkylaromatics in order to increase yield of xylenes from the process.
  • transalkylation process is also preferably integrated with a paraxylene separation zone and a xylene isomerization zone operated as a continuous loop receiving mixed xylenes from the transalkylation zone feedstock and effluent fractionation zones.
  • U.S. Pat. No. 4,642,406 to Schmidt discloses a high severity process for xylene production that employs a transalkylation zone that simultaneously performs as an
  • isomerization zone over a nonmetal catalyst.
  • High quality benzene is produced along with a mixture of xylenes, which allows para-xylene to be separated by absorptive separation from the mixture with the isomer-depleted stream being passed back to the trans alkylation zone.
  • U.S. Pat. No. 5,417,844 to Boitiaux et al. discloses a process for the selective dehydrogenation of olefins in steam cracking petrol in the presence of a nickel catalyst and is characterized in that prior to the use of the catalyst, a sulfur-containing organic compound is incorporated into the catalyst outside of the reactor prior to use.
  • a first embodiment of the invention is a process for the production of para-xylene, comprising passing a mixture of hydrocarbons comprising xylenes to an isomerization reactor, operated at isomerization reaction conditions, to form a reaction mixture over an isomerization catalyst, and to generate an effluent stream comprising p-xylene; wherein the isomerization catalyst is UZM-54.
  • the UZM-54 aluminosilicate zeolite is a microporous crystalline structure comprising a framework of A10 2 and Si0 2 tetrahedral units, and an empirical composition in the as synthesized and anhydrous basis expressed by the empirical formula of M m n+ Ri r i p i + R 2 r 2 p 2 + AlSiyOz
  • M is at least one exchangeable cation selected from the group consisting of alkali and alkaline earth metals
  • m is the mole ratio of M to Al and varies from 0 to 1
  • Ri is at least one organoammonium cation selected from the group consisting of quaternary ammonium cations, diquaternary ammonium cations
  • "ri” is the mole ratio of Ri to Al and has a value of 0.1 to 3.0
  • R 2 is at least one organoammonium cation selected from the group consisting of protonated alkanolamines, proto
  • An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph wherein the isomerization reaction conditions include a temperature between 190°C and 350°C.
  • An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph wherein the isomerization reaction conditions include a temperature between 220°C and 270°C.
  • An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph wherein the isomerization reaction conditions include a pressure sufficient to maintain the reaction mixture in the liquid phase.
  • An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph wherein the pressure is at least 1025 kPa.
  • An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph wherein the mixture of hydrocarbons further includes ethylbenzene.
  • An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph where M in the zeolite is selected from the group consisting of lithium, sodium, potassium, cesium, strontium, calcium, barium and mixtures thereof.
  • An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph where M in the zeolite is a mixture of an alkali metal and an alkaline earth metal.
  • An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph where Ri in the zeolite is selected from the group consisting of dimethyldipropylammonimum, diethyldipropylammonium, propyltrimethylammonium, hexamethonium, and mixtures thereof.
  • R 2 in the zeolite is selected from the group consisting of diethanolamine, N-methylethanolamine, 2- dimethylaminoethanol, N-methyldiethanolamine, 2-diethylamino ethanol, 2-isopropylamino ethanol, 2-diisopropylamino ethanol, 3-dimethylamino propanol and 2-aminopropanol and mixtures thereof.
  • An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph wherein the catalyst, UZM- 54, is characterized by a zeolite having a microporous crystalline structure comprising a framework of A10 2 and Si0 2 tetrahedral units, further including the element E and having the empirical composition in the as synthesized and anhydrous basis expressed by the empirical formula of M m n+ Ri n p i + R 2 r2 P 2 + Ali -x E x Si y O z where "m” is the mole ratio of M to (Al+E) and varies from 0 to 1, “ri” is the mole ratio of Ri to (Al+E) and has a value of 0.1 to 3.0, “r 2 " is the mole ratio of R 2 to (Al+E) and has a value of 0 to 3.0, E is an element selected from the group consisting of gallium, iron, boron, indium and mixtures thereof
  • An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph further comprising passing the effluent stream to a para-xylene separation unit to generate a para-xylene process stream and a second stream comprising meta-xylene and ortho-xylene.
  • An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph wherein the separation unit is an adsorption separation unit and generates and extract stream comprising para-xylene and desorbent and a raffinate stream comprising meta-xylene and ortho-xylene.
  • An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph further comprising passing the extract stream to a fractionation unit to generate a bottoms stream comprising para-xylene and an overhead stream comprising desorbent.
  • An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph wherein the raffinate stream is passed to the isomerization reactor.
  • a second embodiment of the invention is a process for the production of para- xylene, comprising passing a mixture of hydrocarbons comprising xylenes to an
  • isomerization reactor operated at isomerization reaction conditions, to form a reaction mixture over an isomerization catalyst of the aluminosilicate zeolite UZM-54, and to generate an effluent stream comprising para-xylene, wherein the catalyst is a zeolite, UZM- 54, of claim 1 having a microporous crystalline structure comprising a framework of A10 2 and Si0 2 tetrahedral units, further including the element E and having the empirical composition in the as synthesized and anhydrous basis expressed by the empirical formula of M m n+ Ri ri p i + R 2 r 2 p 2 + Ali -x E x Si y O z where "m” is the mole ratio of M to (Al+E) and varies from 0 to 1, "ri” is the mole ratio of Ri to (Al+E) and has a value of 0.1 to 3.0, "r 2 " is the mole ratio of R 2 to (Al+E
  • An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the second embodiment in this paragraph wherein the isomerization reaction conditions include a temperature between 190°C and 350°C.
  • An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the second embodiment in this paragraph wherein the isomerization reaction conditions include a pressure sufficient to maintain the reaction mixture in the liquid phase.
  • An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the second embodiment in this paragraph wherein the pressure is at least 1025 kPa.
  • An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the second embodiment in this paragraph wherein the mixture of hydrocarbons further includes ethylbenzene.
  • Para-xylene production is a valuable commercial process, wherein the reduction of losses can entail a significant economic advantage.
  • One method of improving para-xylene yields is to increase the conversion from C 8 compounds to para-xylene and to reduce losses during that conversion.
  • the operating of a liquid phase xylene isomerization reactor using a conventional MFI catalyst generates a significant xylene loss per pass. The loss is greater than 1.0%.
  • the invention of a new catalyst, UZM-54 allows for a significant reduction in the xylene loss.
  • the new catalyst has a new zeolitic MFI morphology, high meso-surface area and low Si/Al ratios and can achieve comparable para-xylene content with xylene losses of around 0.2% or less.
  • the present invention is a process for the production of para-xylene.
  • the process includes passing a mixture of hydrocarbons including xylenes to an isomerization reactor, operated at isomerization reaction conditions to generate an effluent stream having para- xylene, or p-xylene.
  • the reaction conditions include forming a reaction mixture comprising C7-C9 hydrocarbons and passing the mixture over an isomerization catalyst.
  • the present invention utilizes a new catalyst that reduces the loss of xylenes during the isomerization process.
  • the isomerization catalyst is a zeolite having a microporous crystalline structure comprising a framework of A10 2 and Si0 2 tetrahedral units, and an empirical composition in the as synthesized and anhydrous basis expressed by the empirical formula of:
  • the catalyst comprises M, which is at least one exchangeable cation selected from the group consisting of alkali and alkaline earth metals, "m” is the mole ratio of M to Al and varies from 0 to 1, Ri is at least one organoammonium cation selected from the group consisting of quaternary ammonium cations, diquaternary ammonium cations, “ri” is the mole ratio of Ri to Al and has a value of 0.1 to 3.0, R 2 is at least one organoammonium cation selected from the group consisting of protonated alkanolamines, protonated amines, protonated diamines, and quatemized alkanolammonium cations, “r 2 " is the mole ratio of R 2 to Al and has a value of 0 to 3.0, "n” is the weight average valence of M and has a value of 1 to 2, “pi” is the weighted average valence of Ri and has a value of 1 to
  • the catalyst, UZM-54 can be further characterized by its unique x-ray diffraction pattern as at least the d spacing and intensities set forth in Table A: Table A
  • the M in the zeolite can be a mixture of alkali metals and alkaline earth metals, with a preferred M including one or more metals from lithium, sodium, potassium, cesium, strontium, calcium and barium.
  • the Ri cation can be selected from one or more of quaternary ammonium cations, quaternary phosphonium cations, and methonium cations.
  • the Ri cation can come from an halide compound or a hydroxide compound.
  • Preferred Ri cations include one or more from dimethyldipropylammonimum, diethyldipropylammonium, propyltrimethylammonium and hexamethonium.
  • the R2 cation can come from an halide compound or a hydroxide compound.
  • Preferred R2 cations include one or more from diethanolamine, N-methylethanolamine, 2-dimethylaminoethanol, N-methyldiethanolamine, 2-diethylamino ethanol, 2-isopropylamino ethanol, 2-diisopropylamino ethanol, 3- dimethylamino propanol and 2-aminopropanol.
  • the isomerization reaction conditions include a temperature between 190°C and 350°C, with a preferred reaction temperature between 220°C and 270°C.
  • the reaction conditions include a pressure sufficient to maintain the reaction mixture in the liquid phase.
  • the pressure in the reactor is at least 1025 kPa, with a preferred reactor pressure in the range of 1750 kPa to 2400 kPa.
  • the feedstream preferably comprises C 8 aromatics, having para-xylene, meta- xylene and ortho-xylene.
  • the feedstream can also include ethylbenzene, wherein the isomerization reactor converts the meta-xylene and ortho-xylene to para-xylene, and the ethylbenzene to benzene.
  • the effluent stream leaving the isomerization reactor includes para-xylene is passed to a para-xylene separation unit to generate a para-xylene process stream, and a second stream comprising meta-xylene, ortho-xylene and ethylbenzene.
  • the para-xylene separation unit can comprise an adsorption separation unit, wherein the para-xylene process stream is the extract stream and the second stream is the raffinate stream.
  • the extract stream and raffinate streams can include a desorbent.
  • the extract stream is passed to a fractionation unit to generate a bottoms stream comprising para-xylene and an overhead stream comprising desorbent.
  • the process can further include passing the raffinate stream to the isomerization reactor.
  • the raffinate stream can also be passed to a second fractionation column to separate the desorbent from the raffinate stream before passing the raffinate stream to the
  • the catalyst is characterized by a zeolite having a microporous crystalline structure comprising a framework of A10 2 and Si0 2 tetrahedral units, further including the element E and having the empirical composition in the as synthesized and anhydrous basis expressed by the empirical formula of:
  • An aluminosilicate reaction gel was prepared by first mixing 697.60 g of liquid sodium aluminate (LSA), 2178.08 g of dimethyldipropylammonimum hydroxide (40% SACHEM), 623.14 g of diethanolamine (Aldrich) and 14293.27 g of water while stirring vigorously. After thorough mixing, 3207.91 g of Ultrasil VN SP 89% was added. After the addition was completed, the resulting reaction mixture was homogenized for 1/2 hour, transferred to a 5-gallon hastelloy stir autoclave. The mixture was crystallized at 175°C with stirring at 245 RPM for 92 hours.
  • LSA liquid sodium aluminate
  • SACHEM dimethyldipropylammonimum hydroxide
  • Aldrich diethanolamine
  • the solid product was recovered by centrifugation, washed with de-ionized water and dried at 80°C.
  • the product was identified as UZM-54 by XRD. Representative diffraction lines observed for the product are shown in Table 1.
  • the BET surface area was 416 m 2 /g
  • the micropore area was 229 m 2 /g
  • the mesopore area was 187 m 2 /g
  • the micropore volume was 0.118 cc/g
  • mesopore volume was 0.762 cc/g.
  • Scanning Electron Microscopy (SEM) revealed crystals with a roughly spherical or rosette-like morphology of 10 to 25 nm.
  • the pentasil zeolite of example 1 was formulated into a catalyst containing 70% zeolite and 30% silica.
  • the zeolite was mixed with LUDOX AS-40 and Hi-Sil 250 into a Muller mixer. Additional water was added to the Muller mixer, while mixing, until dough with a proper texture for extrusion was formed.
  • the dough was extruded to form 1/16" diameter trilobes, which were dried at 100°C overnight and then sized to a length to diameter ratio of 3.
  • the dry extrudates was calcined in a box oven with a flowing air at 600°C for 4 hours to remove the template.
  • the calcined support was then exchanged using a 10 wt-% H 4 NO 3 solution at 75°C for one hour. This was followed by water wash using 20 cc of water per cc of extrudates. The H 4 NO 3 exchange and water wash was repeated two more times. The extrudates was then dried at 120°C for 4 hours and then activated at 550°C. The sodium level of the final catalyst was 0.003%. This is Catalyst A.
  • An aluminosilicate reaction gel was prepared by first mixing 697.60 g of liquid sodium aluminate (LSA), 2189.02 g of dimethyldipropylammonimum hydroxide (39.8% SACHEM), 623.14 g of diethanolamine (Aldrich) and 14282.33 g of water while stirring vigorously. After thorough mixing, 3207.91 g of Ultrasil VN SP 89% was added. After the addition was completed, the resulting reaction mixture was homogenized for 1/2 hour, transferred to a 5-gallon hastelloy stir autoclave. The mixture was crystallized at 175°C with stirring at 300 RPM for 89 hours.
  • LSA liquid sodium aluminate
  • SACHEM dimethyldipropylammonimum hydroxide
  • Aldrich diethanolamine
  • the solid product was recovered by centrifugation, washed with de-ionized water and dried at 80°C.
  • the product was identified as UZM-54 by XRD. Representative diffraction lines observed for the product are shown in Table 2.
  • the BET surface area was 483 m 2 /g, the micropore area was 197 m 2 /g and the mesopore area was 286 m 2 /g and the micropore volume was 0.101 cc/g and mesopore volume was 0.796 cc/g.
  • the pentasil zeolite of example 3 was formulated into a catalyst containing 70% zeolite and 30% silica.
  • the zeolite was mixed with LUDOX AS-40 and Hi-Sil 250 into a Muller mixer. Additional water was added to the Muller mixer, while mixing, until dough with a proper texture for extrusion was formed.
  • the dough was extruded to form 1/16" diameter trilobes, which were dried at 100°C overnight and then sized to a length to diameter ratio of 3.
  • the dry extrudates was calcined in a box oven with a flowing air at 600°C for 4 hours to remove the template.
  • the calcined support was then exchanged using a 10 wt-% H 4 NO 3 solution at 75°C for one hour. This was followed by water wash using 20 cc of water per cc of extrudates. The H 4 NO 3 exchange and water wash was repeated two more times. The extrudates was then dried at 120°C for 4 hours and then activated at 550°C. The sodium level of the final catalyst was 0.002%. This is Catalyst B.
  • Pentasil zeolite purchased from Zeolyst International (lot: CBV 2314), was formulated into a catalyst containing 70% zeolite and 30% silica.
  • the zeolite was mixed with LUDOX AS-40 and Hi-Sil 250 into a Muller mixer. Additional water was added to the Muller mixer, while mixing, until dough with a proper texture for extrusion was formed.
  • the dough was extruded to form 1/16" diameter trilobes, which were dried at 100°C overnight and then sized to a length to diameter ratio of 3.
  • the dry extrudates was calcined in a box oven with a flowing air at 600°C for 4 hours to remove the template.
  • the calcined support was then exchanged using a 10 wt-% H 4 NO 3 solution at 75°C for one hour. This was followed by water wash using 20 cc of water per cc of extrudates.
  • Catalysts A-C were evaluated for xylene isomerization and ethyl-benzene retention using a pilot plant upflow reactor processing a non-equilibrium C 8 aromatic feed having the following composition in wt-%:
  • Pilot-plant test conditions and results are as follows.
  • the above feed contacted the Catalyst at a pressure of 3.5 MPa in the liquid phase at a weight hourly space velocity of 10 under a range of temperatures.
  • the resulting performance measures are shown below:
  • Xylene Loss is in wt-% defined as "(l-( para, meta, ortho xylene wt% in product)/( -( para, meta, ortho xylene wt% in feed))* 100", which represents material that has to be circulated to another unit in an aromatics complex. Such circulation is expensive and a low amount of C 8 ring loss is preferred. Al 1+ represents material that is heavier, and generally not recoverable.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Geology (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Water Supply & Treatment (AREA)
  • Inorganic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Nanotechnology (AREA)

Abstract

A process for the production of para-xylene is presented. The process includes the isomerization of C8 aromatics to para-xylene utilizing a new catalyst. The new catalyst and designated as UZM-54 is represented by the empirical composition in the as synthesized and anhydrous basis expressed by the empirical formula of: Mm n+R1 r1 p 1 + R2 r2 p 2 + Al1-xExSiyOz where M is an alkali, alkaline earth, or rare earth metal such as sodium and/or potassium, R1 and R2 are organoammonium cation and E is a framework element such as gallium, iron, boron, or indium. UZM-54 are characterized by unique x-ray diffraction patterns, high meso surface area, low Si/Al ratios.

Description

fflGH MESO-SURFACE AREA PENTASIL ZEOLITE FOR USE IN XYLENE CONVERSION
STATEMENT OF PRIORITY
[OOOl] This application claims priority to U.S. Application No. 14/636624 which was filed March 3, 2015, the contents of which are hereby incorporated by reference to its entirety.
FIELD OF THE Γ VENTION
[0002] The present invention relates to the use of a new family of aluminosilicate zeolites, having a designation of UZM-54. UZM-54 is characterized by unique x-ray diffraction patterns, high meso-surface area and low Si/Al ratio compositions.
BACKGROUND
[0003] Most new aromatics complexes are designed to maximize the yield of benzene and para-xylene. Benzene is a versatile petrochemical building block used in many different products based on its derivation including ethylbenzene, cumene, and cyclohexane. Para- xylene is also an important building block, which is used almost exclusively for the production of polyester fibers, resins, and films formed via terephthalic acid or dimethyl terephthalate intermediates. Accordingly, an aromatics complex may be configured in many different ways depending on the desired products, available feedstocks, and investment capital available. A wide range of options permits flexibility in varying the product slate balance of benzene and para-xylene to meet downstream processing requirements.
[0004] A prior art aromatics complex flow scheme has been disclosed by Meyers in the Handbook of Petroleum Refining Processes, 2d. Edition in 1997 by McGraw-Hill.
[0005] U.S. Pat. No. 3,996,305 to Berger discloses a fractionation scheme primarily directed to trans alkylation of toluene and Cg alkylaromatics in order to produce benzene and xylene. The trans alkylation process is also combined with an aromatics extraction process. The fractionation scheme includes a single column with two streams entering and with three streams exiting the column for integrated economic benefits. [0006] U.S. Pat. No. 4,341,914 to Berger discloses a transalkylation process with recycle of Cg alkylaromatics in order to increase yield of xylenes from the process. The
transalkylation process is also preferably integrated with a paraxylene separation zone and a xylene isomerization zone operated as a continuous loop receiving mixed xylenes from the transalkylation zone feedstock and effluent fractionation zones.
[0007] U.S. Pat. No. 4,642,406 to Schmidt discloses a high severity process for xylene production that employs a transalkylation zone that simultaneously performs as an
isomerization zone over a nonmetal catalyst. High quality benzene is produced along with a mixture of xylenes, which allows para-xylene to be separated by absorptive separation from the mixture with the isomer-depleted stream being passed back to the trans alkylation zone.
[0008] U.S. Pat. No. 5,417,844 to Boitiaux et al. discloses a process for the selective dehydrogenation of olefins in steam cracking petrol in the presence of a nickel catalyst and is characterized in that prior to the use of the catalyst, a sulfur-containing organic compound is incorporated into the catalyst outside of the reactor prior to use.
[0009] The importance of para-xylene production has led to the development of many different processes. However, there are losses associated with these processes.
Improvements to reduce and minimize losses are important for the economics of para-xylene production.
SUMMARY [0010] A first embodiment of the invention is a process for the production of para-xylene, comprising passing a mixture of hydrocarbons comprising xylenes to an isomerization reactor, operated at isomerization reaction conditions, to form a reaction mixture over an isomerization catalyst, and to generate an effluent stream comprising p-xylene; wherein the isomerization catalyst is UZM-54.
[0011] The UZM-54 aluminosilicate zeolite is a microporous crystalline structure comprising a framework of A102 and Si02 tetrahedral units, and an empirical composition in the as synthesized and anhydrous basis expressed by the empirical formula of Mm n+Ri ripi+ R2 r2 p 2 + AlSiyOz where M is at least one exchangeable cation selected from the group consisting of alkali and alkaline earth metals, "m" is the mole ratio of M to Al and varies from 0 to 1, Ri is at least one organoammonium cation selected from the group consisting of quaternary ammonium cations, diquaternary ammonium cations, "ri" is the mole ratio of Ri to Al and has a value of 0.1 to 3.0, R2 is at least one organoammonium cation selected from the group consisting of protonated alkanolamines, protonated amines, protonated diamines, and quaternized alkanolammonium cations, "r2" is the mole ratio of R2 to Al and has a value of 0 to 3.0, "n" is the weight average valence of M and has a value of 1 to 2, "pi" is the weighted average valence of Ri and has a value of 1 to 2, "p2" is the weighted average valence of R2 and has a value of 1 to 2, "y" is the mole ratio of Si to Al and varies from greater than 11 to 30 and "z" is the mole ratio of O to Al and has a value determined by the equation z=(m n+ri pi+r2 p2+3+4 y)/2 and it is characterized in that it has the x-ray diffraction pattern having at least the d spacing and intensities set forth in the following Table:
Table
Figure imgf000004_0001
[0012] An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph wherein the isomerization reaction conditions include a temperature between 190°C and 350°C. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph wherein the isomerization reaction conditions include a temperature between 220°C and 270°C. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph wherein the isomerization reaction conditions include a pressure sufficient to maintain the reaction mixture in the liquid phase. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph wherein the pressure is at least 1025 kPa. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph wherein the mixture of hydrocarbons further includes ethylbenzene. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph where M in the zeolite is selected from the group consisting of lithium, sodium, potassium, cesium, strontium, calcium, barium and mixtures thereof. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph where M in the zeolite is a mixture of an alkali metal and an alkaline earth metal. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph where Ri in the zeolite is selected from the group consisting of dimethyldipropylammonimum, diethyldipropylammonium, propyltrimethylammonium, hexamethonium, and mixtures thereof. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph where R2 in the zeolite is selected from the group consisting of diethanolamine, N-methylethanolamine, 2- dimethylaminoethanol, N-methyldiethanolamine, 2-diethylamino ethanol, 2-isopropylamino ethanol, 2-diisopropylamino ethanol, 3-dimethylamino propanol and 2-aminopropanol and mixtures thereof. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph wherein the catalyst, UZM- 54, is characterized by a zeolite having a microporous crystalline structure comprising a framework of A102 and Si02 tetrahedral units, further including the element E and having the empirical composition in the as synthesized and anhydrous basis expressed by the empirical formula of Mm n+Ri npi+R2 r2 P2+ Ali-xExSiyOz where "m" is the mole ratio of M to (Al+E) and varies from 0 to 1, "ri" is the mole ratio of Ri to (Al+E) and has a value of 0.1 to 3.0, "r2" is the mole ratio of R2 to (Al+E) and has a value of 0 to 3.0, E is an element selected from the group consisting of gallium, iron, boron, indium and mixtures thereof, "x" is the mole fraction of E and has a value from 0 to 1.0, "y" is the mole ratio of Si to (Al+E) and varies from greater than 11 to 30 and "z" is the mole ratio of O to (Al+E) and has a value determined by the equation z=(m n+ri pi+r2 p2+3+4 y)/2. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph further comprising passing the effluent stream to a para-xylene separation unit to generate a para-xylene process stream and a second stream comprising meta-xylene and ortho-xylene. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph wherein the separation unit is an adsorption separation unit and generates and extract stream comprising para-xylene and desorbent and a raffinate stream comprising meta-xylene and ortho-xylene. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph further comprising passing the extract stream to a fractionation unit to generate a bottoms stream comprising para-xylene and an overhead stream comprising desorbent. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph wherein the raffinate stream is passed to the isomerization reactor.
[0013] A second embodiment of the invention is a process for the production of para- xylene, comprising passing a mixture of hydrocarbons comprising xylenes to an
isomerization reactor, operated at isomerization reaction conditions, to form a reaction mixture over an isomerization catalyst of the aluminosilicate zeolite UZM-54, and to generate an effluent stream comprising para-xylene, wherein the catalyst is a zeolite, UZM- 54, of claim 1 having a microporous crystalline structure comprising a framework of A102 and Si02 tetrahedral units, further including the element E and having the empirical composition in the as synthesized and anhydrous basis expressed by the empirical formula of Mm n+Ri ripi+R2 r2 p 2 + Ali-xExSiyOz where "m" is the mole ratio of M to (Al+E) and varies from 0 to 1, "ri" is the mole ratio of Ri to (Al+E) and has a value of 0.1 to 3.0, "r2" is the mole ratio of R2 to (Al+E) and has a value of 0 to 3.0, E is an element selected from the group consisting of gallium, iron, boron, indium and mixtures thereof, "x" is the mole fraction of E and has a value from 0 to 1.0, "y" is the mole ratio of Si to (Al+E) and varies from greater than 11 to 30 and "z" is the mole ratio of O to (Al+E) and has a value determined by the equation z=(m n+ri pi+r2 p2+3+4 y)/2 and it is characterized in that it has the x-ray diffraction pattern having at least the d spacing and intensities set forth in the following Table: Table
Figure imgf000007_0001
[0014] An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the second embodiment in this paragraph wherein the isomerization reaction conditions include a temperature between 190°C and 350°C. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the second embodiment in this paragraph wherein the isomerization reaction conditions include a pressure sufficient to maintain the reaction mixture in the liquid phase. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the second embodiment in this paragraph wherein the pressure is at least 1025 kPa. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the second embodiment in this paragraph wherein the mixture of hydrocarbons further includes ethylbenzene.
[0015] Other objects, advantages and applications of the present invention will become apparent to those skilled in the art from the following detailed description.
DETAILED DESCRIPTION
[0016] Para-xylene production is a valuable commercial process, wherein the reduction of losses can entail a significant economic advantage. One method of improving para-xylene yields is to increase the conversion from C8 compounds to para-xylene and to reduce losses during that conversion. The operating of a liquid phase xylene isomerization reactor using a conventional MFI catalyst generates a significant xylene loss per pass. The loss is greater than 1.0%. The invention of a new catalyst, UZM-54, allows for a significant reduction in the xylene loss. The new catalyst has a new zeolitic MFI morphology, high meso-surface area and low Si/Al ratios and can achieve comparable para-xylene content with xylene losses of around 0.2% or less.
[0017] The present invention is a process for the production of para-xylene. The process includes passing a mixture of hydrocarbons including xylenes to an isomerization reactor, operated at isomerization reaction conditions to generate an effluent stream having para- xylene, or p-xylene. The reaction conditions include forming a reaction mixture comprising C7-C9 hydrocarbons and passing the mixture over an isomerization catalyst. The present invention utilizes a new catalyst that reduces the loss of xylenes during the isomerization process. The isomerization catalyst is a zeolite having a microporous crystalline structure comprising a framework of A102 and Si02 tetrahedral units, and an empirical composition in the as synthesized and anhydrous basis expressed by the empirical formula of:
Mm n+R! rl P ! + R2 r2 p 2 + AlSiyOz.
[0018] The catalyst comprises M, which is at least one exchangeable cation selected from the group consisting of alkali and alkaline earth metals, "m" is the mole ratio of M to Al and varies from 0 to 1, Ri is at least one organoammonium cation selected from the group consisting of quaternary ammonium cations, diquaternary ammonium cations, "ri" is the mole ratio of Ri to Al and has a value of 0.1 to 3.0, R2 is at least one organoammonium cation selected from the group consisting of protonated alkanolamines, protonated amines, protonated diamines, and quatemized alkanolammonium cations, "r2" is the mole ratio of R2 to Al and has a value of 0 to 3.0, "n" is the weight average valence of M and has a value of 1 to 2, "pi" is the weighted average valence of Ri and has a value of 1 to 2, "p2" is the weighted average valence of R2 and has a value of 1 to 2, "y" is the mole ratio of Si to Al and varies from greater than 1 1 to 30 and "z" is the mole ratio of O to Al and has a value determined by the equation:
z=(m n+r i'p i+r2 p2+3 +4'y)/2.
[0019] The catalyst, UZM-54, can be further characterized by its unique x-ray diffraction pattern as at least the d spacing and intensities set forth in Table A: Table A
Figure imgf000009_0001
[0020] The M in the zeolite can be a mixture of alkali metals and alkaline earth metals, with a preferred M including one or more metals from lithium, sodium, potassium, cesium, strontium, calcium and barium. The Ri cation can be selected from one or more of quaternary ammonium cations, quaternary phosphonium cations, and methonium cations. The Ri cation can come from an halide compound or a hydroxide compound. Preferred Ri cations include one or more from dimethyldipropylammonimum, diethyldipropylammonium, propyltrimethylammonium and hexamethonium. The R2 cation can come from an halide compound or a hydroxide compound. Preferred R2 cations include one or more from diethanolamine, N-methylethanolamine, 2-dimethylaminoethanol, N-methyldiethanolamine, 2-diethylamino ethanol, 2-isopropylamino ethanol, 2-diisopropylamino ethanol, 3- dimethylamino propanol and 2-aminopropanol.
[0021] The isomerization reaction conditions include a temperature between 190°C and 350°C, with a preferred reaction temperature between 220°C and 270°C. The reaction conditions include a pressure sufficient to maintain the reaction mixture in the liquid phase. In one embodiment, the pressure in the reactor is at least 1025 kPa, with a preferred reactor pressure in the range of 1750 kPa to 2400 kPa.
[0022] The feedstream preferably comprises C8 aromatics, having para-xylene, meta- xylene and ortho-xylene. The feedstream can also include ethylbenzene, wherein the isomerization reactor converts the meta-xylene and ortho-xylene to para-xylene, and the ethylbenzene to benzene.
[0023] The effluent stream leaving the isomerization reactor includes para-xylene is passed to a para-xylene separation unit to generate a para-xylene process stream, and a second stream comprising meta-xylene, ortho-xylene and ethylbenzene. The para-xylene separation unit can comprise an adsorption separation unit, wherein the para-xylene process stream is the extract stream and the second stream is the raffinate stream. The extract stream and raffinate streams can include a desorbent. The extract stream is passed to a fractionation unit to generate a bottoms stream comprising para-xylene and an overhead stream comprising desorbent. The process can further include passing the raffinate stream to the isomerization reactor. The raffinate stream can also be passed to a second fractionation column to separate the desorbent from the raffinate stream before passing the raffinate stream to the
isomerization reactor.
[0024] In another embodiment, the catalyst is characterized by a zeolite having a microporous crystalline structure comprising a framework of A102 and Si02 tetrahedral units, further including the element E and having the empirical composition in the as synthesized and anhydrous basis expressed by the empirical formula of:
Mm n+Ri rl P ! + R2 r2 p 2 + Al1-xExSiyOz where "m" is the mole ratio of M to (Al+E) and varies from 0 to 1, "ri" is the mole ratio of Ri to (Al+E) and has a value of 0.1 to 3.0, "r2" is the mole ratio of R2 to (Al+E) and has a value of 0 to 3.0, E is an element selected from the group consisting of gallium, iron, boron, indium and mixtures thereof, "x" is the mole fraction of E and has a value from 0 to 1.0, "y" is the mole ratio of Si to (Al+E) and varies from greater than 1 1 to 30 and "z" is the mole ratio of O to (Al+E) and has a value determined by the equation:
z=(m n+ri pi+r2 p2+3+4 y)/2.
[0025] Higher meso-surface area UZM-54 zeolite, show similar results for isomerization activity with respect to the para-xylene/xylene equilibrium, but has a much lower production of heavy components, or Cn+ aromatics, in the reactor. The high meso-surface area UZM-54 produces 50% less heavier alkylated material in the effluent. Heavier alkylated material represents losses that are generally not recoverable in an aromatics complex. EXAMPLE 1
[0026] An aluminosilicate reaction gel was prepared by first mixing 697.60 g of liquid sodium aluminate (LSA), 2178.08 g of dimethyldipropylammonimum hydroxide (40% SACHEM), 623.14 g of diethanolamine (Aldrich) and 14293.27 g of water while stirring vigorously. After thorough mixing, 3207.91 g of Ultrasil VN SP 89% was added. After the addition was completed, the resulting reaction mixture was homogenized for 1/2 hour, transferred to a 5-gallon hastelloy stir autoclave. The mixture was crystallized at 175°C with stirring at 245 RPM for 92 hours. The solid product was recovered by centrifugation, washed with de-ionized water and dried at 80°C. The product was identified as UZM-54 by XRD. Representative diffraction lines observed for the product are shown in Table 1. The product composition was determined by elemental analysis to consist of the following mole ratios: Si/Al = 13.45, Na/Al = 0.0.589. A portion of the material was calcined by ramping to 600°C for 2 hours followed by a 5 hour dwell in air. The BET surface area was 416 m2/g, the micropore area was 229 m2/g and the mesopore area was 187 m2/g and the micropore volume was 0.118 cc/g and mesopore volume was 0.762 cc/g. Scanning Electron Microscopy (SEM) revealed crystals with a roughly spherical or rosette-like morphology of 10 to 25 nm.
Chemical analysis was as follows: 3.07% Al, 42.9 % Si, 1.54 % Na, 0.90 % N, N/A1=0.56, Na/Al=0.59 Si/Al2=26.91.
TABLE 1
Figure imgf000011_0001
EXAMPLE 2
[0027] The pentasil zeolite of example 1 was formulated into a catalyst containing 70% zeolite and 30% silica. In the catalyst preparation, the zeolite was mixed with LUDOX AS-40 and Hi-Sil 250 into a Muller mixer. Additional water was added to the Muller mixer, while mixing, until dough with a proper texture for extrusion was formed. The dough was extruded to form 1/16" diameter trilobes, which were dried at 100°C overnight and then sized to a length to diameter ratio of 3. The dry extrudates was calcined in a box oven with a flowing air at 600°C for 4 hours to remove the template. The calcined support was then exchanged using a 10 wt-% H4NO3 solution at 75°C for one hour. This was followed by water wash using 20 cc of water per cc of extrudates. The H4NO3 exchange and water wash was repeated two more times. The extrudates was then dried at 120°C for 4 hours and then activated at 550°C. The sodium level of the final catalyst was 0.003%. This is Catalyst A.
EXAMPLE 3
[0028] An aluminosilicate reaction gel was prepared by first mixing 697.60 g of liquid sodium aluminate (LSA), 2189.02 g of dimethyldipropylammonimum hydroxide (39.8% SACHEM), 623.14 g of diethanolamine (Aldrich) and 14282.33 g of water while stirring vigorously. After thorough mixing, 3207.91 g of Ultrasil VN SP 89% was added. After the addition was completed, the resulting reaction mixture was homogenized for 1/2 hour, transferred to a 5-gallon hastelloy stir autoclave. The mixture was crystallized at 175°C with stirring at 300 RPM for 89 hours. The solid product was recovered by centrifugation, washed with de-ionized water and dried at 80°C. The product was identified as UZM-54 by XRD. Representative diffraction lines observed for the product are shown in Table 2. The product composition was determined by elemental analysis to consist of the following mole ratios: Si/Al = 13.92, Na/Al = 0.59. A portion of the material was calcined by ramping to 600°C for 2 hours followed by a 5 hour dwell in air. The BET surface area was 483 m2/g, the micropore area was 197 m2/g and the mesopore area was 286 m2/g and the micropore volume was 0.101 cc/g and mesopore volume was 0.796 cc/g. Scanning Electron Microscopy (SEM) revealed crystals with a roughly spherical or rosette-like morphology of 10 to 25 nm. Chemical analysis was as follows: 2.98% Al, 43.1 % Si, 1.50 % Na, 0.93 % N, N/A1=0.60, Na/Al=0.59, Si/Al2=27.85. TABLE 2
Figure imgf000013_0001
EXAMPLE 4
[0029] The pentasil zeolite of example 3 was formulated into a catalyst containing 70% zeolite and 30% silica. In the catalyst preparation, the zeolite was mixed with LUDOX AS-40 and Hi-Sil 250 into a Muller mixer. Additional water was added to the Muller mixer, while mixing, until dough with a proper texture for extrusion was formed. The dough was extruded to form 1/16" diameter trilobes, which were dried at 100°C overnight and then sized to a length to diameter ratio of 3. The dry extrudates was calcined in a box oven with a flowing air at 600°C for 4 hours to remove the template. The calcined support was then exchanged using a 10 wt-% H4NO3 solution at 75°C for one hour. This was followed by water wash using 20 cc of water per cc of extrudates. The H4NO3 exchange and water wash was repeated two more times. The extrudates was then dried at 120°C for 4 hours and then activated at 550°C. The sodium level of the final catalyst was 0.002%. This is Catalyst B.
EXAMPLE 5 (Commercial MFI-23)
[0030] Pentasil zeolite, purchased from Zeolyst International (lot: CBV 2314), was formulated into a catalyst containing 70% zeolite and 30% silica. In the catalyst preparation, the zeolite was mixed with LUDOX AS-40 and Hi-Sil 250 into a Muller mixer. Additional water was added to the Muller mixer, while mixing, until dough with a proper texture for extrusion was formed. The dough was extruded to form 1/16" diameter trilobes, which were dried at 100°C overnight and then sized to a length to diameter ratio of 3. The dry extrudates was calcined in a box oven with a flowing air at 600°C for 4 hours to remove the template. The calcined support was then exchanged using a 10 wt-% H4NO3 solution at 75°C for one hour. This was followed by water wash using 20 cc of water per cc of extrudates. The
H4NO3 exchange and water wash was repeated three more times. The extrudates was then dried at 120°C for 4 hours and then activated at 550°C. The sodium level of the final catalyst was 0.002%. This is Catalyst C.
EXAMPLE 6
[0031] Catalysts A-C were evaluated for xylene isomerization and ethyl-benzene retention using a pilot plant upflow reactor processing a non-equilibrium C8 aromatic feed having the following composition in wt-%:
Figure imgf000014_0001
EXAMPLE 7
[0032] Pilot-plant test conditions and results are as follows. The above feed contacted the Catalyst at a pressure of 3.5 MPa in the liquid phase at a weight hourly space velocity of 10 under a range of temperatures. The resulting performance measures are shown below:
Figure imgf000014_0002
[0033] Note that the "Xylene Loss" is in wt-% defined as "(l-( para, meta, ortho xylene wt% in product)/( -( para, meta, ortho xylene wt% in feed))* 100", which represents material that has to be circulated to another unit in an aromatics complex. Such circulation is expensive and a low amount of C8 ring loss is preferred. Al 1+ represents material that is heavier, and generally not recoverable.
[0034] While the invention has been described with what are presently considered the preferred embodiments, it is to be understood that the invention is not limited to the disclosed embodiments, but it is intended to cover various modifications and equivalent arrangements included within the scope of the appended claims.

Claims

H0041584 WO 2016/140900 PCT/US2016/020007 WHAT IS CLAIMED IS:
1. A process for the production of para-xylene, comprising:
passing a mixture of hydrocarbons comprising xylenes to an isomerization reactor, operated at isomerization reaction conditions, to form a reaction mixture over an
isomerization catalyst, and to generate an effluent stream comprising p-xylene;
wherein the isomerization catalyst is characterized by a zeolite having a microporous crystalline structure comprising a framework of A102 and Si02 tetrahedral units, and an empirical composition in the as synthesized and anhydrous basis expressed by the empirical formula of:
Mm n+R! rl P!+R2 r2 p 2 + AlSiyOz where M is at least one exchangeable cation selected from the group consisting of alkali and alkaline earth metals, "m" is the mole ratio of M to Al and varies from 0 to 1, Ri is at least one organoammonium cation selected from the group consisting of quaternary ammonium cations, diquaternary ammonium cations, "ri" is the mole ratio of Ri to Al and has a value of 0.1 to 3.0, R2 is at least one organoammonium cation selected from the group consisting of protonated alkanolamines, protonated amines, protonated diamines, and quaternized alkanolammonium cations, "r2" is the mole ratio of R2 to Al and has a value of 0 to 3.0, "n" is the weight average valence of M and has a value of 1 to 2, "pi" is the weighted average valence of Ri and has a value of 1 to 2, "p2" is the weighted average valence of R2 and has a value of 1 to 2, "y" is the mole ratio of Si to Al and varies from greater than 11 to 30 and "z" is the mole ratio of O to Al and has a value determined by the equation: z=(m n+ri pi+r2 p2+3+4 y)/2 and it is characterized in that it has the x-ray diffraction pattern having at least the d spacing and intensities set forth in the following Table : H0041584
WO 2016/140900 PCT/US2016/020007
Figure imgf000017_0001
2. The process of claim 1 wherein the isomerization reaction conditions include a temperature between 190°C and 350°C.
3. The process of claim 1 wherein the pressure is at least 1025 kPa.
4. The process of claim 1 wherein the mixture of hydrocarbons further includes ethylbenzene.
5. The process of claim 1 where M in the zeolite is selected from the group consisting of lithium, sodium, potassium, cesium, strontium, calcium, barium and mixtures thereof.
6. The process of claim 1 where M in the zeolite is a mixture of an alkali metal and an alkaline earth metal.
7. The process of claim 1 where Ri in the zeolite is selected from the group consisting of dimethyldipropylammonimum, diethyldipropylammonium, propyltrimethylammonium, hexamethonium, and mixtures thereof.
8. The process of claim 1 where R2 in the zeolite is selected from the group consisting of diethanolamine, N-methylethanolamine, 2-dimethylaminoethanol, N-methyldiethanolamine, H0041584
WO 2016/140900 PCT/US2016/020007
2-diethylamino ethanol, 2-isopropylamino ethanol, 2-diisopropylamino ethanol, 3- dimethylamino propanol and 2-aminopropanol and mixtures thereof.
9. The process of claim 1 wherein the catalyst is characterized by a zeolite having a microporous crystalline structure comprising a framework of A102 and Si02 tetrahedral units, further including the element E and having the empirical composition in the as synthesized and anhydrous basis expressed by the empirical formula of:
Mm n+Ri rl P ! +R2 r2V Al1-xExSiyOz where "m" is the mole ratio of M to (Al+E) and varies from 0 to 1, "ri" is the mole ratio of Ri to (Al+E) and has a value of 0.1 to 3.0, "r2" is the mole ratio of R2 to (Al+E) and has a value of 0 to 3.0, E is an element selected from the group consisting of gallium, iron, boron, indium and mixtures thereof, "x" is the mole fraction of E and has a value from 0 to 1.0, "y" is the mole ratio of Si to (Al+E) and varies from greater than 11 to 30 and "z" is the mole ratio of O to (Al+E) and has a value determined by the equation:
z=(m n+r i'p i+r2 p2+3 +4 y)/2.
10. The process of claim 1 further comprising:
passing the effluent stream to a para-xylene separation unit to generate a para-xylene process stream and a second stream comprising meta-xylene and ortho-xylene.
PCT/US2016/020007 2015-03-03 2016-02-29 High meso-surface area pentasil zeolite for use in xylene conversion Ceased WO2016140900A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US14/636,624 US9890094B2 (en) 2015-03-03 2015-03-03 High meso-surface area and high acid site density pentasil zeolite for use in xylene conversion
US14/636,624 2015-03-03

Publications (1)

Publication Number Publication Date
WO2016140900A1 true WO2016140900A1 (en) 2016-09-09

Family

ID=56848632

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2016/020007 Ceased WO2016140900A1 (en) 2015-03-03 2016-02-29 High meso-surface area pentasil zeolite for use in xylene conversion

Country Status (2)

Country Link
US (1) US9890094B2 (en)
WO (1) WO2016140900A1 (en)

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10166532B2 (en) * 2015-03-03 2019-01-01 Uop Llc High meso-surface area and high acid site density pentasil zeolite for use in xylene conversion
WO2017180509A1 (en) * 2016-04-14 2017-10-19 Uop Llc Liquid phase xylene isomerization in the absence of hydrogen
KR102747277B1 (en) 2019-03-29 2024-12-27 엑손모빌 케미칼 패턴츠 인코포레이티드 Novel zeolite, method for producing same, and use thereof in conversion of aromatic hydrocarbons
KR20210126101A (en) 2019-03-29 2021-10-19 엑손모빌 케미칼 패턴츠 인코포레이티드 MEL-type zeolite for aromatic hydrocarbon conversion, method for preparing the zeolite, and catalyst composition comprising the zeolite
US20220289645A1 (en) 2019-08-23 2022-09-15 Exxonmobil Chemical Patents Inc. Processes for Isomerizing C8 Aromatic Hydrocarbons Using Serial Reactors
KR102811928B1 (en) 2019-08-23 2025-05-22 엑손모빌 케미칼 패턴츠 인코포레이티드 Method for isomerizing C8 aromatic hydrocarbons
US11103859B2 (en) 2020-01-06 2021-08-31 Uop Llc UZM-54 and transalkylation process using same
US10927057B1 (en) * 2020-01-06 2021-02-23 Uop Llc Two bed liquid phase isomerization process
KR102889856B1 (en) * 2020-09-30 2025-11-21 엑손모빌 케미칼 패턴츠 인코포레이티드 Method for converting C8 aromatic hydrocarbons
CN114031510B (en) * 2021-11-25 2023-05-30 万华化学集团股份有限公司 Preparation method of 2-aminopropanol

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2052554A (en) * 1979-06-11 1981-01-28 Ici Ltd Production of aromatic hydrocarbons
US20090093662A1 (en) * 2007-10-08 2009-04-09 Whitchurch Patrick C Aromatic isomerization catalyst
US8058496B2 (en) * 2010-03-31 2011-11-15 Uop Llc Process for xylene and ethylbenzene isomerization using UZM-35
US8071831B1 (en) * 2010-06-21 2011-12-06 Uop Llc Process for xylene and ethylbenzene isomerization using UZM-35
US20140114106A1 (en) * 2010-07-28 2014-04-24 Chevron U.S.A. Inc. Process for the production of para-xylene

Family Cites Families (33)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3996305A (en) 1975-03-27 1976-12-07 Universal Oil Products Company Fractionation of aromatic streams
US4341914A (en) 1980-12-22 1982-07-27 Uop Inc. Transalkylation process with recycle of C10 hydrocarbons
US4381419A (en) * 1981-04-22 1983-04-26 Exxon Research & Engineering Co. Adsorption-desorption separation process with integrated light and heavy desorbents
US4642406A (en) 1985-09-13 1987-02-10 Uop Inc. High severity process for xylene production employing a transalkylation zone for xylene isomerization
US4899012A (en) 1988-10-17 1990-02-06 Uop Catalyst for the isomerization of aromatics
FR2664610A1 (en) 1990-07-13 1992-01-17 Inst Francais Du Petrole SELECTIVE HYDROGENATION OF VAPOCRACKING SPECIES ON CATALYSTS BASED ON A SUPPORTED METAL IN WHICH AN ORGANIC COMPOUND HAS BEEN INCORPORATED BEFORE LOADING INTO THE REACTOR.
US5157183A (en) 1990-12-10 1992-10-20 Cotterman Ronald L Aromatization process using an improved catalyst
GB9600272D0 (en) 1996-01-06 1996-03-06 Univ Nottingham Polymers
US5981817A (en) 1997-04-10 1999-11-09 Exxon Chemical Patents Inc. Xylene isomerization process
US6180550B1 (en) 1998-12-22 2001-01-30 Mobile Oil Corporation Small crystal ZSM-5, its synthesis and use
US6699811B1 (en) 1999-05-05 2004-03-02 Exxon Mobil Chemical Patents Inc. Tailored zeolite bound zeolite catalyst and its use for hydrocarbon conversion
US6355853B1 (en) 2000-02-24 2002-03-12 Uop Llc Selective xylenes isomerization and ethylbenzene conversion
US6303839B1 (en) 2000-06-14 2001-10-16 Uop Llc Process for producing polymer grade olefins
US7483581B2 (en) 2001-07-02 2009-01-27 Qualcomm Incorporated Apparatus and method for encoding digital image data in a lossless manner
US7317133B2 (en) 2002-11-21 2008-01-08 Uop Llc Process for enhanced olefin production
US7375047B1 (en) 2005-09-14 2008-05-20 Uop Llc Ethylbenzene conversion and xylene isomerization processes and catalysts therefor
US7297830B2 (en) 2005-09-14 2007-11-20 Uop Llc Process for isomerizing non-equilibrium xylene-containing feed streams
US8134037B2 (en) 2005-12-12 2012-03-13 Uop Llc Xylene isomerization process and apparatus
KR101470623B1 (en) 2006-11-17 2014-12-12 에스케이이노베이션 주식회사 Xylene isomerization catalyst and method for producing the same
US20080146859A1 (en) 2006-12-18 2008-06-19 Rekoske James E Selective Aromatics Isomerization Process
CA2698854A1 (en) 2007-09-10 2009-03-19 Shell Internationale Research Maatschappij B.V. Zsm-5, its preparation and use in ethylbenzene dealkylation
US7939701B2 (en) 2007-12-12 2011-05-10 Uop Llc Aromatic isomerization catalyst and a process of use thereof
US8022263B2 (en) 2008-11-19 2011-09-20 Uop Llc Selective aromatics isomerization process
US8273934B2 (en) 2008-12-15 2012-09-25 Exxonmobil Chemical Patents Inc. Process for producing para-xylene
US8138385B2 (en) * 2010-03-31 2012-03-20 Uop Llc Process for xylene and ethylbenzene isomerization using UZM-35HS
SG184411A1 (en) 2010-04-21 2012-11-29 Exxonmobil Chem Patents Inc Xylenes isomerization process and catalyst therefor
US8747807B2 (en) * 2010-07-01 2014-06-10 Uop Llc UZM-5, UZM-5P, and UZM-6 crystalline aluminosilicate zeolites and methods for preparing the same
US8889937B2 (en) 2011-06-09 2014-11-18 Uop Llc Process for producing one or more alkylated aromatics
WO2013028303A1 (en) * 2011-08-19 2013-02-28 Exxonmobil Chemical Patents Inc. Emm-22 molecular sieve material, its synthesis and use
CA2851798C (en) * 2011-10-12 2018-01-02 Exxonmobil Research And Engineering Company Synthesis of mse-framework type molecular sieves
US8889940B2 (en) 2011-11-01 2014-11-18 Uop Llc Catalyst and process for hydrocarbon conversion
US8609921B1 (en) * 2012-12-12 2013-12-17 Uop Llc Aromatic transalkylation using UZM-44 aluminosilicate zeolite
FR3008019B1 (en) 2013-07-04 2015-07-17 Sidel Participations HEATING MODULE COMPRISING A LAMP AND A LENGTH FIXED BY A FLANGE ON A NON-EMISSIVE PART OF THE LAMP

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2052554A (en) * 1979-06-11 1981-01-28 Ici Ltd Production of aromatic hydrocarbons
US20090093662A1 (en) * 2007-10-08 2009-04-09 Whitchurch Patrick C Aromatic isomerization catalyst
US8058496B2 (en) * 2010-03-31 2011-11-15 Uop Llc Process for xylene and ethylbenzene isomerization using UZM-35
US8071831B1 (en) * 2010-06-21 2011-12-06 Uop Llc Process for xylene and ethylbenzene isomerization using UZM-35
US20140114106A1 (en) * 2010-07-28 2014-04-24 Chevron U.S.A. Inc. Process for the production of para-xylene

Also Published As

Publication number Publication date
US9890094B2 (en) 2018-02-13
US20160257632A1 (en) 2016-09-08

Similar Documents

Publication Publication Date Title
US9890094B2 (en) High meso-surface area and high acid site density pentasil zeolite for use in xylene conversion
JP5539341B2 (en) Novel transalkylation process
US8481795B2 (en) Processes for transalkylating aromatic hydrocarbons and converting olefins
US8609921B1 (en) Aromatic transalkylation using UZM-44 aluminosilicate zeolite
RU2365573C1 (en) Two-stage method of aromatic compounds isomerisation
US10336665B2 (en) Yields in xylene isomerization using layer MFI zeolites
US8841502B2 (en) Aromatic transalkylation using UZM-39 aluminosilicate zeolite
US8221707B2 (en) Process for isomerizing a non-equilibrium alkylaromatic feed mixture and an aromatic production facility
KR20140034303A (en) Process for transalkylating aromatic hydrocarbons
CA2858726A1 (en) Aromatic transformation using uzm-39 aluminosilicate zeolite
Maftei et al. Conversion of industrial feedstock mainly with butanes and butenes over HZSM-5 and Zn/HZSM-5 (nitrate) catalysts
US20210001312A1 (en) Catalyst for Ethylbenzene Conversion in a Xylene Isomerization Process
US10166532B2 (en) High meso-surface area and high acid site density pentasil zeolite for use in xylene conversion
US20100092351A1 (en) Molecular Sieve and Catalyst Incorporating the Sieve
CN115003414B (en) UZM-54 and transalkylation methods using the same
US8431760B2 (en) Hydrocarbon conversion using an improved molecular sieve
US20100152025A1 (en) Molecular Sieve
WO2017062323A1 (en) A process for making cumene by alkylation of benzene using an organotemplate-free zeolite beta

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 16759313

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 16759313

Country of ref document: EP

Kind code of ref document: A1