CN117945828A - Method for substituting hydrogen on benzene ring and application thereof - Google Patents

Method for substituting hydrogen on benzene ring and application thereof Download PDF

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Publication number
CN117945828A
CN117945828A CN202211268749.5A CN202211268749A CN117945828A CN 117945828 A CN117945828 A CN 117945828A CN 202211268749 A CN202211268749 A CN 202211268749A CN 117945828 A CN117945828 A CN 117945828A
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molecular sieve
hydrogen
crystallization
benzene
pore
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陈俊文
翟云平
王永睿
孙敏
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Sinopec Petrochemical Research Institute Co ltd
China Petroleum and Chemical Corp
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Sinopec Petrochemical Research Institute Co ltd
China Petroleum and Chemical Corp
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

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Abstract

The invention relates to the field of petrochemical industry, and discloses a method for replacing hydrogen on a benzene ring and application thereof. The method for substituting hydrogen on benzene ring of the invention comprises the following steps: and (2) in the presence of a hydrogen type IM-5 molecular sieve, enabling benzene series to contact with olefin for reaction, wherein the total specific surface area of the hydrogen type IM-5 molecular sieve is 250-450m 2/g, the total pore volume is 0.2-0.7cm 3/g, the most probable mesoporous diameter is 4-20nm, and the silicon-aluminum ratio is below 60. The method can react under the low-temperature condition, and has higher target product selectivity under the low-temperature condition; the hydrogen type IM-5 molecular sieve has low silicon-aluminum ratio, and has abundant mesopores on crystal grains, and can have better catalytic performance without acid treatment in the preparation process.

Description

Method for substituting hydrogen on benzene ring and application thereof
Technical Field
The invention relates to the field of petrochemical industry, in particular to a method for replacing hydrogen on benzene rings and application thereof.
Background
The development of petrochemical industry and fine chemical industry, the increasingly stringent sustainable development and environmental production requirements, have led to an increasing demand for new catalytic materials.
In 1997, french Petroleum Co (IFP) in WO98/17581A1, NC 1234012A disclosed an IM-5 molecular sieve for the first time. The molecular sieve has a two-dimensional ten-membered ring channel system, and in a third-dimensional limited short channel, the channel system is very similar to a ZSM-5 molecular sieve, and has good shape selectivity. Meanwhile, the IM-5 molecular sieve has good thermal stability and hydrothermal stability and excellent catalytic performance, and has wide application in petrochemical catalytic reaction, for example, the IM-5 molecular sieve loaded by hydrogenation/dehydrogenation metal elements can be used as a catalyst to effectively improve the paraffin pour point (US 5989410A); the IM-5 molecular sieve and USY are mixed to be used as FCC catalyst, so that the conversion rate of the reaction materials is improved, and propylene and butylene are produced in high yield (US 6007698A).
The IM-5 molecular sieve not only shows better catalytic performance in the oil refining field, but also has better application potential in the chemical industry field, in particular to aromatic hydrocarbon conversion reaction. In the existing technology for preparing ethylbenzene by alkylation of ethylene gas phase method, ZSM-5 molecular sieve is generally adopted as a catalytic active component of alkylation reaction, but the method has the defects of higher reaction temperature, high energy consumption, high content of byproduct dimethylbenzene in ethylbenzene product, generally more than 1000ppm, and difficult realization of the requirement of high-grade product of styrene downstream product.
Disclosure of Invention
The invention aims to overcome the problems in the prior art and provides a method for replacing hydrogen on a benzene ring and an application of an IM-5 molecular sieve. The method can react under the low-temperature condition, and has higher target product selectivity under the low-temperature condition; the hydrogen type IM-5 molecular sieve has low silicon-aluminum ratio, and has abundant mesopores on crystal grains, and can have better catalytic performance without acid treatment in the preparation process.
In order to achieve the above object, the present invention provides, in one aspect, a method for substituting hydrogen on a benzene ring, the method comprising: and (2) in the presence of a hydrogen type IM-5 molecular sieve, enabling benzene series to contact with olefin for reaction, wherein the total specific surface area of the hydrogen type IM-5 molecular sieve is 250-450m 2/g, the total pore volume is 0.2-0.7cm 3/g, the most probable mesoporous diameter is 4-20nm, and the silicon-aluminum ratio is below 60.
In a second aspect, the present invention provides the use of a hydrogen form IM-5 molecular sieve or a sodium form IM-5 molecular sieve as described above in a method of replacing hydrogen on a benzene ring to reduce the reaction temperature and/or increase the selectivity of the target product.
Through the technical scheme, the beneficial effects obtained by the invention at least comprise:
The invention uses the hydrogen type IM-5 molecular sieve with lower silicon aluminum and inner mesoporous as the catalyst, the preparation process of the catalyst does not need acid treatment operation, and the method can be carried out at lower reaction temperature, and can simultaneously obtain higher olefin conversion rate and higher target product selectivity, namely, the content of the target product is improved, and the content of byproducts (such as dimethylbenzene) is reduced. Preferably, when the hydrogen form IM-5 molecular sieve of the invention is used as a catalyst in the alkylation of benzene with ethylene, the xylene content can be made lower than 500ppm.
Drawings
FIG. 1 is an X-ray diffraction pattern (XRD) of a synthetic sample (molecular sieve F) of comparative preparation 1;
FIG. 2 is a transmission electron microscopy Topography (TEM) of the synthetic sample (molecular sieve F) of comparative preparation 1;
FIG. 3 (a) is an adsorption-desorption isotherm of the synthetic sample (molecular sieve F) of comparative preparation 1;
FIG. 3 (b) is a pore size distribution diagram of a synthetic sample (molecular sieve F) of comparative preparation 1;
FIG. 4 (a) is an adsorption-desorption isotherm of the synthetic sample (molecular sieve G) of comparative preparation 2;
FIG. 4 (b) is a pore size distribution diagram of a synthetic sample (molecular sieve G) of comparative preparation 2;
FIG. 5 is an X-ray diffraction pattern (XRD) of a synthetic sample (molecular sieve A) according to preparation example 1 of the present invention;
FIG. 6 is a Transmission Electron Microscope (TEM) morphology of the synthetic sample (molecular sieve A) of preparation example 1 of the present invention;
FIG. 7 (a) is an adsorption-desorption isotherm of a synthetic sample (molecular sieve A) of preparation example 1 of the present invention;
FIG. 7 (b) is a pore size distribution diagram of a synthetic sample (molecular sieve A) according to preparation example 1 of the present invention;
FIG. 8 (a) is an adsorption-desorption isotherm of a synthetic sample (molecular sieve B) of preparation 2 of the present invention;
FIG. 8 (B) is a pore size distribution diagram of a synthetic sample (molecular sieve B) according to preparation example 2 of the present invention;
FIG. 9 is a Transmission Electron Microscope (TEM) morphology of the synthetic sample (molecular sieve C) of preparation example 3 of the present invention;
FIG. 10 (a) is an adsorption-desorption isotherm of a synthetic sample (molecular sieve C) of preparation 3 according to the present invention;
FIG. 10 (b) is a pore size distribution diagram of a synthetic sample (molecular sieve C) according to preparation example 3 of the present invention;
FIGS. 11 (a) and 11 (b) are Transmission Electron Microscope (TEM) morphology diagrams of the synthesized sample (molecular sieve D) of preparation example 4 of the present invention;
FIG. 12 (a) is an adsorption-desorption isotherm of a synthetic sample (molecular sieve D) of preparation example 4 of the present invention;
FIG. 12 (b) is a pore size distribution diagram of a synthetic sample (molecular sieve D) according to preparation example 4 of the present invention;
FIG. 13 (a) is an adsorption-desorption isotherm of a synthetic sample (molecular sieve E) of preparation 5 according to the present invention;
FIG. 13 (b) is a pore size distribution diagram of a synthetic sample (molecular sieve E) according to preparation example 5 of the present invention.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
In a first aspect the present invention provides a method of substituting hydrogen on a benzene ring, the method comprising: and (2) in the presence of a hydrogen type IM-5 molecular sieve, enabling benzene series to contact with olefin for reaction, wherein the total specific surface area of the hydrogen type IM-5 molecular sieve is 250-450m 2/g, the total pore volume is 0.2-0.7cm 3/g, the most probable mesoporous diameter is 4-20nm, and the silicon-aluminum ratio is below 60. "silica to alumina ratio" refers to the molar ratio between SiO 2 and Al 2O3 in the molecular sieve.
The inventors of the present invention have found that when the hydrogen form IM-5 molecular sieve is within the above range, the process can be performed at a lower temperature, and the selectivity of the target product is higher, and the conversion of olefin is higher.
In some embodiments of the present invention, the total specific surface area of the hydrogen form IM-5 molecular sieve may be any one of the values 250m2/g、255m2/g、260m2/g、265m2/g、270m2/g、275m2/g、280m2/g、285m2/g、290m2/g、295m2/g、300m2/g、305m2/g、310m2/g、315m2/g、320m2/g、325m2/g、330m2/g、335m2/g、340m2/g、345m2/g、350m2/g、355m2/g、360m2/g、365m2/g、370m2/g、375m2/g、380m2/g、385m2/g、390m2/g、395m2/g、400m2/g、405m2/g、410m2/g、415m2/g、420m2/g、425m2/g、430m2/g、435m2/g、440m2/g、445m2/g、450m2/g or a range of values consisting of any two of the values. Preferably, the total specific surface area of the hydrogen form IM-5 molecular sieve is 300-450m 2/g, more preferably 320-400m 2/g.
In some embodiments of the present invention, the total pore volume of the hydrogen form IM-5 molecular sieve may be any one of the values in 0.2cm3/g、0.23cm3/g、0.25cm3/g、0.27cm3/g、0.3cm3/g、0.32cm3/g、0.35cm3/g、0.37cm3/g、0.4cm3/g、0.45cm3/g、0.5cm3/g、0.55cm3/g、0.6cm3/g or a range of any two of the values. Preferably, the total pore volume of the hydrogen form IM-5 molecular sieve is from 0.3 to 0.6cm 3/g, more preferably from 0.3 to 0.4cm 3/g.
In some embodiments of the present invention, the most probable mesoporous diameter of the hydrogen form IM-5 molecular sieve may be any one of the values of 4nm、4.2nm、4.5nm、4.7nm、5nm、5.2nm、5.5nm、5.7nm、6nm、6.2nm、6.5nm、6.7nm、7nm、7.2nm、7.5nm、7.7nm、8nm、8.2nm、8.5nm、8.7nm、9nm、9.2nm、9.5nm、9.7nm、10nm、10.2nm、10.5nm、10.7nm、11nm、11.2nm、11.5nm、11.7nm、12nm、12.2nm、12.5nm、12.7nm、13nm、13.2nm、13.5nm、13.7nm、14nm、15nm、17nm、20nm or a range of values consisting of any two of the values. Preferably, the hydrogen form IM-5 molecular sieve has a most probable mesoporous diameter of 5-15nm.
In some embodiments of the invention, the hydrogen form of the IM-5 molecular sieve has a silica to alumina ratio of 30 to 50.
In some embodiments of the invention, the hydrogen form IM-5 molecular sieve has a micropore specific surface area of 220-280m 2/g. In some embodiments of the present invention, the hydrogen form IM-5 molecular sieve may have a micropore specific surface area of any one of the values 220m2/g、221m2/g、222m2/g、223m2/g、224m2/g、225m2/g、226m2/g、227m2/g、228m2/g、229m2/g、230m2/g、231m2/g、232m2/g、233m2/g、234m2/g、235m2/g、236m2/g、237m2/g、238m2/g、239m2/g、240m2/g、241m2/g、242m2/g、243m2/g、244m2/g、245m2/g、246m2/g、247m2/g、248m2/g、249m2/g、250m2/g、251m2/g、252m2/g、253m2/g、254m2/g、255m2/g、256m2/g、257m2/g、258m2/g、259m2/g、260m2/g、261m2/g、262m2/g、263m2/g、264m2/g、265m2/g、266m2/g、267m2/g、268m2/g、269m2/g、270m2/g、271m2/g、272m2/g、273m2/g、274m2/g、275m2/g、276m2/g、277m2/g、278m2/g、279m2/g、280m2/g or a range of any two of the values.
In some embodiments of the invention, the hydrogen form IM-5 molecular sieve has a micropore volume of 0.1 to 0.15cm 3/g. In some embodiments of the invention, the micropore volume of the hydrogen form IM-5 molecular sieve may be any one of 0.1cm3/g、0.112cm3/g、0.114cm3/g、0.116cm3/g、0.118cm3/g、0.12cm3/g、0.125m3/g、0.13m3/g、0.135m3/g、0.14m3/g、0.145m3/g、0.15m3/g or a range of any two of the values recited above.
In some embodiments of the invention, the mesoporous specific surface area (i.e., matrix specific surface area) of the hydrogen form IM-5 molecular sieve is in the range of 60-140m 2/g. In some embodiments of the present invention, the mesoporous specific surface area of the hydrogen form IM-5 molecular sieve may be any one value or a range of values consisting of any two values of 60m2/g、62m2/g、64m2/g、66m2/g、68m2/g、70m2/g、72m2/g、74m2/g、76m2/g、78m2/g、80m2/g、82m2/g、84m2/g、86m2/g、88m2/g、90m2/g、92m2/g、94m2/g、96m2/g、98m2/g、100m2/g、103m2/g、105m2/g、107m2/g、109m2/g、110m2/g、113m2/g、115m2/g、117m2/g、120m2/g、125m2/g、130m2/g、135m2/g、140m2/g.
In some embodiments of the invention, the hydrogen form IM-5 molecular sieve has a mesoporous volume of 0.17 to 0.25cm 3/g. In some embodiments of the present invention, the mesoporous volume of the hydrogen form IM-5 molecular sieve may be any one of 0.17cm3/g、0.18cm3/g、0.19cm3/g、0.2cm3/g、0.21cm3/g、0.22cm3/g、0.23cm3/g、0.24cm3/g、0.25cm3/g or a range of values consisting of any two of the above.
In some embodiments of the invention, the hydrogen form IM-5 molecular sieve crystal grains are long, regular in shape and distributed with intra-crystalline mesopores.
In some embodiments of the invention, the hydrogen form IM-5 molecular sieve has a multistage Kong Yinzi (HIERARCHICAL FACTOR, HF) of 0.09 to 0.11. The calculation method of the multistage Kong Yinzi HF (Hierarchical factor) comprises the following steps: hf= (V micro/Vtotal)x(Smeso/Stotal),Vmicro refers to the volume of micropores, V total refers to the total pore volume, S meso refers to the specific surface area of the mesopores, S total refers to the total specific surface area.
In some embodiments of the invention, the hydrogen form of the IM-5 molecular sieve has a relative crystallinity of 87% or more.
In some embodiments of the present invention, the hydrogen form IM-5 molecular sieve is obtained by subjecting a sodium form IM-5 molecular sieve to an ammonium exchange treatment, and the preparation method of the sodium form IM-5 molecular sieve comprises: sequentially carrying out hydrothermal crystallization, solid collection and drying on a crystallization material containing an aluminum source, an inorganic base containing alkali metal elements, a template agent, a pore-forming agent, a silicon source and water, wherein the consumption of each component in the crystallization material is such that SiO 2：Al2O3: oxides of alkali metals: template agent: the molar ratio of H 2 O is 1: (0.005-0.1): (0.1-0.5): (0.05-0.3): (5-50), preferably 1: (0.0083-0.05): (0.15-0.4): (0.08-0.2): (7-40), wherein SiO 2: the weight ratio of the pore-forming agent is 1: (0.02-0.3), preferably 1: (0.05-0.25). Further preferably, the amounts of the components in the crystallization materials containing the aluminum source, the inorganic alkali containing alkali metal elements, the template agent, the pore-forming agent, the silicon source and the water are such that SiO 2：Al2O3: oxides of alkali metals: template agent: the molar ratio of H 2 O is 1: (0.0167-0.025): (0.15-0.365): (0.10-0.15): (10-40), wherein SiO 2: the weight ratio of the pore-forming agent is 1: (0.05-0.25). Further preferably, the amounts of the components in the crystallization materials containing the aluminum source, the inorganic alkali containing alkali metal elements, the template agent, the pore-forming agent, the silicon source and the water are such that SiO 2：Al2O3: oxides of alkali metals: template agent: the molar ratio of H 2 O is 1: (0.0167-0.025): (0.2-0.365): (0.12-0.15): (14-40), siO 2: the weight ratio of the pore-forming agent is 1: (0.06-0.25).
In some embodiments of the present invention, the crystallization materials containing the aluminum source, the inorganic base containing alkali metal element, the template agent, the pore-forming agent, the silicon source and the water may be solid-liquid mixture or colloid.
In some embodiments of the invention, the hydrothermal crystallization conditions include: the temperature is 120-200deg.C, preferably 130-180deg.C, and further preferably 140-180deg.C; the time is 1-15 days, preferably 4-10 days. Preferably, the hydrothermal crystallization conditions may include: firstly, carrying out hydrothermal crystallization for 1-3 days at 130-140 ℃, and then carrying out hydrothermal crystallization for 3-7 days at 160-180 ℃.
It should be understood that the hydrothermal crystallization is performed in a closed space, and the pressure is autogenous pressure, and is not particularly controlled. It should be understood that the hydrothermal crystallization is dynamic crystallization, which may be rotational crystallization or stirred crystallization. Preferably, the hydrothermal crystallization is a rotational crystallization, wherein the rotational speed during the rotational crystallization is selected as a conventional technique in the art, and may be, for example, 10-50rpm (preferably 15-30 rpm), and will not be described herein.
It should be appreciated that in the process for preparing the sodium form of the IM-5 molecular sieve, the drying is selected as is conventional in the art and may be, for example, from 80 to 120 ℃; the drying time is selected by the conventional technology in the field, and will not be described herein.
In some embodiments of the present invention, the hydrogen form IM-5 molecular sieve is obtained by subjecting a sodium form IM-5 molecular sieve to an ammonium exchange treatment, and the preparation method of the sodium form IM-5 molecular sieve comprises: the method comprises the steps of firstly carrying out first-stage crystallization on a crystallization material containing an aluminum source, inorganic alkali containing alkali metal elements, a template agent, a silicon source and water, cooling to 20-50 ℃, then adding a pore-forming agent, carrying out second-stage crystallization, and then carrying out solid collection and drying, wherein the dosage of each component in the crystallization material is such that SiO 2：Al2O3: oxides of alkali metals: template agent: the molar ratio of H 2 O is 1: (0.005-0.1): (0.1-0.5): (0.05-0.3): (5-50), preferably 1: (0.0083-0.05): (0.15-0.4): (0.08-0.2): (7-40), siO 2: the weight ratio of the pore-forming agent is 1: (0.02-0.3), preferably 1: (0.05-0.25). Further preferably, the amounts of the components in the crystallization materials containing the aluminum source, the inorganic alkali containing alkali metal elements, the template agent, the pore-forming agent, the silicon source and the water are such that SiO 2：Al2O3: oxides of alkali metals: template agent: the molar ratio of H 2 O is 1: (0.0167-0.025): (0.15-0.365): (0.10-0.15): (10-40), siO 2: the weight ratio of the pore-forming agent is 1: (0.05-0.25). Further preferably, the amounts of the components in the crystallization materials containing the aluminum source, the inorganic alkali containing alkali metal elements, the template agent, the pore-forming agent, the silicon source and the water are such that SiO 2：Al2O3: oxides of alkali metals: template agent: the molar ratio of H 2 O is 1: (0.0167-0.025): (0.2-0.365): (0.12-0.15): (14-40), wherein SiO 2: the weight ratio of the pore-forming agent is 1: (0.06-0.25).
In some embodiments of the present invention, the crystallization materials containing the aluminum source, the inorganic base containing alkali metal element, the template agent, the silicon source and the water may be solid-liquid mixture or colloid.
In some embodiments of the present invention, the conditions for the first stage crystallization include: the temperature is 120-150 ℃ and the time is 1-3 days. Further preferably, the conditions for the crystallization of the first stage include: the temperature is 130-140 ℃ and the time is 24-50 hours.
In some embodiments of the present invention, the conditions for the second stage crystallization include: the temperature is 155-200deg.C, and the time is 1-15 days. Further preferably, the conditions for hydrothermal crystallization include: the temperature is 160-180 ℃, and the hydrothermal crystallization time is 3-10 days.
It should be understood that the first stage crystallization and the second stage crystallization are both performed in a closed space, and the pressure is autogenous pressure and is not particularly controlled. It should be understood that the first stage crystallization and the second stage crystallization are dynamic crystallization, and the dynamic crystallization may be rotational crystallization or stirring crystallization. Preferably, the hydrothermal crystallization is a rotational crystallization, wherein the rotational speed during the rotational crystallization is selected as a conventional technique in the art, and may be, for example, 10-50rpm (preferably 15-30 rpm), and will not be described herein.
In some preferred embodiments of the present invention, the method for preparing a sodium form of IM-5 molecular sieve comprises:
(1) Dissolving inorganic alkali containing alkali metal elements, an aluminum source and a template agent in water, uniformly mixing, adding a pore-forming agent and a silicon source into the mixture to prepare a colloid or a solid-liquid mixture, wherein the dosage of each component is such that SiO 2：Al2O3: oxides of alkali metals: template agent: the molar ratio of H 2 O is 1: (0.005-0.1): (0.1-0.5): (0.05-0.3): (5-50), preferably 1: (0.0083-0.05): (0.15-0.4): (0.08-0.2): (7-40), further preferably 1: (0.0167-0.025): (0.15-0.365): (0.10-0.15): (10-40), further preferably 1: (0.0167-0.025): (0.2-0.365): (0.12-0.15): (14-40), siO 2: the weight ratio of the pore-forming agent is 1: (0.02-0.3), preferably 1: (0.05-0.25), further preferably 1: (0.06-0.25);
(2) Transferring the colloid or the solid-liquid mixture obtained in the step (1) into a crystallization kettle, carrying out hydrothermal crystallization at 120-200 ℃ for 1-15 days, collecting a solid product, and drying;
wherein the pressure of the hydrothermal crystallization in the step (2) is autogenous pressure.
In some preferred embodiments of the present invention, the method for preparing a sodium form of IM-5 molecular sieve comprises:
(A) Dissolving inorganic alkali containing alkali metal elements, an aluminum source and a template agent in water, adding a silicon source, uniformly mixing, carrying out first-stage crystallization for 1-3 days at 120-150 ℃, cooling to 20-50 ℃, and then adding a pore-forming agent into the mixture to prepare a colloid or a solid-liquid mixture, wherein the dosage of each component is such that SiO 2：Al2O3: oxides of alkali metals: template agent: the molar ratio of H 2 O is 1: (0.005-0.1): (0.1-0.5): (0.05-0.3): (5-50), preferably 1: (0.0083-0.05): (0.15-0.4): (0.08-0.2): (7-40), further preferably 1: (0.0167-0.025): (0.2-0.365): (0.12-0.15): (14-40), further preferably 1: (0.0167-0.025): (0.2-0.365): (0.12-0.15): (14-40), siO 2: the weight ratio of the pore-forming agent is 1: (0.02-0.3), preferably 1: (0.05-0.25), further preferably 1: (0.06-0.25);
(B) Transferring the colloid or solid-liquid mixture obtained in the step (A) into a crystallization kettle, crystallizing for 1-15 days at the second stage of 155-200 ℃, collecting a solid product, and drying;
wherein the pressure of the second stage crystallization in the step (B) is autogenous pressure.
In the present invention, the ammonium exchange treatment is to remove sodium from the sodium form IM-5 molecular sieve and remove the template agent therefrom, and may be performed by methods well known to those skilled in the art, for example, ammonium exchange, drying and calcination may be performed. Wherein the temperature of the drying may be selected conventionally in the art, and may be, for example, 80 to 120 ℃; the calcination is to remove the template agent and ammonium ions therein, and the calcination temperature is selected conventionally in the art, and may be 550-650 ℃, for example. Preferably, the ammonium exchange is carried out by placing a sodium type IM-5 molecular sieve in an ammonium salt solution for ion exchange. Wherein the ammonium exchange condition is 60-90 ℃ for 3-6 hours. The concentration of the ammonium salt solution may be selected within a wide range, for example, may be 0.2 to 1mol/L. Preferably, the ammonium salt is at least one selected from the group consisting of ammonium nitrate, ammonium chloride, ammonium oxalate and ammonium sulfate.
In some preferred embodiments of the invention, the ammonium exchange process comprises: and (3) placing the sodium type IM-5 molecular sieve in 0.2-1mol/L ammonium salt solution, carrying out ion exchange for 1-3 times at 60-90 ℃ for 2-6 hours each time, washing with deionized water, drying at 80-120 ℃ for 8-12 hours, and roasting at 550-650 ℃ for 3-6 hours.
In the present invention, the aluminum source may be a material commonly used in the art capable of providing Al, and in some embodiments of the present invention, the aluminum source is at least one of aluminum salt, aluminate, meta-aluminate, alumina, and aluminum hydroxide, preferably at least one of sodium aluminate, sodium meta-aluminate, aluminum sulfate, aluminum chloride, aluminum nitrate, aluminum hydroxide, alumina, and pseudo-boehmite. Further preferably, the aluminum source is at least one of sodium metaaluminate, aluminum nitrate, and aluminum sulfate.
In some embodiments of the invention, the inorganic alkali containing alkali metal element is an alkali metal hydroxide, preferably sodium hydroxide and/or potassium hydroxide.
In some embodiments of the invention, the template agent is a salt of a 1, 5-bis (N-methylpyrrolidine) pentylene cation, wherein the structural formula of the 1, 5-bis (N-methylpyrrolidine) pentylene cation is shown in formula (1).
In some embodiments of the present invention, the anion of the salt of the 1, 5-bis (N-methylpyrrolidine) pentylene cation that coordinates to the cation to form a salt may be a halide, preferably a chloride or bromide, more preferably a bromide. Preferably, the templating agent is 1, 5-bis (N-methylpyrrolidine) pentylene dibromo salt.
In some embodiments of the invention, the pore-forming agent is a glucose polymer, preferably at least one of cellulose, sodium carboxymethyl cellulose, and starch, and more preferably sodium carboxymethyl cellulose.
In the present invention, the silicon source may be a material that is commonly used in the art and is capable of providing Si, and in some embodiments of the present invention, the silicon source is at least one of silicate, and silica, preferably at least one of amorphous silica, water glass, silica sol, solid silica gel, diatomaceous earth, white carbon black, and tetraethyl orthosilicate, and further preferably silica sol and/or solid silica gel.
The hydrogen type IM-5 molecular sieve prepared by the method contains micropores and intragranular mesopores, and the generation of mesopores improves the pore channel utilization rate of the IM-5 molecular sieve, so that the catalytic performance of the catalyst can be improved when the catalyst is used for chemical reaction. The inventor of the present invention has found that in the method for substituting hydrogen on benzene ring (such as alkylation reaction of benzene and ethylene), the hydrogen type IM-5 molecular sieve prepared by the method has improved mass transfer and diffusion capability due to the inclusion of the intragranular mesopores, can greatly reduce the reaction temperature, and can simultaneously realize higher olefin conversion rate and improved selectivity of the cloth mark product. When the method for substituting the hydrogen on the benzene ring is alkylation reaction of benzene and ethylene, the alkylation reaction temperature can be reduced to below 330 ℃, and simultaneously, higher ethylene conversion rate can be realized, and the selectivity of the target product ethylbenzene can be improved.
In some embodiments of the invention, the molar ratio of benzene-based material to olefin is from 2 to 20:1, preferably from 4 to 8:1, and more preferably from 7 to 8:1.
In some embodiments of the invention, the benzene series is selected from alkyl-substituted benzene and the alkyl is a C1-C4 alkyl, preferably at least one of benzene, toluene, xylene, and trimethylbenzene. Wherein the dimethylbenzene is at least one of m-xylene, o-xylene and p-xylene. Further preferably, the benzene-based compound is benzene.
In some embodiments of the invention, the olefin is selected from the group consisting of C2-C6 mono-olefins, preferably at least one of ethylene, propylene, butene and pentene. It should be understood that the ethylene, propylene, butene, pentene may be selected as is conventional in the art, for example, butene may be at least one of 1-butene, 2-butene, and pentene may be at least one of 1-pentene, 2-pentene, 3-pentene. Further preferably, the olefin is ethylene.
In some embodiments of the invention, the contacting conditions include: the reaction temperature is 240-360 ℃. The reaction temperature may be any one value or a range of values in the range of any two values of the values of 240 ℃, 250 ℃, 260 ℃, 27 ℃, 280 ℃, 290 ℃,300 ℃, 310 ℃, 320 ℃, 330 ℃, 340 ℃, 350 ℃ and 360 ℃. Preferably, the reaction temperature is 260-350 ℃, more preferably 260-330 ℃.
In some embodiments of the invention, the contacting conditions include: the reaction pressure is 0.2-2MPa. The reaction pressure may be any one of 0.2MPa, 0.3MPa, 0.4MPa, 0.5MPa, 0.6MPa, 0.7MPa, 0.8MPa, 0.9MPa, 1MPa, or a value within a range composed of any two of the above values. Preferably, the reaction pressure is 0.5 to 1MPa.
In some embodiments of the invention, the contacting conditions include: the weight hourly space velocity of the olefin is 0.3-2h -1. The weight hourly space velocity of the olefin may be any one of the values in 0.3h-1、0.4h-1、0.5h-1、0.6h-1、0.7h-1、0.8h-1、0.9h-1、1h-1、1.5h-1、2h-1 or a range of any two of the values recited above. Preferably, the weight hourly space velocity of the olefin is from 0.5 to 1h -1.
In a second aspect, the present invention provides the use of a hydrogen form IM-5 molecular sieve or a sodium form IM-5 molecular sieve as described above in a method of replacing hydrogen on a benzene ring to reduce the reaction temperature and/or increase the selectivity of the target product.
The hydrogen form IM-5 molecular sieve as described above can be used as a catalyst for cracking macromolecular hydrocarbons or for transalkylation or alkylation of aromatic hydrocarbons. The inventors of the present invention have studied and found that when the hydrogen form IM-5 molecular sieve as described above is used as a catalyst, the method of substituting hydrogen on benzene ring is performed at a lower reaction temperature, so that the content of target product (e.g., ethylbenzene) can be increased, and the content of by-product (e.g., xylene) can be reduced, i.e., the selectivity of target product can be increased.
The present invention will be further described in detail by way of examples, but the present invention is not limited thereto.
In the examples and comparative examples of the present invention, the method for measuring physical parameters of molecular sieves by using AS-3, AS-6 static nitrogen adsorption instrument manufactured by Quantachrome instruments company is AS follows:
(1) Placing the sample in a sample treatment system, vacuumizing to 1.33X10 -2 Pa at 300 ℃, preserving heat and pressure for 15h, and purifying the sample;
(2) At a liquid nitrogen temperature of 77K (-196 ℃), measuring the adsorption quantity and the desorption quantity of a purified sample on nitrogen under the condition of different specific pressures P/P 0 (P is the partial pressure of N 2 and P 0 is the saturated vapor pressure of N 2), obtaining an N 2 adsorption-desorption isothermal curve, calculating the total pore specific surface area by using a two-parameter BET formula, calculating the micropore specific surface area and the micropore volume of the sample by using a t-plot method, calculating the total pore volume by taking the adsorption quantity at the specific pressure P/P 0 =0.98, and calculating the specific surface area and the mesopore volume of mesopores according to the following formula: s Specific surface area of mesoporous ＝S Total specific surface area -S Micropore specific surface area ,V Mesoporous volume ＝V Total pore volume -V micropore volume ; and calculating the pore size distribution of the mesoporous part by using a BJH formula to obtain a pore size distribution curve and the most probable mesoporous diameters.
The XRD pattern of the molecular sieve is tested by Cu target, K alpha radiation, ni filter, 3 kV tube voltage, 35mA tube current and 4-55 DEG scanning range. Wherein, the relative crystallinity (R.C.) of the IM-5 molecular sieve refers to the ratio of the sum of peak areas of 5 peaks in the interval of 22-26 degrees of 2 theta of the sample to the sum of five peak areas corresponding to the standard sample of the IM-5 molecular sieve (the crystallinity value of the IM-5 molecular sieve of the comparative preparation example 1 is defined as 100%).
In the following examples and comparative examples, SDA refers to the templating agent and PEA refers to the pore-forming agent. In the following examples and comparative examples, unless otherwise specified, crystallization was rotational crystallization, and the rotational rate during rotational crystallization was 20rpm.
Comparative preparation example 1
IM-5 molecular sieves were synthesized by the method disclosed in literature Determination of the Pore Topology of Zeolite IM-5by Means of CatalyticTest Reactions and Hydrocarbon Adsorption Measurements.(Journal of Catalysis 2000:189,382-394).
A certain amount of 1, 5-bis (N-methylpyrrolidine) pentylene dibromo salt was dissolved in a proper amount of deionized water, 3.00g of white carbon black was then added to the above solution under stirring, sodium aluminate (56 wt% al 2O3), naOH (98 wt%) and NaBr (99 wt%) were added respectively and mixed uniformly to obtain a reaction mixture, and the amounts of the raw materials were such that the molar ratio of SiO 2：Al2O3：Na2O：NaBr：SDA：H2 O in the reaction mixture=1: 0.025:0.283:0.1:0.167:40, wherein SDA is 1, 5-bis (N-methylpyrrolidine) pentylene dibromo salt.
The mixture is stirred for 30 minutes at 25 ℃ to prepare colloid, and the colloid is transferred into a closed crystallization kettle with polytetrafluoroethylene lining and crystallized for 10 days at 175 ℃. Washing the crystallized product with water, filtering, and drying the obtained solid at 80 ℃ for 12 hours to obtain the molecular sieve F.
Taking a part of molecular sieve F, roasting at 550 ℃ for 5 hours, and then carrying out corresponding detection, wherein the XRD pattern is shown as figure 1, the crystallinity is determined as 100%, and the molecular sieve F is an IM-5 molecular sieve; the transmission electron micrograph is shown in FIG. 2, the adsorption-desorption and pore size distribution curves are shown in FIG. 3 (a) and FIG. 3 (b), and the specific surface area and pore volume are shown in Table 1.
Comparative preparation example 2
IM-5 molecular sieves were synthesized by the method disclosed in CN 102452666B.
A certain amount of NaOH solid is dissolved in a proper amount of deionized water, then NaAlO 2 aqueous solution (wherein the mass fraction of Al 2O3 in the aqueous solution is 8.45 percent and the mass fraction of NaOH is 16.17 percent) and 1, 5-bis (N-methylpyrrolidine) pentylene dibromo salt aqueous solution are added, uniformly mixed, and under the condition of stirring, 20g of alkaline silica sol (wherein the content of SiO 2 is 30 mass percent) is slowly added dropwise to prepare a colloid, and stirring is continued for 2 hours. The raw materials are used in such an amount that the molar ratio of SiO 2:Al2O3:Na2 O to 1, 5-bis (N-methylpyrrolidine) pentylene dibromo salt to H 2 O in the colloid=1:0.0167:0.225:0.15:20, wherein SDA is 1, 5-bis (N-methylpyrrolidine) pentylene dibromo salt.
Transferring the prepared colloid into a high-pressure reaction kettle with a polytetrafluoroethylene lining of 100ml, crystallizing at 160 ℃ for 6 days, stopping crystallization reaction, washing and filtering the product, and drying at 80 ℃ for 12 hours to obtain the molecular sieve G.
A portion of molecular sieve G was taken and calcined at 550℃for 5 hours and then examined accordingly, and its XRD pattern showed that it was an IM-5 molecular sieve with a relative crystallinity of 90.0% and its transmission electron micrograph was similar to that of FIG. 2, and adsorption-desorption and pore size distribution curves were shown in FIG. 4 (a) and FIG. 4 (b), respectively, and specific surface areas and pore volumes were shown in Table 1.
Preparation example 1
Dissolving a certain amount of NaAlO 2, naOH and template agent 1, 5-bis (N-methylpyrrolidine) pentylene dibromo salt in a proper amount of deionized water, uniformly stirring, adding sodium carboxymethylcellulose as a pore-forming agent, adding 20.00g of silica sol (SiO 2 content 30 mass%) under stirring, and uniformly mixing to obtain a reaction mixture, wherein the molar ratio of SiO 2：Al2O3：Na2O：SDA：H2 O in the obtained reaction mixture is=1: 0.025:0.20:0.12:14, siO 2: PEA weight ratio = 1:0.06.
Transferring the prepared reaction mixture colloid into a 100mL sealed crystallization kettle with a polytetrafluoroethylene lining, carrying out hydrothermal crystallization for 2 days at 140 ℃, then heating to 175 ℃ and carrying out hydrothermal crystallization for 4 days, washing and filtering the crystallized reaction product, and drying the solid at 80 ℃ for 12 hours to obtain the molecular sieve A.
Taking a part of molecular sieve A, roasting at 550 ℃ for 5 hours, and then carrying out corresponding detection, wherein the relative crystallinity is 95.0%, the XRD pattern is shown in figure 5, the molecular sieve A is an IM-5 molecular sieve, the transmission electron microscope photo is shown in figure 6, the mesoporous particles are uniformly distributed on the crystal grains, the adsorption-desorption and pore size distribution curves are respectively shown in figure 7 (a) and figure 7 (b), the diameter (d p) of the most probable pores is 8.5nm from the pore size distribution curve, and the specific surface area and pore volume are shown in table 1.
Preparation example 2
Dissolving a certain amount of AlCl 3, naOH and template agent 1, 5-bis (N-methylpyrrolidine) pentylene dibromo salt in a proper amount of deionized water, uniformly stirring, adding sodium carboxymethylcellulose as a pore-forming agent, adding 6.51g of solid silica gel (SiO 2 content is 92.17 mass%) under stirring, uniformly mixing, and using the raw materials in such a way that the molar ratio of SiO 2：Al2O3：Na2O：SDA：H2 O in the obtained reaction mixture is=1: 0.025:0.20:0.12:14, siO 2: PEA weight ratio = 1:0.25.
And transferring the prepared reaction mixture colloid into a 100mL sealed crystallization kettle with a polytetrafluoroethylene lining, performing hydrothermal crystallization for 6 days under stirring at 160 ℃, washing and filtering the crystallized reaction product, and drying the solid at 120 ℃ for 8 hours to obtain the molecular sieve B.
A part of the molecular sieve B is taken, calcined at 550 ℃ for 5 hours and then subjected to corresponding detection, the XRD result shows that the molecular sieve B is an IM-5 molecular sieve, the relative crystallinity is 87.3%, the adsorption-desorption and pore size distribution curves are respectively shown in fig. 8 (a) and 8 (B), the most probable pore diameter (d p) is 7.2nm as seen from the pore size distribution curve, and the specific surface area and the pore volume are shown in Table 1.
Preparation example 3
Dissolving a certain amount of NaAlO 2, naOH and a template agent 1, 5-bis (N-methylpyrrolidine) pentane dibromo salt in a proper amount of deionized water, uniformly stirring, adding a certain amount of cellulose, adding 3.00g of white carbon black under stirring, and uniformly mixing to obtain a reaction mixture, wherein the molar ratio of SiO 2：Al2O3：Na2O：SDA：H2 O in the obtained reaction mixture=1: 0.0167:0.365:0.15:40, siO 2: PEA weight ratio = 1:0.15.
And transferring the prepared reaction mixture colloid into a 100ml sealed crystallization kettle with a polytetrafluoroethylene lining, performing hydrothermal crystallization for 10 days under stirring at 160 ℃, stopping the crystallization reaction, washing the product with water, filtering, and drying the solid at 100 ℃ for 10 hours to obtain the molecular sieve C.
Taking a part of molecular sieve C, roasting at 550 ℃ for 5 hours, and then carrying out corresponding detection, wherein XRD results show that the molecular sieve C is an IM-5 molecular sieve, the relative crystallinity of the obtained product is 95.7%, a transmission electron microscope photo is shown in fig. 9, mesoporous uniform distribution is shown on crystal grains, adsorption-desorption and pore size distribution curves are shown in fig. 10 (a) and 10 (b), and the diameter (d p) of the most probable pores is 8.0nm from the pore size distribution curves, and the specific surface area and pore volume are shown in table 1.
Preparation example 4
A certain amount of NaAlO 2, naOH, template 1, 5-bis (N-methylpyrrolidine) pentylene dibromo salt was dissolved in a proper amount of deionized water, and 6.67g of solid silica gel (SiO 2 content 90 mass%) was added with stirring, and mixed uniformly to obtain a colloid. Transferring the prepared colloid into a 100ml closed reaction kettle with polytetrafluoroethylene lining, performing first-stage crystallization at 140 ℃ for 2 days, cooling to 25 ℃, adding sodium carboxymethylcellulose as a pore-forming agent, and uniformly stirring to obtain a reaction mixture. Wherein the amounts of the raw materials are such that the molar ratio of SiO 2：Al2O3：Na2O：SDA：H2 O in the resulting reaction mixture = 1:0.025:0.20:0.12:14, siO 2: PEA weight ratio = 1:0.06.
The reaction mixture is subjected to second stage crystallization for 4 days at 175 ℃ under autogenous pressure, the crystallized reaction product is washed with water and filtered, and the solid is dried at 120 ℃ for 8 hours, so as to obtain the molecular sieve D.
Taking a part of molecular sieve D, roasting at 550 ℃ for 5 hours, and then carrying out corresponding detection, wherein the XRD result shows that the IM-5 molecular sieve has a relative crystallinity of 96.8%, the transmission electron microscope pictures are shown in fig. 11 (a) and 11 (b), the mesoporous particles are uniformly distributed on the crystal grains, the adsorption-desorption and pore size distribution curves are respectively shown in fig. 12 (a) and 12 (b), the diameter (D p) of the most probable pore is 6.0nm from the pore size distribution curve, and the specific surface area and pore volume are shown in table 1.
Preparation example 5
A certain amount of NaAlO 2, naOH, template 1, 5-bis (N-methylpyrrolidine) pentylene dibromo salt was dissolved in a proper amount of deionized water, and 6.67g of solid silica gel (SiO 2 content 90 mass%) was added with stirring, and mixed uniformly to obtain a colloid. Transferring the prepared colloid into a 100ml closed reaction kettle with polytetrafluoroethylene lining, performing first-stage crystallization at 140 ℃ for 2 days, cooling to 25 ℃, adding starch, and stirring uniformly to obtain a reaction mixture. Wherein the amounts of the starting materials are such that the molar ratio of SiO 2：Al2O3：Na2O：SDA：H2 O in the resulting reaction mixture = 1:0.025:0.20:0.12:14, siO 2: PEA weight ratio = 1:0.10.
And (3) carrying out second-stage crystallization on the reaction mixture added with the pore-forming agent for 4 days at 175 ℃ under autogenous pressure, washing and filtering a crystallized product, and drying a solid at 100 ℃ for 10 hours to obtain the molecular sieve E.
Taking a part of molecular sieve E, roasting at 550 ℃ for 5 hours, and then carrying out corresponding detection, wherein XRD results show that the molecular sieve E is an IM-5 molecular sieve, the relative crystallinity is 89.5%, a transmission electron microscope photo is similar to that shown in fig. 6, mesoporous uniform distribution is shown on crystal grains, adsorption-desorption and pore size distribution curves are respectively shown in fig. 13 (a) and 13 (b), and the most probable pore diameter (d p) is 10.0nm as seen from the pore size distribution curves, and the specific surface area and pore volume are shown in table 1.
TABLE 1
The micropores are holes with diameters smaller than 2nm, and the multistage Kong Yinzi HF (Hierarchical factor) calculation method comprises the following steps: hf= (V micro/Vtotal)x(Smeso/Stotal). Wherein V micro refers to the volume of micropores, V total refers to the total pore volume, S meso refers to the specific surface area of mesopores, and S total refers to the total specific surface area. HF (×100) refers to a value after multistage pore factor hf×100.
Comparative examples 1 to 6
(1) Preparation of hydrogen type IM-5 molecular sieve by ammonium exchange treatment of molecular sieve
The unfired molecular sieves F and G prepared in comparative preparation examples 1 and 2 were respectively placed in an ammonium nitrate solution having a concentration of 0.5mol/L and ion-exchanged at 80℃for 2 times, each time for 2 hours, the exchanged molecular sieves were washed with deionized water, dried at 90℃for 10 hours and calcined at 550℃for 5 hours to obtain hydrogen form IM-5 molecular sieves F-1 and hydrogen form IM-5 molecular sieves G-1, respectively, and the molar ratios of SiO 2/Al2O3 (i.e., si/Al ratios) of the molecular sieves F-1 and G-1 were 34 and 49, respectively, as determined by XRF fluorescence elemental analysis.
(2) The catalytic performance of molecular sieves F-1 and G-1 in a gas phase alkylation reaction of benzene with ethylene was examined according to the following procedure:
2.0g of hydrogen type IM-5 molecular sieve is filled in a fixed bed reaction device, and benzene and ethylene are introduced to carry out gas phase alkylation reaction of the benzene and the ethylene. Evaluation conditions: the molar ratio of benzene to ethylene is 7.5, the mass airspeed based on ethylene is 0.7h -1, the reaction pressure is 0.8MPa, the reaction temperature is 280 ℃, 315 ℃, 330 ℃ and 360 ℃, the reaction time of each temperature section is 24h, three instantaneous samples are collected at each temperature point to ensure the reliability of data, the composition of the products is analyzed by chromatography, and then the ethylene conversion rate and the ethylbenzene selectivity are calculated, and the average value is taken.
The reaction results are shown in Table 2.
The ethylene conversion and ethylbenzene selectivity shown in Table 2 are calculated by the following formula:
Ethylene conversion= (ethylene feed mass-ethylene mass in product)/ethylene feed mass x 100%;
Ethylbenzene selectivity = mass fraction of ethylbenzene in product/(mass fraction of benzene in 100-product-mass fraction of ethylene in product) ×100%.
Examples 1 to 15
(1) Preparation of hydrogen type IM-5 molecular sieve by ammonium exchange of molecular sieve
Method for preparing hydrogen form IM-5 molecular sieves according to ammonium exchange treatment of molecular sieves of comparative examples 1-6 the unfired molecular sieves (sodium form IM-5) prepared in preparation examples 1-5 were subjected to ammonium exchange treatment to prepare hydrogen form IM-5 molecular sieves A-1, B-1, C-1, D-1 and E-1, respectively, and SiO 2/Al2O3 molar (i.e., silica-alumina ratio) ratios of the IM-5 molecular sieves A-1, B-1, C-1, D-1 and E-1 were determined to be 35, 34, 50, 33 and 36, respectively, using XRF fluorescence elemental analysis.
(2) The catalytic performance of molecular sieves A-1, B-1, C-1, D-1 and E-1 in a gas phase alkylation reaction of benzene with ethylene was examined according to the following procedure:
2.0g of hydrogen type IM-5 molecular sieve is filled in a fixed bed reaction device, and benzene and ethylene are introduced to carry out gas phase alkylation reaction of the benzene and the ethylene. Evaluation conditions: the molar ratio of benzene to ethylene is 7.5, the mass airspeed based on ethylene is 0.7h -1, the reaction pressure is 0.8MPa, the reaction temperature is 280 ℃, 315 ℃, 330 ℃ and 360 ℃, the reaction time of each temperature section is 24h, three instantaneous samples are collected at each temperature point to ensure the reliability of data, the composition of the products is analyzed by chromatography, and then the ethylene conversion rate and the ethylbenzene selectivity are calculated, and the average value is taken. The reaction results are shown in Table 2.
The xylene content in table 2 refers to the sum of the contents of all xylenes (ortho, meta, para); the ethylene conversion and ethylbenzene selectivity listed are calculated by the following formula:
Ethylene conversion= (ethylene feed mass-ethylene mass in product)/ethylene feed mass x 100%;
Ethylbenzene selectivity = mass fraction of ethylbenzene in product/(mass fraction of benzene in 100-product-mass fraction of ethylene in product) ×100%.
TABLE 2
As can be seen from Table 2, the mesoporous hydrogen-containing IM-5 molecular sieves of the invention are used in the vapor phase alkylation of benzene and ethylene, have higher ethylene conversion and ethylbenzene selectivity under low temperature reaction conditions and lower byproduct xylene production than IM-5 molecular sieves without the intragranular mesopores (i.e., the IM-5 molecular sieves prepared in comparative preparation examples 1 and 2), and have certain application potential.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.

Claims (10)

1. A method for substituting hydrogen on a benzene ring, the method comprising: and (2) in the presence of a hydrogen type IM-5 molecular sieve, enabling benzene series to contact with olefin for reaction, wherein the total specific surface area of the hydrogen type IM-5 molecular sieve is 250-450m 2/g, the total pore volume is 0.2-0.7cm 3/g, the most probable mesoporous diameter is 4-20nm, and the silicon-aluminum ratio is below 60.
2. The process according to claim 1, wherein the hydrogen form IM-5 molecular sieve has a total specific surface area of 300-450m 2/g, a total pore volume of 0.3-0.6cm 3/g, a most probable mesoporous diameter of 5-15nm and a silica to alumina ratio of 30-50.
3. The method according to claim 1 or 2, wherein the hydrogen form IM-5 molecular sieve is obtained by subjecting a sodium form IM-5 molecular sieve to an ammonium exchange treatment, and the preparation method of the sodium form IM-5 molecular sieve comprises the following steps: sequentially carrying out hydrothermal crystallization, solid collection and drying on a crystallization material containing an aluminum source, an inorganic base containing alkali metal elements, a template agent, a pore-forming agent, a silicon source and water, wherein the consumption of each component in the crystallization material is such that SiO 2：Al2O3: oxides of alkali metals: template agent: the molar ratio of H 2 O is 1: (0.005-0.1): (0.1-0.5): (0.05-0.3): (5-50), preferably 1: (0.0083-0.05): (0.15-0.4): (0.08-0.2): (7-40), siO 2: the weight ratio of the pore-forming agent is 1: (0.02-0.3), preferably 1: (0.05-0.25).
4. A method according to claim 3, wherein the aluminium source is at least one of an aluminium salt, aluminate, meta-aluminate, alumina and aluminium hydroxide, preferably at least one of sodium aluminate, sodium meta-aluminate, aluminium sulphate, aluminium chloride, aluminium nitrate, aluminium hydroxide, alumina and pseudo-boehmite;
and/or the inorganic alkali containing alkali metal element is alkali metal hydroxide, preferably sodium hydroxide and/or potassium hydroxide;
And/or the template agent is a salt of a1, 5-bis (N-methylpyrrolidine) pentylene cation, preferably a1, 5-bis (N-methylpyrrolidine) pentylene dibromo salt;
And/or the pore-forming agent is a glucose polymer, preferably at least one of cellulose, sodium carboxymethyl cellulose and starch;
and/or the silicon source is at least one of silicate, silicate and silicon dioxide, preferably at least one of amorphous silicon dioxide, water glass, silica sol, solid silicon oxide, solid silica gel, diatomite, white carbon black and tetraethoxysilane.
5. A method according to claim 3, wherein the conditions of hydrothermal crystallization comprise: the temperature is 120-200deg.C, preferably 130-180deg.C; the time is 1-15 days, preferably 4-10 days.
6. The process according to claim 1 or 2, wherein the molar ratio of benzene-series to olefin is 2-20:1, preferably 4-8:1.
7. The process according to claim 1 or 2, wherein the benzene series is selected from alkyl substituted benzenes and alkyl is a C1-C4 alkyl, preferably at least one of benzene, toluene, xylene and trimethylbenzene.
8. The process according to claim 1 or 2, wherein the olefin is selected from C2-C6 mono-olefins, preferably at least one of ethylene, propylene, butene and pentene.
9. The method of claim 1 or 2, wherein the contacting conditions comprise: the reaction temperature is 240-360 ℃, preferably 260-350 ℃, more preferably 260-330 ℃; the reaction pressure is 0.2-2MPa, preferably 0.5-1MPa; the weight hourly space velocity of the olefin is from 0.3 to 2h -1, preferably from 0.5 to 1h -1.
10. Use of a hydrogen form IM-5 molecular sieve or a sodium form IM-5 molecular sieve as defined in any one of claims 1 to 5 for reducing the reaction temperature and/or increasing the selectivity of the target product in a process for replacing hydrogen on a benzene ring.
CN202211268749.5A 2022-10-17 2022-10-17 Method for substituting hydrogen on benzene ring and application thereof Pending CN117945828A (en)

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