CN115501907A - ZSM-5/mordenite composite phase full-crystalline molecular sieve catalyst and preparation and application thereof - Google Patents

ZSM-5/mordenite composite phase full-crystalline molecular sieve catalyst and preparation and application thereof Download PDF

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CN115501907A
CN115501907A CN202110698254.5A CN202110698254A CN115501907A CN 115501907 A CN115501907 A CN 115501907A CN 202110698254 A CN202110698254 A CN 202110698254A CN 115501907 A CN115501907 A CN 115501907A
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catalyst
mordenite
zsm
molecular sieve
phase
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CN115501907B (en
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石张平
李经球
顾士庆
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
    • 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
    • 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
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/615—100-500 m2/g
    • 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
    • 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
    • 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
    • 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
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    • 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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Abstract

The invention discloses a ZSM-5/mordenite composite phase full-crystalline molecular sieve catalyst and a preparation method and application thereof. SiO of the catalyst 2 /Al 2 O 3 The molar ratio is 20-150; the ZSM-5 phase crystal grain size of the catalyst is 100-500 nm; the specific surface area of the catalyst is 400-500 m 2 (ii) in terms of/g. The catalyst is used in toluene disproportionation, heavy aromatic hydrocarbon transalkylation reaction and benzene and heavy aromatic hydrocarbon transalkylation reaction, and has the advantages ofHigh activity and high selectivity.

Description

ZSM-5/mordenite composite phase full-crystalline molecular sieve catalyst and preparation and application thereof
Technical Field
The invention relates to the field of synthesis of molecular sieve catalysts, in particular to a ZSM-5/mordenite composite phase full-crystalline molecular sieve catalyst, a preparation method thereof and application of the catalyst in toluene disproportionation and transalkylation reactions and benzene and heavy aromatic transalkylation reactions.
Background
The molecular sieve has unique pore channels and acid properties, and is widely applied to the fields of adsorption, separation, catalysis and the like. Composite phase molecular sieves are typically composite crystals formed chemically from two or more molecular sieves. The structure of the composite phase molecular sieve not only has the characteristics of a single component, but also has unique structural characteristics and acid properties, shows unique synergistic effect and special reaction performance different from those of a pure phase molecular sieve in catalytic reaction, and shows more potential application value in industries such as petrochemical industry and the like, in particular to a ZSM-5/mordenite composite phase molecular sieve. The ZSM-5 molecular sieve and the mordenite have 10-membered ring and 12-membered ring channel structures respectively, have good hydrothermal stability and shape-selective catalytic performance, and are widely applied to the fields of petrochemical industry and the like. Because the two molecular sieves have uniform and single pore diameters and respectively have special acid distribution and cannot independently process complex raw material components, the composite phase molecular sieve containing ZSM-5 and mordenite also has compound microporous pore passages, and the strong and weak acids have wide distribution range and can simultaneously process complex raw material components with different molecular diameters and different requirements on the acidity. However, the performance requirements for the composite phase molecular sieve of ZSM-5/mordenite are also greatly different for different raw materials and different reactions.
In practical industrial application, the molecular sieve powder has poor strength and is easy to pulverize and run off in the reaction process. Therefore, an inert binder is usually added for molding, so as to ensure the overall shape and mechanical strength of the catalyst. However, the use of inert binders brings with it two problems: (1) The inert binder has no activity, and the introduction of the inert binder can reduce the density of the active center of the catalyst integral molecular sieve; (2) The inert binder has an undeveloped pore structure, and wraps the molecular sieve in the forming process, so that part of molecular sieve pore passages are blocked, and the specific surface area and the diffusion speed of the catalyst are reduced. Both of the above negative effects directly affect the reaction performance of the catalyst, so that the activity of the catalyst is reduced and the deactivation rate of carbon deposition is increased. In the prior art, a general method is to convert a binder introduced in the molecular sieve forming process into an effective component of the molecular sieve by a secondary crystallization method, so that the whole catalyst does not contain the binder component and keeps high mechanical strength, and the molecular sieve catalyst is called as a full-crystalline molecular sieve catalyst, so that the density of an active center and the diffusion performance of the catalyst can be effectively improved.
CN200910201647.X discloses a binderless ZSM-5/mordenite coexisting molecular sieve catalyst and a preparation method thereof. The method adopts a ZSM-5 molecular sieve as a body, firstly, the ZSM-5 molecular sieve, an alkaline substance, an aluminum source and silica sol are molded, the molded ZSM-5 molecular sieve catalyst is crystallized in steam of organic amine, and a binder is converted into mordenite to obtain the ZSM-5/mordenite full-crystalline molecular sieve catalyst. Although the method can effectively solve the problem of the binder in the composite phase molecular sieve catalyst, the basicity of the mordenite synthesis is higher than that of ZSM-5, the ZSM-5 catalyst formed by the binder is used as a body, and the binder is converted into the mordenite, so that the ZSM-5 molecular sieve is dissolved and then crystallized into the mordenite due to the high basicity, the influence of crystallization condition control on the phase ratio of the ZSM-5 and the mordenite is large, and the phase composition fluctuation is easily caused due to the deviation of the crystallization condition control, so that the catalyst performance is influenced.
CN102188993B discloses a preparation method of a binderless MFI/MOR composite zeolite molecular sieve catalyst. The method takes an MOR zeolite molecular sieve as a body, mixes and kneads the MOR zeolite molecular sieve with silicon source and aluminum source raw materials for molding, and then crystallizes the silicon source and the aluminum source into MFI by a gas-solid phase crystallization method, thereby obtaining the MFI/MOR composite zeolite molecular sieve catalyst. However, the method can cause the reduction of the mesoporous volume in the secondary crystallization process of the molecular sieve, reduce the external diffusion performance of the composite phase molecular sieve catalyst and influence the performance of the catalyst.
Disclosure of Invention
The invention aims to solve the technical problem that the activity and selectivity of the existing ZSM-5/mordenite composite phase full-crystalline molecular sieve catalyst are low, and provides a ZSM-5/mordenite composite phase full-crystalline molecular sieve catalyst and a preparation method and application thereof. The catalyst is used in toluene disproportionation and heavy aromatic hydrocarbon transalkylation reaction and benzene and heavy aromatic hydrocarbon transalkylation reaction, and has high activity and high selectivity.
The invention provides a ZSM-5/mordenite composite phase full-crystalline molecular sieve catalyst, and SiO of the catalyst 2 /Al 2 O 3 The molar ratio is 20-150; the ZSM-5 phase crystal grain size of the catalyst is 100-500 nm; the specific surface area of the catalyst is 400-500 m 2 /g。
In the technical scheme, the mesoporous volume of the catalyst is 0.2-0.4 cm 3 (ii)/g; the mesopore volume accounts for 60-85% of the total pore volume.
In the technical scheme, in the catalyst, the weight ratio of a ZSM-5 phase to a mordenite phase is 1:9 to 9:1.
in the technical scheme, the catalyst is an epitaxial eutectic molecular sieve; the catalyst is a composite with a ZSM-5 phase and a mordenite phase with a complete crystal structure. In the catalyst, a ZSM-5 phase and a mordenite phase are arranged at a crystal boundary in a staggered and uniform manner.
In the technical scheme, the ZSM-5 phase SiO in the catalyst 2 /Al 2 O 3 The molar ratio is higher than that of the mordenite phase SiO 2 /Al 2 O 3 A molar ratio; ZSM-5 phase of SiO 2 /Al 2 O 3 The molar ratio being mordenite phase SiO 2 /Al 2 O 3 1.2 to 2 times of the molar ratio.
In the above technical scheme, the catalyst is a catalyst without a binder. In the catalyst, the mass fraction of the binder in the catalyst is less than or equal to 0.5%.
The second aspect of the present invention provides a method for preparing the catalyst, comprising the steps of:
(1) Carrying out first mixing on the mordenite and a binder, kneading and forming, then carrying out first drying and first roasting to obtain a formed object;
(2) Secondly, mixing the molded object obtained in the step (1) with an alkali source, a template agent, an aluminum source, water and organic alcohol, pretreating, and carrying out hydrothermal crystallization to obtain a molecular sieve catalyst precursor;
(3) And (3) performing ammonium exchange, washing, secondary drying and secondary roasting on the molecular sieve catalyst precursor obtained in the step (2) to obtain the ZSM-5/mordenite composite phase full-crystalline molecular sieve catalyst.
In the above technical scheme, the binder in the step (1) is silica sol. In the silica sol, siO 2 The mass content of (A) is 20-40%.
In the above technical scheme, the mordenite in the step (1) is Na-type mordenite or SiO 2 /Al 2 O 3 The molar ratio is 20 to 100.
In the technical scheme, the mordenite and the binder in the step (1) are SiO 2 The weight ratio of (1): 9 to 9:1.
in the above technical solution, the first mixing in step (1) is conventional mechanical mixing, and may be achieved by using a mechanical stirring method. The kneading molding can be made into a conventional catalyst shape by a conventional molding method, for example, the molding method can be extrusion molding, rotational molding, etc., and the shape can be a strip shape, a ball shape, etc. The particle size of the molded product may be 1 to 10mm. The conditions of the first drying were as follows: the drying temperature is 50-150 ℃, and the drying time is 1-24 h. The conditions of the first calcination are as follows: the roasting temperature is 400-600 ℃, and the roasting time is 1-24 h.
In the above technical solution, the organic alcohol in the step (2) includes any one or more of monohydric alcohols having 1 to 6 carbon atoms, preferably any one or more of methanol, ethanol and propanol. The adding amount of the organic alcohol is 0.01-5 percent of the mass of the binder, and preferably 0.5-4 percent. The alkali source is inorganic alkali; the inorganic base comprises one or more of NaOH, KOH and ammonia water. The template agent comprises one or more of ethylamine, n-butylamine, tetrapropylammonium hydroxide and tetrapropylammonium bromide. The aluminum source comprises any one or more of sodium metaaluminate, aluminum hydroxide, aluminum sulfate, aluminum chloride and aluminum nitrate. The water is deionized water.
In the above technical scheme, in the step (2), the formed product is SiO in the binder 2 The alkali source is calculated by OH - Metering, template agent, aluminum source and Al 2 O 3 Metering water by H 2 The molar ratio of O is 20-100: 5 to 10:0.01 to 2:0 to 5:600 to 2000.
In the above technical solution, in the step (2), preferably, the alkali source, the templating agent, the aluminum source, the water, and the organic alcohol are prepared into a solution, and then mixed with the molded product obtained in the step (1). The second mixing in the step (2) is conventional mechanical mixing, and can be realized by adopting a mechanical stirring method. The pretreatment conditions were as follows: the pretreatment temperature is 80-120 ℃, and the pretreatment time is 1-10 hours. The hydrothermal crystallization conditions are as follows: the crystallization temperature is 140-200 ℃, and the crystallization time is 10-200 h.
In the above technical scheme, the ammonium exchange in step (3) can be performed by using a conventional method, for example, the molecular sieve catalyst precursor obtained in step (2) is contacted with an ammonium salt aqueous solution to perform ammonium exchange. The mass concentration of the ammonium salt aqueous solution is 5-20%; the ammonium salt can be any one or more of ammonium chloride, ammonium nitrate and ammonium sulfate. The temperature of the ammonium exchange is 50-95 ℃, the time of the ammonium exchange is 1-10 h, and the number of times of the ammonium exchange is 1-5. The mass ratio of the ammonium salt aqueous solution to the molecular sieve catalyst precursor is 1-10: 1. the conditions of the second drying in step (3) are as follows: the drying temperature is 50-150 ℃, and the drying time is 1-24 h. The conditions of the second roasting are as follows: the roasting temperature is 400-600 ℃, and the roasting time is 1-24 h. The washing liquid used for washing is preferably deionized water.
The third aspect of the invention provides the application of the catalyst in toluene disproportionation and heavy aromatics transalkylation reaction.
In the above technical solution, the applying includes: toluene and heavy aromatics are used as raw materials, and the raw materials are in contact reaction with the catalyst to obtain the products of benzene and xylene. The heavy aromatic hydrocarbon source is catalytically reformed or catalytically cracked, and specifically comprises at least one monocyclic aromatic hydrocarbon mixture with the carbon atom number more than or equal to 9, such as trimethylbenzene, methyl ethylbenzene, propyl benzene, indane, tetramethylbenzene, diethylbenzene, dimethyl ethylbenzene and the like.
In the above technical scheme, the reaction conditions of toluene disproportionation and heavy aromatic transalkylation are as follows: the reaction temperature is 300-500 ℃, and the mass space velocity of the raw material is 2-6 h -1 The reaction pressure is 2-4 MPa, and the hydrogen-hydrocarbon molar ratio is 2-4: 1. the mass ratio of the toluene to the heavy aromatics in the raw material is 90/10-10/90.
The invention provides the application of the catalyst in benzene and heavy aromatic hydrocarbon transalkylation reaction.
In the above technical solution, the applying includes: benzene and heavy aromatics are used as raw materials, and the raw materials are in contact reaction with the catalyst to obtain toluene and xylene which are products. The heavy aromatic hydrocarbon source is subjected to catalytic reforming or catalytic cracking, and specifically comprises at least one monocyclic aromatic hydrocarbon mixture with the carbon atom number more than or equal to 9, such as trimethylbenzene, methyl ethylbenzene, propylbenzene, indane, tetramethylbenzene, diethylbenzene, dimethyl ethylbenzene and the like.
In the above technical scheme, the reaction conditions of the benzene and heavy aromatic hydrocarbon transalkylation reaction are as follows: the reaction temperature is 300-500 ℃, and the mass space velocity of the raw material is 2-6 h -1 The reaction pressure is 2-4 MPa, the hydrogen-hydrocarbon molar ratio is 2-4: 1. the composition of hydrocarbon in the raw material is that the mass ratio of benzene to heavy aromatics is 90/10-10/90.
Compared with the prior art, the invention has the following beneficial effects:
(1) The catalyst is a ZSM-5/mercerized composite phase full-crystalline molecular sieve catalyst, wherein the ZSM-5 phase of the catalyst has a nano-scale grain size of 100-500 nm; the catalyst has a large specific surface area of 400-500 m 2 (ii)/g; preferably, the catalyst of the invention does not contain a binder basically, has high crystallinity, large mesoporous volume, higher active center density of the catalyst and higher diffusion performance of the catalyst, and is applied to toluene disproportionation and heavy aromatic transalkylationThe reaction and the benzene and heavy aromatic hydrocarbon transalkylation reaction have the characteristics of high activity, high selectivity and low ethylbenzene.
(2) In the preparation method of the catalyst, the mordenite with higher synthetic alkalinity is used as a body, the raw material binder is converted into the ZSM-5 molecular sieve with lower synthetic alkalinity requirement, so that the dissolution and recrystallization of the mordenite in the crystallization process are effectively avoided, and the accurate regulation and control of the phase ratio of the ZSM-5 molecular sieve to the mordenite in a large range can be realized by controlling the dosage of the binder; in the preparation method of the catalyst, the organic alcohol is added into the raw materials and is pretreated before crystallization, so that a proper amount of crystal nucleus can be formed before crystal transformation, the organic alcohol modifier and the crystal transformation process are subjected to nucleation treatment, the growth speed of a ZSM-5 phase is reduced, the grain diameter of the ZSM-5 molecular sieve obtained by crystal transformation is reduced, and the specific surface area of the catalyst is improved. The catalyst of the present invention is applied in toluene disproportionation and alkyl transfer reaction, and benzene and heavy arene alkyl transfer reaction, and has the features of high activity, high selectivity and low ethyl benzene.
(3) The ZSM-5/mercerized composite phase full-crystalline molecular sieve catalyst is applied to toluene disproportionation and transalkylation reactions and benzene and heavy aromatic hydrocarbon transalkylation reactions, and has the characteristics of high activity and high selectivity. The catalyst is applied to toluene disproportionation and heavy aromatic hydrocarbon transalkylation reactions, the total conversion rate can reach more than 46%, the total selectivity can reach more than 90%, the quality purity of a benzene product can reach more than 99.9%, and the content of a byproduct ethylbenzene can reach less than 0.3%. The catalyst of the invention is applied to the transalkylation reaction of benzene and heavy aromatics, the total conversion rate can reach more than 49 percent, the total selectivity can reach more than 90 percent, and the content of ethylbenzene can reach less than 0.5 percent.
Drawings
FIG. 1 is an XRD spectrum of a molecular sieve catalyst of an example and a comparative example;
wherein, line 1 is the XRD spectrogram of the formed product obtained in the step (1) in the example 1, the comparative example 1 and the comparative example 2, line 2 is the XRD spectrogram of the ZSM-5/mordenite composite phase all-crystalline molecular sieve catalyst finally obtained in the example 1, line 3 is the XRD spectrogram of the ZSM-5/mordenite composite phase all-crystalline molecular sieve catalyst finally obtained in the example 2, and line 4 is the XRD spectrogram of the ZSM-5/mordenite composite phase all-crystalline molecular sieve catalyst finally obtained in the example 3; line a is an XRD standard spectrogram of ZSM-5; line b is an XRD standard spectrogram of the mordenite;
FIG. 2 is a scanning electron micrograph of the ZSM-5/mordenite composite phase fully crystalline molecular sieve catalyst of example 1;
FIG. 3 is an XRD spectrum of a comparative molecular sieve catalyst;
wherein, the line 1 is the XRD spectrogram of the ZSM-5/mordenite composite phase fully-crystallized molecular sieve catalyst finally obtained in the comparative example 1, and the line 2 is the XRD spectrogram of the ZSM-5/mordenite composite phase fully-crystallized molecular sieve catalyst finally obtained in the comparative example 2.
Detailed Description
While the present invention will be described in detail with reference to the following examples, it should be understood that the following examples are illustrative of the present invention and are not to be construed as limiting the scope of the present invention.
The starting materials used in the embodiments of the present invention are commercially available in a purity of analytical grade (AR).
In the invention, the XRD test equipment is a D/max-1400 type full-automatic X-ray diffractometer produced by Japan science company, and the parameters are as follows: the test voltage is 40kV, the current is 40mA, the scanning range is 5-50 degrees, and the scanning speed is 2 degrees/min.
In the invention, the weight ratio of ZSM-5 to mordenite and the mass fraction of the binder in the catalyst are obtained by Rietveld refinement of XRD data.
In the invention, the testing equipment of the specific surface area is a 3 Flex-Physiorption type full-automatic specific surface and pore size distribution analyzer of Micromeritics company, the specific surface area is obtained by calculation of a Brunauer-Emmett-Teller method, and the mesoporous volume is obtained by calculation of a Barrett-Joyner-Halenda method.
In the invention, a ZSM-5 molecular sieve particle size testing device Hitachi S-4800 type cold field emission high resolution scanning electron microscope of Hitachi corporation of Japan is adopted, the particle size of the molecular sieve is obtained by average calculation of the particle sizes of 50 molecular sieve particles, and the parameters are as follows: the acceleration voltage was 20kV.
In the present invention, the relative SiO of ZSM-5 and mordenite in the fully crystalline catalyst 2 /Al 2 O 3 And analyzing the content of the micro-area component elements by adopting the EDS energy spectrometer equipped in the scanning electron microscope according to the molar ratio.
In the invention, the calculation formula of toluene disproportionation and heavy aromatics transalkylation performance is as follows:
conversion (%) = (mass of toluene and heavy aromatics reacted and/mass of toluene and heavy aromatics fed to reactor) × 100%;
selectivity (%) = (mass of produced benzene and xylene and/mass of toluene and heavy aromatic hydrocarbons which are reacted off) x 100%;
benzene product mass purity (%) = (mass of benzene/mass of benzene and C5-C7 non-aromatic hydrocarbons sum) × 100%;
in the invention, the benzene and heavy aromatic hydrocarbon transalkylation performance calculation formula is as follows:
conversion (%) = (mass benzene and heavy aromatics reacted off and/mass sum of benzene and heavy aromatics fed to reactor) × 100%;
selectivity (%) = (mass of toluene and xylene produced and/mass of benzene and heavy aromatic hydrocarbons reacted up) × 100%.
In the examples and comparative examples of the present invention, the compositions of heavy aromatics used in the toluene disproportionation and heavy aromatic transalkylation reactions and the benzene and heavy aromatic transalkylation reactions were in weight percent: wherein the mass fraction of trimethylbenzene in the heavy aromatics is 53.3 percent, the mass fraction of methyl ethyl benzene is 22.3 percent, the mass fraction of propyl benzene is 4.5 percent, the mass fraction of indene series substances is 0.8 percent, and the mass fraction of carbon deca-aromatics is 19.1 percent.
Example 1
(1) Taking SiO 2 /Al 2 O 3 Sodium mordenite with molar ratio of 35, adding binder silica Sol (SiO) 2 40 percent of mass content), kneading, extruding, molding, drying at 120 ℃ for 12 hours, and roasting at 550 ℃ for 5 hours in an air atmosphere to obtain a molded product. Wherein the mordenite is mixed with a binder, such as SiO 2 The weight ratio is 3:1. pellets of molded bodyThe diameter is 0.3cm.
(2) Preparing a solution from an alkali source NaOH, a template agent n-butylamine, an aluminum source aluminum sulfate, water and ethanol according to a metering ratio, adding the formed object obtained in the step (1), uniformly mixing, pretreating at 100 ℃ for 4 hours, and crystallizing at 170 ℃ for 24 hours to obtain a molecular sieve catalyst precursor. In the step (2), the shaped article is formed by SiO in the binder 2 The alkali source is calculated by OH - Metering, template agent and aluminum source are Al 2 O 3 Water in H 2 The molar ratio of O is 40:5:0.1:0.1:1200. the adding amount of the ethanol is 1 percent of the mass of the adhesive.
(3) Mixing an ammonium nitrate solution with the weight content of 10% with the molecular sieve catalyst precursor obtained in the step (2) according to the mass ratio of 5:1, mixing and carrying out ammonium exchange. The temperature of the ammonium exchange was 95 ℃ and the ammonium exchange time was 5 hours, repeated four times. Washing with deionized water, drying at 120 ℃ for 24h, and roasting at 550 ℃ for 4h to obtain the ZSM-5/mordenite composite phase full-crystalline molecular sieve catalyst A.
The test results show that the SiO content of the obtained catalyst A 2 /Al 2 O 3 The molar ratio was 40.
The weight ratio of the mordenite phase to the ZSM-5 phase in the obtained ZSM-5/mordenite composite phase full-crystalline molecular sieve catalyst A is 3.01:1. the quality of the ZSM-5 molecular sieve is very close to that of a binder SiO 2 The feeding quality shows that the crystallization route adopting the mordenite as the body can effectively ensure that the mordenite can not be dissolved and recrystallized, the proportion of ZSM-5 and the mordenite in the full-crystallization catalyst A is accurately controllable, and the content of the binder is 0.25 percent.
The obtained ZSM-5 phase SiO in catalyst A 2 /Al 2 O 3 The molar ratio is higher than that of SiO in mordenite phase 2 /Al 2 O 3 A molar ratio; ZSM-5 phase of SiO 2 /Al 2 O 3 The molar ratio being mordenite phase SiO 2 /Al 2 O 3 1.5 times of the molar ratio.
The mesoporous volume of the obtained catalyst A is 0.26cm 3 (ii)/g; the mesopore volume accounts for 65% of the total pore volume.
The specific surface area of the resulting catalyst A was426m 2 (ii) in terms of/g. The grain diameter of the ZSM-5 molecular sieve obtained by crystal transformation is 200nm. The XRD pattern is shown in figure 1, wherein line 2 is the XRD pattern of ZSM-5/mordenite composite phase fully crystalline molecular sieve catalyst A in example 1, and line 1 is the XRD pattern of the shaped body in step (1) of the preparation method. Comparing with the standard spectrograms of lines a and b in FIG. 1, the typical ZSM-5 and mordenite diffraction peaks appear in the crystallized fully-crystallized catalyst A shown in line 2 in FIG. 1, which indicates that the binder is converted into ZSM-5, and the scanning electron microscope shows that the obtained catalyst is an epitaxial eutectic molecular sieve; the obtained catalyst is a complex with a ZSM-5 phase and a mordenite phase complete crystal structure. Wherein, ZSM-5 phase and mordenite phase are arranged at the crystal boundary position in a staggered and uniform way, and a scanning electron micrograph is shown in figure 2.
The obtained ZSM-5/mordenite composite phase full-crystallization catalyst A is used for toluene disproportionation and heavy aromatic hydrocarbon transalkylation reaction, the reaction temperature is 380 ℃, and the mass space velocity of the raw material is 5h -1 The reaction pressure is 3MPa, the molar ratio of hydrogen to hydrocarbon is 3, the mass ratio of toluene to heavy aromatic hydrocarbon in the raw materials is 45, the total conversion rate is 48%, the total selectivity is 92%, the mass purity of the benzene product is 99.96%, and the content of the byproduct ethylbenzene is 0.1%.
The full-crystallization catalyst A is used for the transalkylation reaction of benzene and heavy aromatics, the reaction temperature is 385 ℃, and the mass space velocity of the raw material is 5h -1 Under the conditions that the reaction pressure is 3MPa, the molar ratio of reaction hydrogen to hydrocarbon is 3, and the mass ratio of the raw material benzene to heavy aromatic hydrocarbon is 40.
Comparative example 1
(1) Taking SiO 2 /Al 2 O 3 Sodium mordenite with molar ratio of 35, adding binder silica Sol (SiO) 2 40 percent of mass content), kneading, extruding, molding, drying at 120 ℃ for 12 hours, and roasting at 550 ℃ for 5 hours in an air atmosphere to obtain a molded product. Wherein the mordenite is mixed with a binder, such as SiO 2 The weight ratio is 3:1. the particle size of the molded article was 0.3cm.
(2) Preparing a solution from an alkali source NaOH, a template agent n-butylamine, an aluminum source aluminum sulfate and water according to a metering ratio, adding the formed product, uniformly mixing, and pretreating at 100 DEG CAnd treating for 4 hours, and crystallizing at 170 ℃ for 24 hours to obtain the molecular sieve catalyst precursor. In the step (2), the shaped article is formed by SiO in the binder 2 The alkali source is calculated by OH - Metering, template agent and aluminum source are Al 2 O 3 Water in H 2 The molar ratio of O is 40:5:0.1:0.1:1200.
(3) Mixing an ammonium nitrate solution with the weight content of 10% with the molecular sieve catalyst precursor obtained in the step (2) according to the mass ratio of 5:1, mixing and performing ammonium exchange. And the ammonium exchange is carried out at the temperature of 95 ℃ for 5 hours, the ammonium exchange is repeated for four times, the mixture is washed by deionized water, dried for 24 hours at the temperature of 120 ℃, and roasted for 4 hours at the temperature of 550 ℃ to obtain the ZSM-5/mordenite composite phase full-crystalline molecular sieve catalyst DA.
The test results show that the SiO of the obtained catalyst DA 2 /Al 2 O 3 The molar ratio was 41.
The XRD patterns are shown in fig. 1 and 3. In FIG. 1, line 1 is the XRD spectrum of the shaped product obtained in step (1) of comparative example 1. In FIG. 3, line 1 is the XRD pattern of the ZSM-5/mordenite composite phase fully crystalline molecular sieve catalyst DA of comparative example 1. The weight ratio of the mordenite phase to the ZSM phase in the ZSM-5/mordenite composite phase full-crystalline molecular sieve catalyst DA is calculated to be 2.95, 1, the mass of the ZSM-5 molecular sieve is very close to that of a binder SiO 2 The feeding quality and the content of the binder are about 0.54 percent.
ZSM-5 phase SiO in the obtained catalyst DA 2 /Al 2 O 3 The molar ratio being mordenite phase SiO 2 /Al 2 O 3 1.4 times of the molar ratio.
The mesoporous volume of the obtained catalyst DA is 0.11cm 3 (ii)/g; the mesopore volume accounts for 40% of the total pore volume.
The specific surface area of the catalyst DA thus obtained was 378m 2 And/g, the grain diameter of the ZSM-5 molecular sieve obtained by crystal transformation is 1 mu m.
The full-crystallization catalyst DA is used for the disproportionation of toluene and the transalkylation of heavy aromatics at the reaction temperature of 380 ℃ and the mass space velocity of the raw material of 5h -1 The reaction pressure is 3MPa, the molar ratio of reaction hydrogen to hydrocarbon is 3, the mass ratio of the raw material toluene to the heavy aromatic hydrocarbon is 45, the total conversion rate is 39%, and the total selectivity is as follows88 percent, the quality purity of the benzene product is 99.78 percent, and the content of the ethylbenzene is 3.2 percent.
The full-crystallization catalyst DA is used for the transalkylation reaction of benzene and heavy aromatics at the reaction temperature of 385 ℃ and the mass space velocity of the raw material of 5h -1 The reaction pressure is 3MPa, the molar ratio of reaction hydrogen to hydrocarbon is 3, the mass ratio of the raw material benzene to the heavy aromatic hydrocarbon is 40.
Comparative example 2
(1) Taking SiO 2 /Al 2 O 3 Sodium mordenite with molar ratio of 35, adding binder silica Sol (SiO) 2 40 percent of mass content), kneading, extruding, molding, drying at 120 ℃ for 12 hours, and roasting at 550 ℃ for 5 hours in an air atmosphere to obtain a molded product. Wherein the mordenite is mixed with a binder, in the form of SiO 2 The weight ratio is 3:1. the particle size of the molded article was 0.3cm.
(2) Preparing an alkali source NaOH, a template agent n-butylamine, an aluminum source aluminum sulfate and water into a solution according to a metering ratio, adding the formed objects, uniformly mixing, and carrying out crystallization treatment at 170 ℃ for 24 hours to obtain a molecular sieve catalyst precursor. In the step (2), the formed product is SiO in the binder 2 The alkali source is calculated by OH - Metering, template agent and aluminum source are Al 2 O 3 Water in H 2 The molar ratio of O is 40:5:0.1:0.1:1200.
(3) Mixing an ammonium nitrate solution with the weight content of 10% with the molecular sieve catalyst precursor obtained in the step (2) according to the mass ratio of 5:1, mixing and carrying out ammonium exchange. And the ammonium exchange is carried out at the temperature of 95 ℃ for 5 hours, the ammonium exchange is repeated for four times, the obtained product is washed by deionized water, dried for 24 hours at the temperature of 120 ℃, and roasted for 4 hours at the temperature of 550 ℃ to obtain the ZSM-5/mordenite composite phase full-crystalline molecular sieve catalyst DB.
The test results show that the SiO of the obtained catalyst DB 2 /Al 2 O 3 The molar ratio was 39.5.
The XRD patterns are shown in figures 1 and 3. In FIG. 1, line 1 is the XRD spectrum of the shaped product obtained in step (1) of comparative example 2. In FIG. 3, line 2 is the XRD pattern of the ZSM-5/mordenite composite phase fully crystalline molecular sieve catalyst DB of comparative example 2.The weight ratio of the mordenite phase to the ZSM phase in the ZSM-5/mordenite composite phase full-crystalline molecular sieve catalyst DB is calculated to be 3.01, 1, the mass of the ZSM-5 molecular sieve is very close to that of a binder SiO 2 The feeding quality and the content of the binder are 0.62 percent.
ZSM-5 phase SiO in the obtained catalyst DB 2 /Al 2 O 3 The molar ratio being mordenite phase SiO 2 /Al 2 O 3 1.4 times of the molar ratio.
The mesoporous volume of the obtained catalyst DB is 0.09cm 3 (ii)/g; the mesopore volume accounts for 38% of the total pore volume.
The specific surface area of the resulting catalyst DB was 369m 2 The grain diameter of the ZSM-5 molecular sieve obtained by crystal transformation is 1.2 mu m.
The full-crystallization catalyst DB is used for the disproportionation of toluene and the heavy transalkylation reaction, the reaction temperature is 380 ℃, and the mass space velocity of the raw material is 5h -1 The reaction pressure is 3MPa, the molar ratio of hydrogen to hydrocarbon is 3, the mass ratio of the toluene/heavy aromatic hydrocarbon as the raw material is 45, the total conversion rate is 38%, the total selectivity is 89%, the mass purity of the benzene product is 99.72%, and the content of ethylbenzene is 2.2%.
The full-crystallization catalyst DB is used for the transalkylation reaction of benzene and heavy aromatics, and the mass space velocity of the raw material is 5h at the reaction temperature of 385 DEG C -1 The reaction pressure is 3MPa, the molar ratio of reaction hydrogen to hydrocarbon is 3, the mass ratio of the raw material benzene to heavy aromatic hydrocarbon is 40.
Example 2
(1) Taking SiO 2 /Al 2 O 3 Sodium mordenite with molar ratio of 20, adding binder silica Sol (SiO) 2 Mass content of 20 percent), kneading, extruding and molding, drying at 100 ℃ for 24 hours, and roasting at 550 ℃ for 10 hours in air atmosphere to obtain a molded product. Wherein the mordenite is mixed with a binder, such as SiO 2 The weight ratio is 1:1. the particle size of the molded article was 0.1cm.
(2) Preparing NaOH, tetrapropylammonium bromide, aluminum nitrate, water and methanol into solution according to a metering ratio, adding the formed product, uniformly mixing, and pretreating at 80 ℃ for 6 hoursThen crystallization treatment is carried out for 190 hours at 165 ℃ to obtain the molecular sieve catalyst precursor. In the step (2), the formed product is SiO in the binder 2 The alkali source is calculated by OH - Metering, template agent and aluminum source are Al 2 O 3 Water in H 2 The molar ratio of O is 100:10:1.5:4.5:1800. the addition of methanol is 1% of the mass of the binder.
(3) Mixing an ammonium nitrate solution with the weight content of 20% with the molecular sieve catalyst precursor obtained in the step (2) according to the mass ratio of 2:1, mixing and carrying out ammonium exchange. The temperature of the ammonium exchange was 55 ℃ and the ammonium exchange time was 10 hours, which was repeated four times. Washing with deionized water, drying at 50 ℃ for 24h, and roasting at 550 ℃ for 10h to obtain the ZSM-5/mordenite composite phase full-crystalline molecular sieve catalyst B.
The test results show that the SiO content of the catalyst B is 2 /Al 2 O 3 The molar ratio was 27.
The weight ratio of the mordenite phase to the ZSM-5 phase in the ZSM-5/mordenite composite phase fully-crystalline molecular sieve catalyst B is 1:1.03. the quality of the ZSM-5 molecular sieve is very close to that of a binder SiO 2 The feeding quality shows that the crystallization route adopting the mordenite as the body can effectively ensure that the mordenite can not be dissolved and recrystallized, the proportion of ZSM-5 and the mordenite in the full-crystallization catalyst B is accurately controllable, and the content of the binder is 0.22 percent.
The obtained ZSM-5 phase SiO in the catalyst B 2 /Al 2 O 3 The molar ratio is higher than that of the mordenite phase SiO 2 /Al 2 O 3 A molar ratio; ZSM-5 phase of SiO 2 /Al 2 O 3 The molar ratio being mordenite phase SiO 2 /Al 2 O 3 1.3 times of the molar ratio.
The mesoporous volume of the obtained catalyst B is 0.28cm 3 (iv) g; the mesopore volume accounts for 67% of the total pore volume.
The specific surface area of the resulting catalyst B was 413m 2 (ii) in terms of/g. The grain diameter of the ZSM-5 molecular sieve obtained by crystal transformation is 180nm. The XRD pattern is shown in FIG. 1, wherein line 3 is the XRD pattern of ZSM-5/mordenite composite phase fully crystalline molecular sieve catalyst B of example 2. Comparing with standard spectrogram of line a and b in FIG. 1, and looking at line 3 in FIG. 1Typical ZSM-5 and mordenite diffraction peaks appear in the crystallized full-crystalline catalyst B, which indicates that the formed binder is converted into ZSM-5, and a scanning electron microscope shows that the obtained catalyst is an epitaxial eutectic molecular sieve; the obtained catalyst is a complex with a ZSM-5 phase and a mordenite phase complete crystal structure; ZSM-5 phase and mordenite phase are arranged in a staggered and uniform way at the crystal boundary.
The obtained ZSM-5/mordenite composite phase full-crystallization catalyst B is used for toluene disproportionation and heavy aromatic hydrocarbon transalkylation reaction, the reaction temperature is 390 ℃, and the mass space velocity of the raw material is 5h -1 The reaction pressure is 3MPa, the molar ratio of hydrogen to hydrocarbon is 2, the mass ratio of the toluene/heavy aromatic hydrocarbon as the raw material is 90, the total conversion rate is 51%, the total selectivity is 97%, the mass purity of the benzene product is 99.96%, and the content of ethylbenzene is 0.1%.
The full-crystallization catalyst B is used for the transalkylation reaction of benzene and heavy aromatics, and the mass space velocity of the raw material is 5h at the reaction temperature of 390 DEG C -1 Under the conditions that the reaction pressure is 3MPa, the molar ratio of hydrogen to hydrocarbon is 2, and the mass ratio of the raw material benzene to the heavy aromatic hydrocarbon is 90.
Example 3
(1) Taking SiO 2 /Al 2 O 3 Sodium mordenite with a molar ratio of 100, adding a binder silica Sol (SiO) 2 Mass content of 20 percent), kneading, extruding and molding, drying at 120 ℃ for 12 hours, and roasting at 600 ℃ for 1 hour in air atmosphere to obtain a molded product. Wherein the mordenite is mixed with a binder, in the form of SiO 2 The weight ratio is 2:1. the particle size of the molded article was 0.5cm.
(2) Preparing KOH, tetrapropylammonium bromide, aluminum chloride, water and methanol into a solution according to a metering ratio, adding the formed product, uniformly mixing, pretreating at 80 ℃ for 6 hours, and crystallizing at 155 ℃ for 190 hours to obtain a molecular sieve catalyst precursor. In the step (2), the shaped article is formed by SiO in the binder 2 Counting alkali source as OH - Metering, template agent and aluminum source are Al 2 O 3 Metering water by H 2 The molar ratio of O is 80:7:2:2:900. the quantity of methanol added is the mass of the binder0.5％。
(3) And (3) mixing an ammonium nitrate solution with the weight content of 10% with the molecular sieve catalyst precursor obtained in the step (2) according to the mass ratio of 7:1, mixing and carrying out ammonium exchange. The temperature of the ammonium exchange was 75 ℃ and the ammonium exchange time was 6 hours, repeated four times. Washing with deionized water, drying at 120 ℃ for 24h, and roasting at 550 ℃ for 4h to obtain the ZSM-5/mordenite composite phase full-crystalline molecular sieve catalyst C.
The test results show that the SiO content of the catalyst C obtained 2 /Al 2 O 3 The molar ratio was 108.
The weight ratio of the mordenite phase to the ZSM-5 phase in the obtained ZSM-5/mordenite composite phase full-crystalline molecular sieve catalyst C is 1:1.98. the quality of the ZSM-5 molecular sieve is very close to that of a binder SiO 2 The feeding quality shows that the crystallization route adopting the mordenite as the body can effectively ensure that the mordenite can not be dissolved and recrystallized, the proportion of ZSM-5 and the mordenite in the full-crystallization catalyst C is accurately controllable, and the content of the binder is 0.12 percent.
The obtained catalyst C contains ZSM-5 phase SiO 2 /Al 2 O 3 The molar ratio is higher than that of the mordenite phase SiO 2 /Al 2 O 3 The molar ratio; ZSM-5 phase SiO 2 /Al 2 O 3 The molar ratio being mordenite phase SiO 2 /Al 2 O 3 1.23 times of the molar ratio.
The mesoporous volume of the obtained catalyst C is 0.30cm 3 (ii)/g; the mesopore volume accounts for 71% of the total pore volume.
The specific surface area of the obtained catalyst C was 437m 2 (iv) g. The grain diameter of the ZSM-5 molecular sieve obtained by crystal transformation is 250nm. The XRD pattern is shown in FIG. 1, where line 4 is the XRD pattern of ZSM-5/mordenite composite phase fully crystalline molecular sieve catalyst C of example 3. Comparing with the standard spectrograms of lines a and b in FIG. 1, typical ZSM-5 and mordenite diffraction peaks appear in the crystallized fully-crystallized catalyst C shown in line 4 in FIG. 1, which indicates that the formed binder is converted into ZSM-5, and the scanning electron microscope shows that the obtained catalyst is an epitaxial eutectic molecular sieve; the obtained catalyst is a complex with a ZSM-5 phase and a mordenite phase complete crystal structure; ZSM-5 phase and mordenite phase are arranged uniformly at the crystal boundary in a staggered way。
The obtained ZSM-5/mordenite composite phase full-crystallization catalyst C is used for toluene disproportionation and heavy aromatic hydrocarbon transalkylation reaction at the reaction temperature of 360 ℃ and the mass space velocity of the raw material of 6h -1 Under the conditions that the reaction pressure is 2MPa, the molar ratio of reaction hydrogen to hydrocarbon is 4, the mass ratio of the toluene/heavy aromatic hydrocarbon as a raw material is 30.
The full-crystallization catalyst C is used for the transalkylation reaction of benzene and heavy aromatics at the reaction temperature of 375 ℃ and the mass space velocity of the raw material of 2h -1 The reaction pressure is 2MPa, the molar ratio of reaction hydrogen to hydrocarbon is 4, the mass ratio of the raw material benzene to the heavy aromatic hydrocarbon is 30.
Example 4
(1) Taking SiO 2 /Al 2 O 3 Sodium mordenite with molar ratio of 50, adding binder silica Sol (SiO) 2 Mass content of 20 percent), kneading, extruding and molding, drying at 120 ℃ for 6 hours, and roasting at 500 ℃ for 20 hours in air atmosphere to obtain a molded product. Wherein the mordenite is mixed with a binder, such as SiO 2 The weight ratio is 1:9. the particle size of the molded article was 0.3cm.
(2) Preparing ammonia water, ethylamine, sodium metaaluminate, water and propanol into a solution according to a metering ratio, adding the formed product, uniformly mixing, pretreating at 80 ℃ for 6 hours, and crystallizing at 185 ℃ for 10 hours to obtain a molecular sieve catalyst precursor. In the step (2), the formed product is SiO in the binder 2 The alkali source is calculated by OH - Metering, template agent, aluminum source and Al 2 O 3 Water in H 2 The molar ratio of O is 40:8:0.3:0.03:600. the addition amount of the propanol is 4 percent of the mass of the adhesive.
(3) Mixing an ammonium nitrate solution with the weight content of 10% with the molecular sieve catalyst precursor obtained in the step (2) according to the mass ratio of 10:1, mixing and performing ammonium exchange. The temperature of the ammonium exchange was 85 ℃ and the ammonium exchange time was 5 hours, which was repeated four times. Washing with deionized water, drying at 90 ℃ for 24h, and roasting at 450 ℃ for 12h to obtain the ZSM-5/mordenite composite phase full-crystalline molecular sieve catalyst D.
The test results show that the SiO content of the resulting catalyst D 2 /Al 2 O 3 The molar ratio was 56.
The weight ratio of the mordenite phase to the ZSM-5 phase in the ZSM-5/mordenite composite phase fully-crystalline molecular sieve catalyst D is 1:8.90. the quality of the ZSM-5 molecular sieve is very close to that of a binder SiO 2 The feeding quality shows that the crystallization route adopting the mordenite as the body can effectively ensure that the mordenite can not be dissolved and recrystallized, the proportion of ZSM-5 and the mordenite in the full-crystallization catalyst D is accurately controllable, and the content of the binder is 0.41 percent.
The obtained catalyst D contains ZSM-5 phase SiO 2 /Al 2 O 3 The molar ratio is higher than that of the mordenite phase SiO 2 /Al 2 O 3 A molar ratio; ZSM-5 phase SiO 2 /Al 2 O 3 The molar ratio being mordenite phase SiO 2 /Al 2 O 3 2 times of the molar ratio.
The mesoporous volume of the obtained catalyst D is 0.35cm 3 (ii)/g; the mesopore volume accounts for 84% of the total pore volume.
The specific surface area of the obtained catalyst D was 482m 2 (ii) in terms of/g. The grain diameter of the ZSM-5 molecular sieve obtained by crystal transformation is 100nm. XRD results show that typical ZSM-5 and mordenite diffraction peaks appear in the crystallized full-crystalline catalyst D, which indicates that the formed binder is converted into ZSM-5, and a scanning electron microscope shows that the obtained catalyst is an epitaxial eutectic molecular sieve; the obtained catalyst is a complex with a ZSM-5 phase and a mordenite phase complete crystal structure; ZSM-5 phase and mordenite phase are arranged in a staggered and uniform way at the crystal boundary.
The obtained ZSM-5/mordenite composite phase full-crystallization catalyst D is used for toluene disproportionation and heavy aromatic hydrocarbon transalkylation reaction, the reaction temperature is 380 ℃, the mass space velocity of the raw material is 5h -1 The reaction pressure is 3MPa, the molar ratio of hydrogen to hydrocarbon is 3, the mass ratio of the toluene/heavy aromatic hydrocarbon as the raw material is 50, the total conversion rate is 49%, the total selectivity is 95%, the mass purity of the benzene product is 99.90%, and the content of ethylbenzene is 0.2%.
The full-crystallization catalyst D is used for benzene and heavy aromaticsTransalkylation reaction at 385 deg.C and 5 hr of space velocity -1 The reaction pressure is 3MPa, the molar ratio of reaction hydrogen to hydrocarbon is 3, the mass ratio of the raw material benzene to heavy aromatic hydrocarbon is 50, the total conversion rate is 50%, the total selectivity is 93%, and the ethylbenzene content is 0.9%.
Example 5
(1) Taking SiO 2 /Al 2 O 3 Sodium mordenite with molar ratio of 10, adding binder silica Sol (SiO) 2 40 percent of mass content), kneading, extruding, forming, drying at 50 ℃ for 24 hours, and roasting at 400 ℃ in an air atmosphere for 24 hours to obtain a formed product. Wherein the mordenite is mixed with a binder, such as SiO 2 The weight ratio is 9:1. the particle size of the molded article was 1cm.
(2) Preparing NaOH, tetrapropylammonium bromide, aluminum hydroxide, water and ethanol into a solution according to a metering ratio, adding the formed product, uniformly mixing, pretreating at 80 ℃ for 6 hours, and crystallizing at 185 ℃ for 10 hours to obtain a molecular sieve catalyst precursor. In the step (2), the formed product is SiO in the binder 2 Counting alkali source as OH - Metering, template agent, aluminum source and Al 2 O 3 Metering water by H 2 The molar ratio of O is 100:10:0.3:2:2000. the adding amount of the ethanol is 1.5 percent of the mass of the adhesive.
(3) Mixing an ammonium nitrate solution with the weight content of 10% with the molecular sieve catalyst precursor obtained in the step (2) according to the mass ratio of 5:1, mixing and performing ammonium exchange. The temperature of the ammonium exchange was 90 ℃ and the ammonium exchange time was 4 hours, repeated four times. Washing with deionized water, drying at 150 deg.C for 1h, and calcining at 400 deg.C for 10h to obtain ZSM-5/mordenite composite phase full-crystalline molecular sieve catalyst E.
The test results show that SiO of the resulting catalyst E 2 /Al 2 O 3 The molar ratio was 103.
The weight ratio of the mordenite phase to the ZSM-5 phase in the obtained ZSM-5/mordenite composite phase fully-crystalline molecular sieve catalyst E is 8.98:1. the quality of the ZSM-5 molecular sieve is very close to that of a binder SiO 2 The feeding quality shows that the crystallization route adopting the mordenite as the body can effectively ensure that the mordenite is not mixed with the mordeniteThe catalyst can be dissolved and recrystallized, the proportion of ZSM-5 and mordenite in the full-crystallization catalyst E is accurately controllable, and the content of the binder is 0.21 percent.
The obtained ZSM-5 phase of SiO in the catalyst E 2 /Al 2 O 3 The molar ratio is higher than that of SiO in mordenite phase 2 /Al 2 O 3 The molar ratio; ZSM-5 phase of SiO 2 /Al 2 O 3 In the mordenite phase SiO 2 /Al 2 O 3 1.8 times of the molar ratio.
The mesoporous volume of the obtained catalyst E is 0.24cm 3 (ii)/g; the mesopore volume accounts for 71% of the total pore volume.
The specific surface area of the resulting catalyst E was 406m 2 (iv) g. The grain diameter of the ZSM-5 molecular sieve obtained by crystal transformation is 100nm. XRD results show that typical ZSM-5 and mordenite diffraction peaks appear in the crystallized full-crystalline catalyst E, which indicates that the formed binder is converted into ZSM-5, and a scanning electron microscope shows that the obtained catalyst is an epitaxial eutectic molecular sieve; the obtained catalyst is a complex with a complete crystal structure of a ZSM-5 phase and a mordenite phase; ZSM-5 phase and mordenite phase are arranged in a staggered and uniform way at the crystal boundary.
The obtained ZSM-5/mordenite composite phase full-crystallization catalyst E is used for toluene disproportionation and heavy aromatic hydrocarbon transalkylation reaction, the reaction temperature is 350 ℃, and the mass space velocity of the raw material is 3h -1 The reaction pressure is 3MPa, the molar ratio of reaction hydrogen to hydrocarbon is 3, the mass ratio of the toluene/heavy aromatic hydrocarbon as raw materials is 20, the total conversion rate is 52%, the total selectivity is 90%, the mass purity of the benzene product is 99.91%, and the content of ethylbenzene is 0.1%.
The full-crystallization catalyst E is used for the transalkylation reaction of benzene and heavy aromatic hydrocarbon, the reaction temperature is 355 ℃, and the mass space velocity of the raw material is 3h -1 The reaction pressure is 3MPa, the molar ratio of hydrogen to hydrocarbon is 3, the mass ratio of the raw material benzene to heavy aromatic hydrocarbon is 20, the total conversion rate is 55%, the total selectivity is 90%, and the ethylbenzene content is 0.3%.
Example 6
(1) Taking SiO 2 /Al 2 O 3 Sodium mordenite with molar ratio of 70, adding binder silica Sol (SiO) 2 30 percent of mass content,Kneading, extruding to form strips, drying at 150 deg.C for 10 hr, and calcining at 500 deg.C in air atmosphere for 8 hr to obtain the final product. Wherein the mordenite is mixed with a binder, in the form of SiO 2 The weight ratio is 3:1. the particle size of the molded article was 0.5cm.
(2) Preparing NaOH, tetrapropylammonium bromide, aluminum sulfate, water and methanol into a solution according to a metering ratio, adding the formed product, uniformly mixing, pretreating at 100 ℃ for 10 hours, and crystallizing at 170 ℃ for 10 hours to obtain a molecular sieve catalyst precursor. In the step (2), the shaped article is formed by SiO in the binder 2 Counting alkali source as OH - Metering, template agent and aluminum source are Al 2 O 3 Metering water by H 2 The molar ratio of O is 50:6:0.3:1.5:700. the adding amount of the methanol is 1.0 percent of the mass of the adhesive.
(3) Mixing an ammonium nitrate solution with the weight content of 20% with the molecular sieve catalyst precursor obtained in the step (2) according to the mass ratio of 3:1, mixing and carrying out ammonium exchange. The temperature of the ammonium exchange was 90 ℃ and the ammonium exchange time was 4 hours, repeated four times. Washing with deionized water, drying at 120 deg.C for 24 hr, and calcining at 550 deg.C for 4 hr to obtain ZSM-5/mordenite composite phase full-crystalline molecular sieve catalyst F.
The test results show that SiO of the obtained catalyst F 2 /Al 2 O 3 The molar ratio was 74.
The weight ratio of the mordenite phase to the ZSM-5 phase in the ZSM-5/mordenite composite phase fully-crystalline molecular sieve catalyst F is 3.04:1. the quality of the ZSM-5 molecular sieve is very close to that of a binder SiO 2 The feeding quality shows that the crystallization route adopting the mordenite as the body can effectively ensure that the mordenite can not be dissolved and recrystallized, the proportion of ZSM-5 and the mordenite in the full-crystallization catalyst F is accurately controllable, and the content of the binder is 0.23 percent.
The obtained catalyst F contains ZSM-5 phase SiO 2 /Al 2 O 3 The molar ratio is higher than that of the mordenite phase SiO 2 /Al 2 O 3 The molar ratio; ZSM-5 phase SiO 2 /Al 2 O 3 The molar ratio being mordenite phase SiO 2 /Al 2 O 3 1.3 times of the molar ratio.
The mesoporous volume of the obtained catalyst F is 0.29cm 3 (iv) g; the mesopore volume accounts for 70% of the total pore volume.
The specific surface area of the resulting catalyst F was 432m 2 (ii) in terms of/g. The grain diameter of the ZSM-5 molecular sieve obtained by crystal transformation is 200nm. XRD results show that the crystallized full-crystalline catalyst F has typical ZSM-5 and mordenite diffraction peaks, which indicates that the formed binder is converted into ZSM-5, and a scanning electron microscope shows that the obtained catalyst is an epitaxial eutectic molecular sieve; the obtained catalyst is a complex with a ZSM-5 phase and a mordenite phase complete crystal structure; the ZSM-5 phase and the mordenite phase are arranged in a staggered and uniform way at the crystal boundary.
The obtained ZSM-5/mordenite composite phase full-crystallization catalyst F is used for toluene disproportionation and heavy aromatic hydrocarbon transalkylation reaction at the reaction temperature of 380 ℃ and the mass space velocity of the raw material of 6h -1 Under the conditions that the reaction pressure is 3MPa, the molar ratio of hydrogen to hydrocarbon is 3, and the mass ratio of the toluene to the heavy aromatic hydrocarbon is 40.
The full-crystallization catalyst F is used for the transalkylation reaction of benzene and heavy aromatic hydrocarbon, the reaction temperature is 380 ℃, the mass space velocity of the raw material is 6h -1 Under the conditions that the reaction pressure is 3MPa, the molar ratio of reaction hydrogen to hydrocarbon is 3, and the mass ratio of the raw material benzene to heavy aromatic hydrocarbon is 40.
Example 7
(1) Taking SiO 2 /Al 2 O 3 Sodium mordenite with molar ratio of 30, adding binder silica Sol (SiO) 2 30 percent of mass content), kneading, extruding, molding, drying at 150 ℃ for 1 hour, and roasting at 600 ℃ for 1 hour in an air atmosphere to obtain a molded product. Wherein the mordenite is mixed with a binder, such as SiO 2 The weight ratio is 3:1. the particle size of the molded article was 0.3cm.
(2) Preparing NaOH, tetrapropylammonium hydroxide, water and ethanol into solution according to the metering ratio, adding the formed product, uniformly mixing, pretreating for 10 hours at 110 ℃, crystallizing for 12 hours at 185 ℃ to obtain the molecular sieve catalystAnd (3) agent precursor. In the step (2), the shaped article is formed by SiO in the binder 2 The alkali source is calculated by OH - Counting, template agent and water in H 2 The molar ratio of O is 50:8:0.5:800. the adding amount of the ethanol is 0.7 percent of the mass of the adhesive.
(3) Mixing an ammonium nitrate solution with the weight content of 20% with the molecular sieve catalyst precursor obtained in the step (2) according to the mass ratio of 3:1, mixing and carrying out ammonium exchange. The temperature of the ammonium exchange was 95 ℃ and the ammonium exchange time was 4 hours, which was repeated four times. Washing with deionized water, drying at 120 ℃ for 24h, and roasting at 500 ℃ for 10h to obtain the ZSM-5/mordenite composite phase full-crystalline molecular sieve catalyst G.
The test results showed that SiO of the resulting catalyst G 2 /Al 2 O 3 The molar ratio was 41.
The weight ratio of the mordenite phase to the ZSM-5 phase in the obtained ZSM-5/mordenite composite phase fully-crystalline molecular sieve catalyst G is 3.01:1. the quality of the ZSM-5 molecular sieve is very close to that of a binder SiO 2 The feeding quality shows that the crystallization route adopting the mordenite as the body can effectively ensure that the mordenite can not be dissolved and recrystallized, the proportion of ZSM-5 and the mordenite in the full-crystallization catalyst G is accurately controllable, and the content of the binder is 0.20 percent.
The obtained ZSM-5 phase SiO in the catalyst G 2 /Al 2 O 3 The molar ratio is higher than that of SiO in mordenite phase 2 /Al 2 O 3 The molar ratio; ZSM-5 phase SiO 2 /Al 2 O 3 The molar ratio being mordenite phase SiO 2 /Al 2 O 3 1.5 times of the molar ratio.
The mesoporous volume of the obtained catalyst G was 0.31cm 3 (ii)/g; the mesopore volume accounts for 73% of the total pore volume.
The specific surface area of the obtained catalyst G was 437m 2 (iv) g. The grain diameter of the ZSM-5 molecular sieve obtained by crystal transformation is 140nm. XRD results show that the crystallized full-crystalline catalyst G has typical ZSM-5 and mordenite diffraction peaks, which indicates that the formed binder is converted into ZSM-5, and a scanning electron microscope shows that the obtained catalyst is an epitaxial eutectic molecular sieve; the obtained catalyst is a complex with a complete crystal structure of a ZSM-5 phase and a mordenite phase;the ZSM-5 phase and the mordenite phase are arranged in a staggered and uniform way at the crystal boundary.
The obtained ZSM-5/mordenite composite phase full-crystallization catalyst G is used for toluene disproportionation and heavy aromatic hydrocarbon transalkylation reaction, the reaction temperature is 385 ℃, and the material mass space velocity is 5h -1 Under the conditions that the reaction pressure is 3MPa, the molar ratio of reaction hydrogen to hydrocarbon is 3, and the mass ratio of the raw material toluene to heavy aromatic hydrocarbon is 40.
The full-crystallization catalyst G is used for the transalkylation reaction of benzene and heavy aromatics at the reaction temperature of 385 ℃ and the mass space velocity of the raw material of 5h -1 The reaction pressure is 3MPa, the molar ratio of reaction hydrogen to hydrocarbon is 3, the mass ratio of the raw material benzene to heavy aromatic hydrocarbon is 40.

Claims (13)

1. ZSM-5/mordenite composite phase full-crystalline molecular sieve catalyst, siO of the catalyst 2 /Al 2 O 3 The molar ratio is 20-150; the grain diameter of ZSM-5 phase crystal grains in the catalyst is 100-500 nm; the specific surface area of the catalyst is 400-500 m 2 /g。
2. The catalyst according to claim 1, wherein the catalyst has a mesopore volume of 0.2 to 0.4cm 3 (ii)/g; the mesopore volume accounts for 60-85% of the total pore volume.
3. The catalyst of claim 1, wherein the catalyst is a ZSM-5 phase of SiO 2 /Al 2 O 3 The molar ratio is higher than that of SiO in mordenite phase 2 /Al 2 O 3 The molar ratio;
further, ZSM-5 phase of SiO 2 /Al 2 O 3 The molar ratio being mordenite phase SiO 2 /Al 2 O 3 1.2 to 2 times of the molar ratio.
4. The catalyst of claim 1, wherein the weight ratio of ZSM-5 phase to mordenite phase in the catalyst is from 1:9 to 9:1.
5. the catalyst of claim 1, wherein the catalyst is an epitaxial eutectic molecular sieve; the catalyst is a complex with a ZSM-5 phase and a mordenite phase complete crystal structure.
6. The catalyst of claim 1, wherein the catalyst is a binderless catalyst in which the binder comprises less than or equal to 0.5% by weight of the catalyst.
7. A method for preparing a catalyst as claimed in any one of claims 1 to 6, comprising the steps of:
(1) Carrying out first mixing on the mordenite and a binder, kneading and forming, then carrying out first drying and first roasting to obtain a formed object;
(2) Secondly, mixing the molded object obtained in the step (1) with an alkali source, a template agent, an aluminum source, water and organic alcohol, pretreating, and carrying out hydrothermal crystallization to obtain a molecular sieve catalyst precursor;
(3) And (3) carrying out ammonium exchange, washing, secondary drying and secondary roasting on the molecular sieve catalyst precursor obtained in the step (2) to obtain the ZSM-5/mordenite composite phase full-crystalline molecular sieve catalyst.
8. The preparation method according to claim 7, wherein the organic alcohol in the step (2) comprises any one or more of monohydric alcohols with 1-6 carbon atoms, preferably any one or more of methanol, ethanol and propanol;
and/or, the adding amount of the organic alcohol in the step (2) is 0.01-5 percent of the mass of the binder, preferably 0.5-4 percent;
and/or, the alkali source in the step (2) is inorganic alkali; the inorganic base comprises any one or more of NaOH, KOH and ammonia water;
and/or, the template agent in the step (2) comprises any one or more of ethylamine, n-butylamine, tetrapropylammonium hydroxide and tetrapropylammonium bromide;
and/or, the aluminum source in the step (2) comprises any one or more of sodium metaaluminate, aluminum hydroxide, aluminum sulfate, aluminum chloride and aluminum nitrate;
and/or, the water in the step (2) is deionized water;
and/or, in the step (2), the formed product is SiO in the binder 2 The alkali source is calculated by OH - Metering, template agent and aluminum source are Al 2 O 3 Water in H 2 The molar ratio of O is 20-100: 5 to 10:0.01 to 2:0 to 5:600 to 2000;
and/or, in the step (2), preferably, after preparing the alkali source, the template agent, the aluminum source, water and the organic alcohol into a solution, mixing the solution with the formed product obtained in the step (1).
9. The production method according to claim 7, wherein the conditions of the pretreatment in the step (2) are as follows: the pretreatment temperature is 80-120 ℃, and the pretreatment time is 1-10 hours;
and/or, the hydrothermal crystallization conditions in the step (2) are as follows: the crystallization temperature is 140-200 ℃, and the crystallization time is 10-200 h.
10. The production method according to claim 7, wherein the binder in the step (1) is silica sol; in the silica sol, siO 2 The mass content of (A) is 20-40%;
and/or, in the step (1), the mordenite is Na-type mordenite, siO 2 /Al 2 O 3 The molar ratio is 20-100;
and/or, in step (1), the mordenite and the binder are SiO 2 The weight ratio of (1): 9 to 9:1;
and/or, the kneading molding in the step (1) is at least one of extrusion molding and rotation molding; the particle size of the formed product is 1-10 mm;
and/or, the conditions of the first drying in the step (1) are as follows: the drying temperature is 50-150 ℃, and the drying time is 1-24 h;
and/or, the conditions of the first roasting in the step (1) are as follows: the roasting temperature is 400-600 ℃, and the roasting time is 1-24 h.
11. The preparation method according to claim 7, wherein the mass concentration of the ammonium salt aqueous solution in the ammonium exchange in the step (3) is 5-20%; the ammonium salt is any one or more of ammonium chloride, ammonium nitrate and ammonium sulfate;
and/or the temperature of the ammonium exchange is 50-95 ℃, the time of the ammonium exchange is 1-10 h, and the number of times of the ammonium exchange is 1-5;
and/or, the mass ratio of the ammonium salt aqueous solution to the molecular sieve catalyst precursor is 1-10: 1.
12. use of a catalyst as claimed in any one of claims 1 to 6 or prepared by a process as claimed in any one of claims 7 to 11 in toluene disproportionation and heavy aromatics transalkylation reactions.
13. Use of a catalyst according to any one of claims 1 to 6 or prepared by a process according to any one of claims 7 to 11 in benzene and heavy aromatics transalkylation reactions.
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