CN115532306A - Composite catalyst for transalkylation and preparation method and application thereof - Google Patents

Composite catalyst for transalkylation and preparation method and application thereof Download PDF

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CN115532306A
CN115532306A CN202110740217.6A CN202110740217A CN115532306A CN 115532306 A CN115532306 A CN 115532306A CN 202110740217 A CN202110740217 A CN 202110740217A CN 115532306 A CN115532306 A CN 115532306A
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molecular sieve
layer
catalyst
zsm
catalytic
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CN115532306B (en
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丁键
李经球
孔德金
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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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
    • 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
    • B01J35/51—Spheres
    • 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
    • B01J29/80—Mixtures of different zeolites
    • 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
    • B01J37/024—Multiple impregnation or coating
    • B01J37/0244—Coatings comprising several layers
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C6/00—Preparation of hydrocarbons from hydrocarbons containing a different number of carbon atoms by redistribution reactions
    • C07C6/08—Preparation of hydrocarbons from hydrocarbons containing a different number of carbon atoms by redistribution reactions by conversion at a saturated carbon-to-carbon bond
    • C07C6/12—Preparation of hydrocarbons from hydrocarbons containing a different number of carbon atoms by redistribution reactions by conversion at a saturated carbon-to-carbon bond of exclusively hydrocarbons containing a six-membered aromatic ring
    • C07C6/126—Preparation of hydrocarbons from hydrocarbons containing a different number of carbon atoms by redistribution reactions by conversion at a saturated carbon-to-carbon bond of exclusively hydrocarbons containing a six-membered aromatic ring of more than one hydrocarbon
    • 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
    • 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
    • B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
    • B01J29/10—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing iron group metals, noble metals or copper
    • B01J29/14—Iron group metals or copper
    • B01J29/146—Y-type faujasite
    • 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
    • B01J29/18—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type
    • B01J29/26—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • 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
    • B01J29/42—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 iron group metals, noble metals or copper
    • B01J29/46—Iron group metals or copper
    • 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
    • B01J29/48—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 arsenic, antimony, bismuth, vanadium, niobium tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • 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
    • B01J29/65—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the ferrierite type, e.g. types ZSM-21, ZSM-35 or ZSM-38, as exemplified by patent documents US4046859, US4016245 and US4046859, respectively
    • B01J29/69—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the ferrierite type, e.g. types ZSM-21, ZSM-35 or ZSM-38, as exemplified by patent documents US4046859, US4016245 and US4046859, respectively containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • 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
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/78—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J29/7815—Zeolite Beta
    • 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

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  • Crystallography & Structural Chemistry (AREA)
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Abstract

The invention discloses a composite catalyst for transalkylation and a preparation method and application thereof, wherein the composite catalyst comprises a plurality of catalyst layers and an optional base layer positioned in the centers of the plurality of catalyst layers, at least one of the plurality of catalyst layers is a hydrogenation catalyst layer, and the rest layers are respectively and independently selected from at least one of a dealkylation catalyst layer, a transalkylation catalyst layer and a hydrogenation catalyst layer. The composite catalyst is used for transalkylation, in particular transalkylation of methylbenzene and inferior heavy aromatic hydrocarbon. Compared with the scheme of multi-bed layer and layered filling, the scheme of the layered filling needs to be matched with the reaction conditions of the multi-bed layers at the same time, and channeling is easy to form. The invention does not need to match the reaction conditions of a plurality of beds, is not easy to form channeling, and has uniform temperature of the whole bed and no temperature gradient.

Description

Composite catalyst for transalkylation and preparation method and application thereof
Technical Field
The invention belongs to the field of transalkylation, and particularly relates to transalkylation of methylbenzene and inferior heavy aromatic hydrocarbon.
Background
The catalytic reforming process in petroleum processing is one of the main processes for producing aromatic hydrocarbons, and it converts naphtha with low octane number into aromatic products such as xylene, benzene, toluene or fuel with high octane number. As the processing depth of chemical processes increases, the weight of upstream monoliths is increasing. The standard of the clean oil product is increasingly improved, and more inferior heavy aromatics are produced as byproducts. By using toluene or benzene and C9 or more heavy aromatic hydrocarbon + A) Transalkylation is an effective method for increasing the yield of xylene and is widely used. In recent years, catalytic reforming has been developed mainly for gasoline production and mainly for aromatic hydrocarbon production, and the size of a reformer has been increased, and a low-pressure continuous regeneration process is the dominant reforming technology. In the process of producing the aromatic hydrocarbon product by the naphtha catalytic reforming process, certain amount of impurities including olefin, polycyclic and polycyclic aromatic hydrocarbon cannot be avoided, the impurities not only influence the purity and specification of the aromatic hydrocarbon product, but also seriously influence the subsequent process procedures due to unqualified quality of the aromatic hydrocarbon product and influence of colloid formation caused by active properties of part of the impurities, and further influence the further processing and utilization of the aromatic hydrocarbon. In the case of olefin impurities, such as benzene reacted with sulfuric acid to produce benzenesulfonic acid, the presence of small amounts of olefin in the benzene can cause the olefin to react simultaneously and result in a colored product; in the production of 120# rubber industrial solvent oil, the olefin can significantly affect the extraction effect.
Catalytic reforming is the leading point of an overall aromatics complex. In order to obtain more aromatics and high octane gasoline to meet market demand, reforming technology is increasingly developed, resulting in an increase in severity of reforming reactions and an increase in the content of inferior products in reformate, thus resulting in an increase in the degree of feedstock deterioration in downstream units thereof, particularly in aromatic transalkylation units. The main impurity types comprise polycyclic aromatic hydrocarbon, heavy polycyclic aromatic hydrocarbon, unsaturated aromatic hydrocarbon and other impurities such as moisture, carbon oxide and the like. The traditional transalkylation catalyst mainly comprises a molecular sieve, a carrier and metal components, and the activity of the traditional transalkylation catalyst mainly comes from an acid center and a metal center of the molecular sieve. Polycyclic aromatic hydrocarbon is easy to be adsorbed on the surface of the catalyst to cover the active center of the reaction. The coke generated after the reaction is deposited on the surface of the catalyst, and has great influence on the activity of the catalyst; heavy polycyclic aromatic hydrocarbons accelerate the coking of the catalyst surface and influence the service life of the catalyst; unsaturated bonds on unsaturated aromatic hydrocarbon are easy to condense on the surface of the catalyst to form coke, and free water is easy to cause that high-temperature water can remove skeleton atoms in a molecular sieve crystal structure, so that the activity of the catalyst is permanently reduced or lost, and the activity and the stability of the catalyst are influenced; carbon oxides tend to adsorb on the catalyst active sites, poison the catalyst, affect the activity of the catalyst, affect product quality, and cause corrosion and damage to equipment.
CN1282733C discloses a catalyst for selective hydrogenation and olefin removal of reformate, which mainly aims at providing high-quality raw materials for subsequent units and reducing the content of olefin in the raw materials. It contains 0.1-1.0wt% of noble metal and 0.05-0.50wt% of alkali metal or alkaline earth metal as auxiliary agents. Under the conditions of the hydrogen reaction, the reaction temperature is 150-250 ℃, the pressure is 1.5-3.0MPa, and the volume space velocity is 2.0-4.0h < -1 >, the bromine index of the product is less than 100mgBr/100g of oil, and the loss of aromatic hydrocarbon is less than 0.5wt%. The olefin removal catalyst only aims at olefin removal of a C8 component, only aims at ensuring that the bromine index of PX adsorption separation feeding is qualified, and often neglects olefin removal in C9 and above components and C7 and below components in order to prolong the service life of the PX adsorption separation feeding, so that carbon deposition is accelerated and the activity of the catalyst is rapidly reduced after C9 heavy aromatic hydrocarbon enters an alkyl transfer unit.
CN105272803A discloses a method for disproportionation and transalkylation of toluene and heavy aromatics, which divides the reactions in the disproportionation and transalkylation of toluene and heavy aromatics into different regions by distinguishing the reaction characteristics of different reactions, wherein the first layer of catalyst is used for partial hydrocracking and lightening of naphthalene series in the heavy aromatics, the second layer of catalyst is used for the disproportionation and transalkylation of methylbenzene to maximize the production of dimethylbenzene and benzene, and the third layer of catalyst selectively cracks non-aromatic hydrocarbons with boiling points close to that of benzene and formed in a hydrogenation side reaction to generate light hydrocarbon components, thereby improving the quality of benzene products. The process can integrate the advantages of catalysts of all layers, improve the conversion rate of heavy aromatics, and simultaneously co-produce qualified benzene products. However, due to the formation of indanes and tetralins, which are hydrogenation products, generated after the raw materials pass through the first layer of catalyst, in the subsequent process of preparing monocyclic aromatic hydrocarbons by hydrocracking, unsaturated hydrocarbons generated by cracking of cycloalkanes formed by excessive hydrogenation easily cause the coverage of the active sites of the second layer of catalyst and the reduction of mass transfer efficiency and activity caused by the blockage of pore channels caused by coke and coke precursors. Moreover, the acid properties and metal hydrogenation performance required for each reaction process are different, and therefore, it is difficult to achieve the optimal reaction state for each reaction system in the same reactor or the same catalyst system.
Disclosure of Invention
In order to overcome the problems in the prior art, the invention provides a transalkylation catalyst, a preparation method and application thereof, wherein the composite catalyst comprises a plurality of composite catalyst layers, and the purpose of realizing multiple functional reactions by one catalyst is realized.
One of the objects of the present invention is to provide a composite catalyst for transalkylation, which comprises a plurality of catalytic layers and an optional base layer disposed at the center of the plurality of catalytic layers, wherein at least one of the plurality of catalytic layers is a hydrogenation catalytic layer, and the remaining layers are each independently selected from at least one of a dealkylation catalytic layer, a transalkylation catalytic layer, and a hydrogenation catalytic layer.
In a preferred embodiment, at least two of the catalytic layers are a hydrogenation catalytic layer and a transalkylation catalytic layer, respectively, and when the catalytic layers are more than two, the remaining layers are each independently selected from at least one of a dealkylation catalytic layer, a transalkylation catalytic layer, and a hydrogenation catalytic layer (and preferably at least one of the remaining layers is a dealkylation catalytic layer).
In a further preferred embodiment, among the plurality of catalytic layers, the outermost layer is a hydrogenation catalytic layer, and at least one of the inner layers is a transalkylation catalytic layer, and when the plurality of catalytic layers is more than two, the remaining layers are each independently selected from at least one of a dealkylation catalytic layer, a transalkylation catalytic layer, and a hydrogenation catalytic layer (and preferably at least one of the remaining layers is a dealkylation catalytic layer).
The plurality of catalytic layers may be two or more, preferably 2 to 6, for example, 2, 3, 4, 5, or 6 layers. When N catalyst layers are arranged, the catalyst layers are 1 layer and 2 layers from inside to outside in sequence, the outermost Nth layer is a hydrogenation catalyst layer, at least one of the 1 st to the N-1 th layers is an alkyl transfer catalyst layer, and the rest layers are respectively and independently selected from at least one of a dealkylation catalyst layer, an alkyl transfer catalyst layer and a hydrogenation catalyst layer (and preferably at least one of the rest layers is a dealkylation catalyst layer).
In a preferred embodiment, when the plurality of catalytic layers are two layers, the outermost layer is a hydrogenation catalytic layer; the internal layer is at least one selected from the group consisting of a dealkylation catalytic layer and a transalkylation catalytic layer.
In a further preferred embodiment, when the plurality of catalytic layers are two layers, the outermost layer is a hydrogenation catalytic layer; the inner layer is a transalkylation catalytic layer.
In a preferred embodiment, when the plurality of catalytic layers is more than two, the outermost layer is a hydrogenation catalytic layer; at least one of the internal layers is a transalkylation catalytic layer, and the remaining layers are each independently selected from at least one of a dealkylation catalytic layer, a transalkylation catalytic layer, and a hydrogenation catalytic layer.
In a further preferred embodiment, when the plurality of catalytic layers is more than two, the outermost layer is a hydrogenation catalytic layer; at least one of the internal layers is a transalkylation catalytic layer and at least one of the remaining layers is a dealkylation catalytic layer.
In the present invention, multiple catalytic layers on a particulate catalyst comprise different reaction functions to achieve a combination of hydrogenation, transalkylation, and optionally dealkylation on the same catalyst particle.
In a preferred embodiment, the hydrocatalytic, dealkylcatalytic and transalkylation catalytic layers each comprise a respective (corresponding) catalyst matrix comprising a support, an optional metal component and an optional molecular sieve.
For example, the hydrogenation catalytic layer comprises a hydrogenation catalyst matrix, the dealkylation catalytic layer comprises a dealkylation catalyst matrix, and the transalkylation catalytic layer comprises a transalkylation catalyst matrix.
In a further preferred embodiment:
the carrier is selected from at least one of alpha alumina, gamma alumina, silicon dioxide and silicon carbide, and preferably, the carriers of each layer are the same or different; and/or the presence of a gas in the gas,
the metal component is selected from at least one of elements in groups IB-VIIB and VIII in the periodic table of elements, and preferably, the metal components of each layer are the same or different; and/or the presence of a gas in the atmosphere,
the molecular sieve is selected from at least one of a silicon-aluminum molecular sieve, a silicon-phosphorus-aluminum molecular sieve and a silicon-titanium-aluminum molecular sieve, preferably selected from a ZSM-5 molecular sieve, a FER molecular sieve, a PTY molecular sieve, an MEI molecular sieve, a ZSM-11 molecular sieve, an MOR molecular sieve, a Y molecular sieve, an STF molecular sieve, an ITQ molecular sieve, a BEA molecular sieve, an MTW molecular sieve, a ZSM-5/ZSM-11 molecular sieve, an MOR/ZSM-5 molecular sieve, an MOR/ZSM-11 molecular sieve, a ZSM-5/Y molecular sieve, a BEA/ZSM-5 molecular sieve and a Y/ZSM-11 molecular sieve, and more preferably, the molecular sieves of each layer are the same or different.
In a further preferred embodiment, the weight of each catalytic layer is 100wt%, wherein the content of the carrier is 5-100 wt%, the content of the metal component is 0-60 wt%, and the content of the molecular sieve is 0-90 wt%.
Preferably, the content of the carrier is 20 to 99wt%, the content of the metal component is 0.1 to 20wt%, and the content of the molecular sieve is 0 to 60wt%, based on 100wt% of each catalytic layer.
In a preferred embodiment, the hydrocatalytic layer comprises a hydrocatalytic catalyst matrix comprising the support I, metal component I and optionally molecular sieve I.
In a further preferred embodiment, the support I is selected from the group consisting of alumina and/or silica; and/or, the metal component I is selected from at least one metal (such as one or two) in group VA or VIII metal and group IVA, preferably at least one (such as one or two) of Co, ni, pd, pt and Sn, and more preferably at least one (such as one or two) of Co, pt and Ni; and/or, the molecular sieve I is selected from at least one (such as one or two) of ZSM-5 molecular sieve, ZSM-11 molecular sieve, ZSM-5/ZSM-11 molecular sieve, Y molecular sieve, ZSM-5/Y molecular sieve, Y/ZSM-11 molecular sieve, STF molecular sieve, MEI molecular sieve and MTW molecular sieve, and more preferably, the molecular sieve is selected from at least one (such as one or two) of ZSM-5 molecular sieve, ZSM-11 molecular sieve, ZSM-5/ZSM-11 molecular sieve, Y molecular sieve, ZSM-5/Y molecular sieve and Y/ZSM-11 molecular sieve.
More preferably, the content of the carrier I is 60-99.9 wt%, the content of the metal component I is 1-5 wt%, and the content of the molecular sieve I is 0-25 wt%, based on 100wt% of the total weight of the hydrogenation catalyst layer.
For example, the carrier I is 30wt%, 40wt%, 50wt%, 60wt%, 70wt%, 80wt% or 90wt%, the metal component I is 1wt%, 2wt%, 3wt%, 4wt% or 5wt%, and the molecular sieve I is 0wt%, 10wt%, 15wt%, 20wt% or 25wt%, based on 100wt% of the total weight of the hydrocatalytic layer.
In a preferred embodiment, the transalkylation catalytic layer comprises a transalkylation catalyst matrix comprising a support II, a molecular sieve II, and optionally a metal component II.
In a further preferred embodiment, the transalkylation catalyst matrix comprises a support II, a molecular sieve II, and optionally a metal component II; preferably, the carrier II is selected from at least one (e.g., one or two) of γ -alumina, silica gel, and silicon carbide; and/or, the metal component II is selected from at least one metal (such as one or two) in VIIB group, VIB group and VIII group, preferably at least one (such as one or two) of Mo, re, rh, zn, ru, ir and Cr, and more preferably at least one (such as one or two) of Mo, re, zn and Cr; and/or, the molecular sieve II is selected from at least one (such as one or two) of PTY molecular sieve, MOR molecular sieve, FER molecular sieve, ZSM-5 molecular sieve, Y molecular sieve, BEA molecular sieve, MOR/ZSM-11 molecular sieve, ITQ molecular sieve, BEA/ZSM-5 molecular sieve and MOR/ZSM-5 molecular sieve, preferably at least one (such as one or two) of Y molecular sieve, MOR molecular sieve, BEA molecular sieve, MOR/ZSM-11 molecular sieve, BEA/ZSM-5 molecular sieve and MOR/ZSM-5 molecular sieve.
In a further preferred embodiment, the content of the carrier II is 10 to 90wt%, the content of the metal component II is 0 to 10wt%, and the content of the molecular sieve II is 20 to 70wt%, based on the total weight of the transalkylation catalyst layer being 100 wt%.
For example, the carrier II is contained in an amount of 10wt%, 20wt%, 30wt%, 40wt%, 50wt%, 60wt%, 70wt%, 80wt% or 90wt%, the metal component II is contained in an amount of 0wt%, 2wt%, 4wt%, 6wt%, 8wt%, 10wt%, and the molecular sieve II is contained in an amount of 20wt%, 30wt%, 40wt%, 50wt%, 60wt% or 70wt%, based on the total weight of the transalkylation catalyst layer being 100 wt%.
In a preferred embodiment, the dealkylation catalytic layer comprises a dealkylation catalyst matrix comprising a support III, a molecular sieve III and optionally a metal component III.
In a further preferred embodiment, the carrier III is selected from at least one (e.g., one or two) of γ -alumina, α -alumina, silica; and/or, the metal component III is selected from at least one metal (e.g. one or two) of group VIII, VA metals, preferably from at least one (e.g. one or two) of Fe, bi, ni, co, more preferably Bi and/or Ni; and/or, the molecular sieve III is selected from at least one of ZSM-5 molecular sieve, ZSM-11 molecular sieve, Y molecular sieve, ZSM-5/Y molecular sieve, Y/ZSM-11 molecular sieve and ZSM-5/ZSM-11 molecular sieve, preferably at least one (such as one or two) of ZSM-5 molecular sieve, ZSM-11 molecular sieve, Y molecular sieve and ZSM-5/Y molecular sieve;
more preferably, the content of the carrier III is 10 to 90wt%, the content of the metal component III is 0 to 20wt%, and the content of the molecular sieve III is 20 to 90wt%, based on 100wt% of the total weight of the dealkylation catalyst layer.
For example, the amount of the carrier III is 10wt%, 20wt%, 30wt%, 40wt%, 50wt%, 60wt%, 70wt%, 80wt%, or 90wt%, the amount of the metal component III is 0wt%, 5wt%, 10wt%, 15wt%, or 20wt%, and the amount of the molecular sieve III is 20wt%, 30wt%, 40wt%, 50wt%, 60wt%, 70wt%, 80wt%, or 90wt%, based on 100wt% of the total weight of the dealkylation catalytic layer.
In a preferred embodiment, the substrate is selected from at least one of gamma-alumina, alpha-alumina, porous silica gel.
In a preferred embodiment, the total weight of the base layer is 0-50wt%, the total content of the hydrogenation catalytic layer is 2-60 wt%, the total content of the transalkylation catalytic layer is 30-95 wt%, and the total content of the dealkylation catalytic layer is 0-60 wt%, based on the total weight of the composite catalyst being 100 wt%.
In a further preferred embodiment, the total weight of the base layer is 0 to 15wt%, the total content of the hydrogenation catalytic layer is 5 to 40wt%, the total content of the transalkylation catalytic layer is 30 to 80wt%, and the total content of the dealkylation catalytic layer is 0 to 60wt%, based on the total weight of the catalytic layers being 100 wt%.
For example, the base layer can have a total weight of 0, 5, 10, 15, 20, 30, 40, or 50wt%, the hydrogenation catalytic layer can have a total content of 5wt%, 10wt%, 15wt%, 20wt%, 25wt%, 30wt%, 35wt%, or 40wt%, the transalkylation catalytic layer can have a total content of 10wt%, 20wt%, 30wt%, 40wt%, 50wt%, 60wt%, 70wt%, or 80wt%, and the dealkylation catalytic layer can have a total content of 0wt%, 10wt%, 20wt%, 30wt%, 40wt%, 50wt%, or 60wt%, based on the total weight of the catalytic layers taken as 100 wt%.
The invention integrates a plurality of functional areas on the composite catalyst, and multi-bed and layered filling is not needed.
In the prior art, the first bed layer is a hydrogenation bed layer, and the hydrogenation is an exothermic reaction, so that the temperature of the hydrogenation bed layer is too high, and a large temperature difference is generated between the hydrogenation bed layer and a subsequent bed layer, so that the whole bed layer system generates a temperature gradient, and the conversion rate and the selectivity are influenced. In addition, the multi-bed layer adopted by the prior art has the problem that a plurality of different bed layers are easily and wrongly filled in the actual operation, and has requirements on the filling of the bed layers, and the channeling phenomenon can be generated when the filling is not good or the filling is uneven.
Compared with the scheme of multi-bed layer and layered filling, the scheme of the multi-bed layer is matched with the reaction conditions of the multi-bed layer at the same time, and channeling is easy to form. The invention does not need to match the reaction conditions of a plurality of beds, is not easy to form channeling, and has uniform temperature of the whole bed and no temperature gradient.
The second purpose of the invention is to provide a preparation method of the composite catalyst of the first purpose of the invention, and the preparation method comprises the following steps that, assuming that the composite catalyst comprises N catalytic layers and optional base layers, N is more than or equal to 2:
(1) Preparing a catalyst substrate corresponding to each catalyst layer;
(2) Optionally taking the base layer as an inner core, and carrying out rolling ball treatment on the catalyst substrate of the innermost catalyst layer to obtain a catalytic ball 1;
(3) Carrying out rolling ball treatment on the catalyst substrate with the penultimate layer inside by taking the catalytic ball 1 as an inner core to obtain a catalytic ball 2;
(4) And (3) repeating the process of the step (3) for 0 to (N-2) times to obtain the composite catalyst.
The hydrogenation catalyst layer corresponds to a hydrogenation catalyst matrix, the dealkylation catalyst layer corresponds to a dealkylation catalyst matrix, and the transalkylation catalyst layer corresponds to a transalkylation catalyst matrix.
In a preferred embodiment, the catalyst substrate is obtainable by the methods disclosed in the prior art, and may also be obtained by: mixing the amount of carrier and the optional amount of molecular sieve, and then loading the optional amount of metal component.
Wherein, the metal component can be loaded by adopting an impregnation method.
The third purpose of the invention is to provide an application of the composite catalyst of the first purpose of the invention or the composite catalyst obtained by the preparation method of the second purpose of the invention in transalkylation, in particular an application in transalkylation of toluene and poor heavy aromatics.
The fourth purpose of the invention is to provide a method for transalkylation of toluene and inferior heavy aromatics, which comprises the following steps: in the presence of the composite catalyst according to the first object of the present invention or the composite catalyst obtained by the preparation method according to the second object of the present invention, raw materials including toluene and inferior heavy aromatics are reacted.
In a preferred embodiment, the inferior heavy aromatics are C9's containing impurities + And A, the impurities comprise one or more of olefin, polycyclic aromatic hydrocarbon (indene, indane) and heavy polycyclic aromatic hydrocarbon.
Wherein the olefin is (aromatic) compound with unsaturated double bond and/or triple bond, and the polycyclic aromatic hydrocarbon comprises
Figure BDA0003139881920000091
Or structures, e.g. indene and/or indan, in the heavy fused ring aromatics
Figure BDA0003139881920000092
Structures, adjacent phenyl rings have two carbons in common, such as naphthalene and/or naphthalene series.
In a preferred embodiment, the reaction temperature is 200-600 ℃, the pressure is 1.0-6.0MPa, and the weight hourly space velocity is 0.5-5.0h -1 The hydrogen-hydrocarbon molecular ratio is 1.0-6.0.
In a further preferred embodiment, the reaction temperature is 340-420 ℃, the pressure is 2-4MPa, and the weight hourly space velocity is 1.5-4.5h -1 The molecular ratio of hydrogen to hydrocarbon is 2-4.5.
In a preferred embodiment, the weight ratio of toluene to heavy aromatics of poor quality is from 100/0 (preferably excluding 0) to 0/100, preferably from 30/70 to 90/10.
The endpoints of the ranges and any values disclosed in the present application are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein. In the following, various technical solutions can in principle be combined with each other to obtain new technical solutions, which should also be regarded as specifically disclosed herein.
Compared with the prior art, the invention has the following beneficial effects: compared with the scheme of multi-bed layer and layered filling, the scheme of the multi-bed layer is matched with the reaction conditions of the multi-bed layer at the same time, and channeling is easy to form. The invention does not need to match the reaction conditions of a plurality of beds, is not easy to form channeling, and has uniform temperature of the whole bed and no temperature gradient.
Drawings
FIG. 1 shows a schematic structural diagram of a composite catalyst according to the present invention;
FIG. 2 shows an SEM image of the composite catalyst obtained in example 1;
fig. 3 shows an SEM image of the composite catalyst obtained in example 2.
Detailed Description
While the present invention will be described in detail and with reference to the specific embodiments thereof, it should be understood that the following detailed description is merely illustrative of the present invention and should not be taken as limiting the scope of the present invention, but is intended to cover modifications and variations thereof that would occur to those skilled in the art upon reading the present disclosure.
It is to be further understood that the various features described in the following detailed description may be combined in any suitable manner without departing from the scope of the invention. The invention is not described in detail in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention can be made, as long as the technical solution formed by the combination does not depart from the idea of the present invention, and the technical solution formed by the combination is part of the original disclosure of the present specification, and also falls into the protection scope of the present invention.
The raw materials used in the examples and comparative examples are disclosed in the prior art if not particularly limited, and may be, for example, directly purchased or prepared according to the preparation methods disclosed in the prior art.
The contents of the products obtained in the examples and comparative examples in the components of table 1 were obtained by the raw material use amount detection method.
[ example 1 ]
1. Preparation of layer (substrate) of component 4 (from outside to inside)
Firstly rolling 8g of alumina into a ball by using a small amount of distilled water to obtain a base layer structure A4;
2. preparation of layer 3 (dealkylation) (outside-in)
30.8g of silicon oxide and 8g of ammonium Y molecular sieve are uniformly mixed, 5.91g of nickel nitrate hexahydrate is dissolved by a small amount of distilled water and then loaded into the mixed powder by adopting an initial impregnation method, and a rolling ball process is carried out by taking A4 as an inner core to obtain the catalyst bead A3. The pellet A3 obtained.
3. Preparation of component 2 layer (transalkylation) (outside-in)
After 18.5g of alumina and 30g of ammonium BEA molecular sieve are uniformly mixed, 1.84g of ammonium heptamolybdate and 1.05g of zinc chloride are dissolved by a small amount of distilled water and loaded into the mixed powder by adopting an initial impregnation method, and a rolling ball process is carried out by taking A3 as an inner core to obtain a catalyst bead A2.
4. Preparation of layer 1 (hydrogenation) (outside-in)
1.7g of alumina and 0.2g of ammonium ZSM-5 molecular sieve are uniformly mixed, 0.64g of cobalt sulfate heptahydrate is dissolved by a small amount of distilled water and then loaded into the mixed powder by adopting an initial impregnation method, and the catalyst bead A1 is obtained by carrying out a rolling ball process by taking A2 as an inner core.
After drying A1, roasting at 500 ℃ for 3 hours, and then reducing at 400 ℃ under the pressure of 3MPa for 4 hours to obtain the catalyst A, wherein the physical properties of the catalyst are shown in Table 1.
Comparative example 1
28.2g of alumina, 30.8g of silicon oxide, 8g of ammonium Y molecular sieve, 30g of ammonium BEA molecular sieve and 0.2g of ammonium ZSM-5 molecular sieve are uniformly mixed, 5.91g of nickel nitrate hexahydrate, 1.84g of ammonium heptamolybdate, 1.05g of zinc chloride and 0.64g of cobalt sulfate heptahydrate are dissolved by a small amount of distilled water and then loaded into the mixed powder by adopting an initial impregnation method, a rolling ball process is carried out to obtain a catalyst pellet B1, the obtained pellet B1 is dried, roasted at 500 ℃ for 3 hours and reduced at 400 ℃ and under the pressure of 3MPa for 4 hours to obtain a catalyst B, and the physical properties of the catalyst are shown in Table 1.
[ example 2 ]
1. Preparation of layer 3 (base) (from outside to inside)
Firstly rolling balls with 5g of alumina/silica (mass ratio is 1: 1) and a small amount of distilled water to obtain a base layer structure C3;
2. preparation of component 2 layer (transalkylation) (outside-in)
59.5g of silicon oxide and 21.25g of ammonium MOR molecular sieve are uniformly mixed, 7.82g of ammonium heptamolybdate is dissolved by a small amount of distilled water and then loaded into the mixed powder by adopting an initial impregnation method, and the catalyst bead C2 is obtained by carrying out a rolling ball process by taking C3 as an inner core.
3. Preparation of component 1 layer (hydrogenation) (outside-in)
0.08g of chloroplatinic acid is dissolved by a small amount of distilled water and then loaded into 9.97 aluminum oxide by adopting an initial impregnation method, and a rolling ball process is carried out by taking C2 as an inner core to obtain a catalyst ball C1.
After drying C1, roasting at 500 deg.C for 3 hours, and then reducing at 400 deg.C under 3MPa for 4 hours to obtain catalyst C, the physical properties of which are shown in Table 1.
Comparative example 2
After uniformly mixing 12.47g of alumina, 62g of silica, 8g of ammonium Y molecular sieve and 21.25g of ammonium MOR molecular sieve, dissolving 7.82g of ammonium heptamolybdate and 0.08g of chloroplatinic acid by using a small amount of distilled water, loading the mixture into the mixed powder by adopting an initial impregnation method, carrying out a rolling ball process to obtain a catalyst pellet D1, drying the obtained pellet D1, roasting at 500 ℃ for 3 hours, and reducing at 400 ℃ and under the pressure of 3MPa for 4 hours to obtain a catalyst D, wherein the physical properties of the catalyst are shown in Table 1.
[ example 3 ]
1. Preparation of layer (substrate) of component 4 (outside-in)
Firstly rolling 10g of silicon oxide by using a small amount of distilled water to obtain a base layer structure E4;
2. preparation of layer 3 (transalkylation) (outside-in)
After 20.125g of silicon oxide/aluminum oxide (mass ratio of 1: 1) and 14g of FER/BEA molecular sieve (mass ratio of 2: 1) are uniformly mixed, 0.28g of rhenium trichloride and 1.29g of ammonium heptamolybdate are dissolved by a small amount of distilled water and then loaded into the mixed powder by adopting an initial impregnation method, and a rolling ball process is carried out by taking E4 as an inner core to obtain a catalyst bead E3. The pellet E3 obtained is then used.
3. Preparation of layer 2 (dealkylation) (outside-in)
After 19.25g of alumina and 14g of ammonium ZSM-11 molecular sieve are uniformly mixed, 3.31g of bismuth nitrate is dissolved by a small amount of distilled water and then loaded into the mixed powder by adopting an initial impregnation method, and a rolling ball process is carried out by taking E3 as an inner core to obtain a catalyst pellet E2.
4. Preparation of component 1 layer (hydrogenation) (outside-in)
2.56g of cobalt sulfate heptahydrate and 0.16g of chloroplatinic acid are dissolved by a small amount of distilled water, and then loaded into 19.54g of alumina by adopting an initial impregnation method, and a rolling ball process is carried out by taking E2 as an inner core to obtain a catalyst bead E1.
Drying E1, roasting at 500 deg.C for 3 hr, and reducing at 400 deg.C under 3MPa for 4 hr to obtain catalyst E with the physical properties shown in Table 1.
[ COMPARATIVE EXAMPLE 3 ]
48.85g of alumina, 20.06g of silica, 14g of FER/BEA molecular sieve (mass ratio 2.
[ example 4 ]
1. Preparation of layer 3 (dealkylation) (outside-in)
After 2.3G of silicon oxide and 2.5G of ammonium ZSM-5 molecular sieve are uniformly mixed, 0.25G of nickel nitrate hexahydrate and 0.28G of bismuth nitrate are dissolved by a small amount of distilled water and then loaded into the mixed powder by adopting an initial impregnation method, and a rolling ball process is carried out to obtain a catalyst pellet G3.
2. Preparation of layer 2 (transalkylation) (outside-in)
30.6G of alumina/silica (mass ratio of 2: 1) and 54G of ammonium MOR/ZSM-5 molecular sieve (mass ratio of 2: 1) are uniformly mixed, 1.42G of rhenium trichloride and 9.44G of zinc chloride are dissolved by a small amount of distilled water and then loaded into the mixed powder by adopting an initial impregnation method, and a rolling ball process is carried out by taking G3 as an inner core to obtain a catalyst pellet G2.
3. Preparation of layer 1 (hydrogenation) (outside-in)
0.08G of palladium chloride is dissolved by a small amount of distilled water and then loaded into 0.25G of Y molecular sieve and 4.7G of alumina by an initial impregnation method, and the catalyst pellet G1 is obtained by carrying out a rolling ball process with G2 as an inner core.
After drying G1, roasting at 500 ℃ for 3 hours, and then reducing at 400 ℃ under the pressure of 3MPa for 4 hours to obtain the catalyst G, wherein the physical properties of the catalyst are shown in Table 1.
Comparative example 4
After 25.1g of alumina, 12.5g of silica, 0.25g of ammonium Y molecular sieve, 54g of ammonium MOR/ZSM-5 molecular sieve (mass ratio is 2: 1) and 2.5g of ammonium ZSM-5 molecular sieve are uniformly mixed, 7.82g of ammonium heptamolybdate and 0.08g of chloroplatinic acid are dissolved by a small amount of distilled water and then loaded into the mixed powder by adopting an initial impregnation method, a rolling ball process is carried out to obtain a catalyst pellet H1, the obtained pellet H1 is dried, calcined at 500 ℃ for 3 hours and reduced at 400 ℃ and under the pressure of 3MPa for 4 hours to obtain the catalyst H, and the physical properties of the catalyst are shown in Table 1.
[ example 5 ] A method for producing a polycarbonate
1. Preparation of component 3 layer (transalkylation) (outside-in)
After 39.435g of alumina and 4g of ammonium BEA molecular sieve were mixed uniformly, 0.69g of chromium nitrate and 0.05g of ammonium heptamolybdate were dissolved in a small amount of distilled water and loaded into the above mixed powder by an initial impregnation method, and a rolling ball process was performed to obtain catalyst pellets 13.
2. Preparation of component 2 layer (dealkylation) (outside-in)
After 11.4g of silicon oxide and 28g of ammonium FER molecular sieve are uniformly mixed, 0.99g of nickel nitrate hexahydrate and 0.76g of bismuth nitrate are dissolved by a small amount of distilled water and then loaded into the mixed powder by adopting an initial impregnation method, and a rolling ball process is carried out by taking I3 as an inner core to obtain the catalyst bead 12.
3. Preparation of layer 1 (hydrogenation) (outside-in)
10.54g of cobalt sulfate heptahydrate and 0.28g of palladium chloride are dissolved by a small amount of distilled water, and then loaded into a mixture of 13.75g of ZSM-5/ZSM-11 molecular sieve (the mass ratio is 3: 1) and 4.7g of alumina by adopting an initial impregnation method, and the catalyst pellet I1 is obtained by carrying out a rolling ball process by taking I2 as an inner core.
Drying the I1, roasting at 500 ℃ for 3 hours, and then reducing at 400 ℃ under the pressure of 3MPa for 4 hours to obtain a catalyst I, wherein the physical properties of the catalyst are shown in Table 1.
Comparative example 5
After 40.26g of alumina, 11.4g of silica, 4g of ammonium BEA molecular sieve, 13.75g of ammonium ZSM-5/ZSM-11 molecular sieve (the mass ratio is 3: 1) and 28g of ammonium FER molecular sieve are uniformly mixed, 0.69g of chromium nitrate, 0.05g of ammonium heptamolybdate, 0.99g of nickel nitrate hexahydrate, 0.76g of bismuth nitrate, 10.54g of cobalt sulfate heptahydrate and 0.28g of palladium chloride are dissolved by a small amount of distilled water and loaded into the mixed powder by adopting an initial impregnation method, a rolling ball process is carried out to obtain a catalyst pellet J1, the obtained pellet J1 is dried, roasted at 500 ℃ for 3 hours and reduced at 400 ℃ under the pressure of 3MPa for 4 hours to obtain the catalyst J, and the physical properties of the catalyst are shown in Table 1.
[ example 6 ]
1. Preparation of layer (substrate) of component 4 (from outside to inside)
Rolling a ball by using a small amount of distilled water on 10g of silicon oxide to obtain a base layer structure K4;
2. preparation of layer 3 (dealkylation) (outside-in)
After 19.25g of alumina and 14g of ammonium ZSM-11 molecular sieve are uniformly mixed, 3.31g of bismuth nitrate is dissolved by a small amount of distilled water and then loaded into the mixed powder by adopting an initial impregnation method, and a rolling ball process is carried out by taking E4 as an inner core to obtain the catalyst pellet k3.
3. Preparation of layer 2 (transalkylation) (outside-in)
After 20.125g of silicon oxide/aluminum oxide (mass ratio of 1: 1) and 14g of FER/BEA molecular sieve (mass ratio of 2: 1) are uniformly mixed, 0.28g of rhenium trichloride and 1.29g of ammonium heptamolybdate are dissolved by a small amount of distilled water and then loaded into the mixed powder by adopting an initial impregnation method, and a ball rolling process is carried out by taking K3 as an inner core to obtain a catalyst bead K2.
4. Preparation of component 1 layer (hydrogenation) (outside-in)
2.56g of cobalt sulfate heptahydrate and 0.16g of chloroplatinic acid are dissolved by a small amount of distilled water, and then loaded into 19.54g of alumina by adopting an initial impregnation method, and a rolling ball process is carried out by taking K2 as an inner core to obtain a catalyst pellet K1.
After drying K1, roasting at 500 ℃ for 3 hours, and then reducing at 400 ℃ and under the pressure of 3MPa for 4 hours to obtain the catalyst K, wherein the physical properties of the catalyst are shown in Table 1.
[ example 7 ] A method for producing a polycarbonate
1. Preparation of layer 3 (dealkylation) (outside-in)
After 11.4g of silicon oxide and 28g of ammonium FER molecular sieve are uniformly mixed, 0.99g of nickel nitrate hexahydrate and 0.76g of bismuth nitrate are dissolved by a small amount of distilled water and then loaded into the mixed powder by adopting an initial impregnation method, and a rolling ball process is carried out to obtain the catalyst pellet M1.
2. Preparation of layer 2 (transalkylation) (outside-in)
After 39.435g of alumina and 4g of ammonium BEA molecular sieve are uniformly mixed, 0.69g of chromium nitrate and 0.05g of ammonium heptamolybdate are dissolved by a small amount of distilled water and then loaded into the mixed powder by adopting an initial impregnation method, and a rolling ball process is carried out by taking M1 as an inner core to obtain a catalyst bead M2.
3. Preparation of component 1 layer (hydrogenation) (outside-in)
10.54g of cobalt sulfate heptahydrate and 0.28g of palladium chloride are dissolved by a small amount of distilled water, and then loaded into a mixture of 13.75g of ZSM-5/ZSM-11 molecular sieve (the mass ratio is 3: 1) and 4.7g of alumina by an initial impregnation method, and a rolling ball process is carried out by taking M2 as an inner core to obtain the catalyst bead M1.
After drying M1, roasting at 500 ℃ for 3 hours, and then reducing at 400 ℃ under the pressure of 3MPa for 4 hours to obtain the catalyst M, wherein the physical properties of the catalyst are shown in Table 1.
Figure BDA0003139881920000171
Figure BDA0003139881920000181
Figure BDA0003139881920000191
Figure BDA0003139881920000201
Table 2: reaction conditions (feed composition C7/C9+ = 50/50)
Figure BDA0003139881920000211
Table 3: catalyst Performance of examples and comparative examples
Figure BDA0003139881920000212
Figure BDA0003139881920000221
The invention has been described in detail with reference to specific embodiments and illustrative examples, but the description is not intended to be construed in a limiting sense. Those skilled in the art will appreciate that various equivalent substitutions, modifications or improvements may be made to the technical solution of the present invention and its embodiments without departing from the spirit and scope of the present invention, which fall within the scope of the present invention. The scope of the invention is defined by the appended claims.

Claims (14)

1. A composite catalyst for transalkylation comprising a plurality of catalytic layers and an optional base layer centrally located between the plurality of catalytic layers, at least one of the plurality of catalytic layers being a hydrogenation catalytic layer, the remaining layers each being independently selected from at least one of a dealkylation catalytic layer, a transalkylation catalytic layer, and a hydrogenation catalytic layer.
2. The composite catalyst of claim 1, wherein at least two of the plurality of catalytic layers are a hydrodecatalytic layer and a transalkylation catalytic layer, respectively, and when the plurality of catalytic layers is more than two, the remaining layers are each independently selected from at least one of a dealkylation catalytic layer, a transalkylation catalytic layer, and a hydroprocessing catalytic layer.
3. The composite catalyst according to claim 1, wherein, among the plurality of catalytic layers, the outermost layer is a hydrogenation catalytic layer, and at least one of the inner layers is a transalkylation catalytic layer, and when the plurality of catalytic layers is more than two, the remaining layers are each independently selected from at least one of a dealkylation catalytic layer, a transalkylation catalytic layer, and a hydrogenation catalytic layer.
4. The composite catalyst of claim 1, wherein the hydrocatalytic layer, dealkylation catalytic layer, and transalkylation catalytic layer each comprise a respective catalyst matrix comprising a support, an optional metal component, and an optional molecular sieve; preferably, the first and second electrodes are formed of a metal,
the carrier is selected from at least one of alpha alumina, gamma alumina, silicon dioxide and silicon carbide, and preferably, the carriers of all layers are the same or different; and/or the presence of a gas in the atmosphere,
the metal component is selected from at least one of elements in groups IB-VIIB and VIII in the periodic table of elements, and preferably, the metal components of each layer are the same or different; and/or the presence of a gas in the gas,
the molecular sieve is selected from at least one of a silicon-aluminum molecular sieve, a silicon-phosphorus-aluminum molecular sieve and a silicon-titanium-aluminum molecular sieve, preferably selected from ZSM-5 molecular sieve, FER molecular sieve, PTY molecular sieve, MEI molecular sieve, ZSM-11 molecular sieve, MOR molecular sieve, Y molecular sieve, STF molecular sieve, ITQ molecular sieve, BEA molecular sieve, MTW molecular sieve, ZSM-5/ZSM-11 molecular sieve, MOR/ZSM-5 molecular sieve, MOR/ZSM-11 molecular sieve, ZSM-5/Y molecular sieve, BEA/ZSM-5 molecular sieve and Y/ZSM-11 molecular sieve, and more preferably, the molecular sieves of each layer are the same or different.
5. The composite catalyst according to claim 4, wherein the weight of each catalytic layer is 100wt%, and the content of the carrier is 5 to 100wt%, the content of the metal component is 0 to 60wt%, and the content of the molecular sieve is 0 to 90wt%.
6. The composite catalyst of claim 4 wherein the hydrocatalytic layer comprises a hydrocatalytic catalyst matrix comprising the support I, metal component I and optionally molecular sieve I;
preferably, the support I is selected from alumina and/or silica; and/or the presence of a gas in the gas,
the metal component I is at least one metal selected from VA group or VIII group and IVA group, preferably at least one of Co, ni, pd, pt and Sn; and/or the presence of a gas in the gas,
the molecular sieve I is selected from at least one of a ZSM-5 molecular sieve, a ZSM-11 molecular sieve, a ZSM-5/ZSM-11 molecular sieve, a Y molecular sieve, a ZSM-5/Y molecular sieve, a Y/ZSM-11 molecular sieve, an STF molecular sieve, an MEI molecular sieve and an MTW molecular sieve;
more preferably, the content of the carrier I is 60-99.9 wt%, the content of the metal component I is 0.1-5 wt%, and the content of the molecular sieve I is 0-25 wt%, based on 100wt% of the total weight of the hydrogenation catalyst layer.
7. The composite catalyst of claim 4 wherein the transalkylation catalytic layer comprises a transalkylation catalyst matrix comprising a support II, a molecular sieve II, and optionally a metal component II;
preferably, the carrier II is selected from at least one of gamma-alumina, silica gel and silicon carbide; and/or the metal component II is selected from at least one metal in VIIB group, VIB group and VIII group, preferably at least one metal in Mo, re, rh, zn, ru, ir and Cr; and/or the molecular sieve II is at least one selected from PTY molecular sieve, MOR molecular sieve, FER molecular sieve, ZSM-5 molecular sieve, Y molecular sieve, BEA molecular sieve, MOR/ZSM-11 molecular sieve, ITQ molecular sieve, BEA/ZSM-5 molecular sieve and MOR/ZSM-5 molecular sieve;
more preferably, the content of the carrier II is 10-90 wt%, the content of the metal component II is 0-10 wt%, and the content of the molecular sieve II is 20-70 wt%, based on the total weight of the transalkylation catalyst layer being 100 wt%.
8. The composite catalyst of claim 4 wherein the dealkylation catalytic layer comprises a dealkylation catalyst matrix comprising a support III, molecular sieve III, and optionally a metal component III;
preferably, the carrier III is selected from at least one of gamma-alumina, alpha-alumina and white carbon black; and/or the metal component III is at least one metal selected from VIII group and VA group metals, preferably at least one metal selected from Fe, bi, ni and Co; and/or the molecular sieve III is selected from at least one of a ZSM-5 molecular sieve, a ZSM-11 molecular sieve, a Y molecular sieve, a ZSM-5/Y molecular sieve, a Y/ZSM-11 molecular sieve and a ZSM-5/ZSM-11 molecular sieve;
more preferably, the content of the carrier III is 10 to 90wt%, the content of the metal component III is 0 to 20wt%, and the content of the molecular sieve III is 20 to 90wt%, based on the total weight of the dealkylation catalyst layer being 100 wt%.
9. The composite catalyst according to claim 1, wherein the base layer is at least one selected from the group consisting of γ -alumina, α -alumina, and porous silica gel.
10. The composite catalyst according to one of claims 1 to 9, wherein the total weight of the base layer is 0 to 50wt%, the total content of the hydrogenation catalyst layer is 2 to 60wt%, the total content of the transalkylation catalyst layer is 30 to 95wt%, and the total content of the dealkylation catalyst layer is 0 to 60wt%, based on 100wt% of the total weight of the plurality of catalyst layers.
11. A method for preparing the composite catalyst according to any one of claims 1 to 10, wherein the composite catalyst comprises N catalyst layers and an optional base layer, wherein N is greater than or equal to 2, the method comprises the following steps:
(1) Preparing a catalyst substrate corresponding to each catalyst layer;
(2) Optionally taking the base layer as an inner core, and carrying out rolling ball treatment on the catalyst substrate of the innermost catalyst layer to obtain a catalytic ball 1;
(3) Carrying out rolling ball treatment on the catalyst substrate with the penultimate layer inside by taking the catalytic ball 1 as an inner core to obtain a catalytic ball 2;
(4) And (3) repeating the process of the step (3) for 0 to (N-2) times to obtain the composite catalyst.
12. Use of the composite catalyst according to any one of claims 1 to 10 or the composite catalyst obtained by the preparation method according to claim 11 in transalkylation, in particular in transalkylation of toluene and poor quality heavy aromatics.
13. A method for transalkylation of toluene and poor-quality heavy aromatic hydrocarbon comprises the following steps: reacting raw materials including toluene and inferior heavy aromatics in the presence of the composite catalyst according to any one of claims 1 to 10 or the composite catalyst obtained by the preparation method according to claim 11.
14. The method of claim 13,
the inferior heavy aromatic hydrocarbon is C9 containing impurities + The impurities comprise one or more of olefin, polycyclic aromatic hydrocarbon and heavy polycyclic aromatic hydrocarbon; and/or the presence of a gas in the gas,
the reaction temperature is 200-600 ℃, the pressure is 1.0-6.0MPa, and the weight hourly space velocity is 0.5-5.0h -1 The molecular ratio of hydrogen to hydrocarbon is 1.0-6.0; and/or the presence of a gas in the atmosphere,
toluene and C 9 + The weight ratio of heavy aromatic hydrocarbon A is 100/0-0/100.
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