CN113880110A - Nanometer hierarchical pore MOR/MTW eutectic molecular sieve and preparation method and application thereof - Google Patents

Nanometer hierarchical pore MOR/MTW eutectic molecular sieve and preparation method and application thereof Download PDF

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CN113880110A
CN113880110A CN202111238049.7A CN202111238049A CN113880110A CN 113880110 A CN113880110 A CN 113880110A CN 202111238049 A CN202111238049 A CN 202111238049A CN 113880110 A CN113880110 A CN 113880110A
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molecular sieve
mor
mtw
hierarchical pore
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CN113880110B (en
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冯刚
刘清华
张荣斌
文志辉
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Nanchang University
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Abstract

The invention relates to a nanometer hierarchical pore MOR/MTW eutectic molecular sieve and a preparation method and application thereof, wherein the eutectic molecular sieve comprises 1.0-99.99% of MTW structure molecular sieve, and the balance is MOR structure molecular sieve; the Si/Al atomic ratio in the nano hierarchical pore eutectic molecular sieve is 1-7000: 1; the grain size of the nanometer hierarchical pore MOR/MTW molecular sieve is 20-1000 nm; the value of medium pore volume/micropore volume of the nanometer hierarchical pore MOR/MTW eutectic molecular sieve is about 1.0-10.0: 1. According to the invention, by utilizing an ordered synthesis method, firstly, a solution of the MOR molecular sieve is prepared, then, the solution is mixed with a silicon source, an aluminum source, water, a template agent, a surfactant and the like, the mixture is crystallized for 0.5-100 days at the temperature of 110-200 ℃, and the nanometer multilevel pore MOR/MTW-containing eutectic molecular sieve is obtained through the steps of washing, drying, roasting and the like. The preparation method provided by the invention overcomes the problem that the prior art can not prepare and provide the nanometer hierarchical pore MOR/MTW eutectic molecular sieve, and the eutectic molecular sieve has wide application prospects in the aspects of catalysis, adsorption separation and the like in the fields of fine chemical industry, coal chemical industry, petrochemical industry and the like.

Description

Nanometer hierarchical pore MOR/MTW eutectic molecular sieve and preparation method and application thereof
Technical Field
The invention belongs to the technical field of molecular sieves, and particularly relates to a nanometer hierarchical pore MOR/MTW eutectic molecular sieve, and a preparation method and application thereof.
Background
The MTW structure molecular sieve has one-dimensional linear non-crossed pore canal composed of twelve-membered ring, and the MOR structure molecular sieve has eight-membered ring and twelve-membered ring straight pore canal.
The eutectic molecular sieve refers to a molecular sieve with more than two crystal structures, and because the eutectic energy of the molecular sieve can modulate the pore structure and the acid property of the molecular sieve, the eutectic molecular sieve has respective reaction characteristics of the two molecular sieves in a catalytic reaction and is different from the performances of a mechanical mixed sample, thereby having attracted extensive attention of people. There are many technical methods for synthesizing composite molecular sieves. In 1978, Silicate-1 and ZSM-5 core-shell composite molecular sieves are synthesized by Rollmann for the first time by an alkali dissolution method, but the molecular sieves synthesized by the alkali dissolution method are deficient in appearance; the Mobil company firstly develops a ZSM-5/ZSM-11 eutectic molecular sieve in 1980, but the application range of the composite molecular sieve prepared by the eutectic method is very limited, and any two molecular sieves can not be synthesized by the eutectic one-step method, so that the synthesis of the eutectic molecular sieve is limited; goosens and the like firstly use a wrapping method to synthesize the FAU/EMT composite molecular sieve in 1999, but the preparation process using the wrapping method is very complicated, the time cost and the economic cost are very high, and the method is not suitable for large-scale production; CN107619054B discloses a preparation method of a ten-membered ring nano hierarchical pore ZSM-5/ZSM-11 eutectic zeolite molecular sieve, which prepares the nano hierarchical pore ZSM-5/ZSM-11 eutectic molecular sieve by a one-step method. However, the existing synthesis technology for the composite eutectic molecular sieve has many defects and shortcomings, so that the physicochemical properties of the composite molecular sieve have some shortcomings. Because the synthesis system is more complex than that of a single molecular sieve, the synthesis of the component molecular sieve as a component in the composite molecular sieve is difficult, and particularly, the physicochemical properties of the component molecular sieve are extremely difficult to control and are difficult to meet the requirements of catalytic reaction, thereby limiting the application of the component molecular sieve in industrial catalysis.
The nano molecular sieve is a molecular sieve with the particle size of 0.1-1000 nm, has the characteristics of small crystal grains, large specific surface area and short pore channels, is favorable for reducing mass transfer resistance, and can effectively reduce catalyst inactivation caused by the blockage of orifices by reactants or carbon deposition, thereby improving the stability of the catalyst. The patent CN107673370B applies the nano SAPO-34 molecular sieve catalyst to MTO reaction, the catalyst shows excellent catalytic performance, and the service life of the catalyst is obviously prolonged.
Compared with a molecular sieve with a single pore channel structure, the hierarchical pore molecular sieve has excellent mass transfer performance in a catalytic reaction. The reactant has better shape selectivity in the molecular sieve with a single microporous structure, but the mass transfer resistance is large; the macroporous and mesoporous molecular sieves are beneficial to mass transfer, but the shape-selective catalytic capability of the macropores and the mesopores is poor. The mesoporous and macroporous structures are introduced into the microporous molecular sieve or the microporous structure is introduced into the macroporous molecular sieve, so that the molecular sieve with the hierarchical pore structure is prepared, and the mass transfer process in the catalytic reaction is facilitated. The hierarchical porous molecular sieve not only has the characteristics of a microporous molecular sieve, but also has the characteristics of a mesoporous molecular sieve, can improve the mass transfer rate of molecules, effectively reduces mass transfer resistance, is beneficial to reducing carbon deposition and prolongs the service life of a catalyst. Multi-stage pore ZSM-5 is applied to the normal hexane cracking reaction by, for example, Wang (Wang Darui et al. post synthesis of mesoporous ZSM-5 zeolite by piperidine-assisted purification and super organic catalytic properties in hydrocarbon cracking [ J ]. Journal of Materials Chemistry A, 2015, 3 (7): 3), etc., and the result shows that the multi-stage pore molecular sieve has higher normal hexane conversion rate and propylene selectivity;
if the characteristics of eutectic, nanocrystallization and hierarchical pores can be combined into a molecular sieve, the catalytic performance of the molecular sieve is certainly and greatly improved. The patent CN103539619A provides a ten-membered ring nano hierarchical pore ZSM-5/ZSM-11 applied to aromatizing mixed carbon four to prepare aromatic hydrocarbon, and better solves the problem that the catalyst in the prior art is easy to deposit carbon and deactivate.
MTW and MOR molecular sieves are molecular sieves with twelve-membered ring channel structures, and have wide application prospects in the field of industrial catalysis. If the MTW and MOR molecular sieves can be prepared into the nano eutectic hierarchical pore molecular sieve, the catalytic performance of the nano eutectic hierarchical pore molecular sieve can be greatly improved. CN110451519A discloses a preparation method of MOR/MTW eutectic molecular sieve, but the nanometer and multi-level pore formation of the MOR/MTW eutectic molecular sieve cannot be realized.
Therefore, the market urgently needs a method for providing a nanometer hierarchical pore MOR/MTW eutectic molecular sieve.
Therefore, the patent provides a nano hierarchical pore MOR/MTW eutectic molecular sieve and a preparation method and application thereof, which combine an ordered synthesis method, sequentially synthesize MOR molecular sieve solution according to a specific material proportion, and then use the MOR molecular sieve solution and a surfactant to induce and form the nano hierarchical pore MOR/MTW eutectic molecular sieve; the method can effectively solve the preparation problem of the nanometer hierarchical pore MOR/MTW eutectic molecular sieve, and can solve the problems of complicated and complex process for preparing the nanometer hierarchical pore eutectic molecular sieve; the nanometer hierarchical pore MOR/MTW eutectic molecular sieve can be used for the production of 2, 6-dimethylnaphthalene and p-xylene, and the reaction for preparing ethylene by acetylene hydrogenation.
Disclosure of Invention
One of the technical problems to be solved by the invention is to provide a nano hierarchical pore MOR/MTW eutectic molecular sieve, which overcomes the problem that the component molecular sieve in the nano hierarchical pore MOR/MTW eutectic molecular sieve can not be accurately regulated and controlled in the prior art. The technical scheme adopted by the invention is as follows:
a nanometer hierarchical pore MOR/MTW eutectic molecular sieve comprises 1.0-99.99% of MTW structural material by mass percent, and the balance of MOR structural molecular sieve; the atomic ratio of Si to Al in the eutectic molecular sieve is 1-7000: 1, and the value of medium pore volume/micropore volume in the molecular sieve is about 1.0-10.0: 1;
the nanometer hierarchical pore MOR/MTW eutectic molecular sieve has MOR type molecular sieve and MTW type molecular sieve crystal phases at the same time, and the specific surface area of the eutectic molecular sieve is 50-1000 m2Per g, pore volume of 0.001-0.93 cm3Per g, the particle diameter is 20 to 1000nm, and the acid content is 0.0001 to 18.5 mmol/g.
Preferably, the content of the MTW molecular sieve in the nanometer hierarchical pore MOR/MTW eutectic molecular sieve is 5-96%.
Preferably, the mass percentage of alumina in the nanometer hierarchical pore MOR/MTW eutectic molecular sieve is 1-45%.
The second technical problem to be solved by the invention is to provide a preparation method of the nanometer hierarchical pore MOR/MTW eutectic molecular sieve corresponding to the first technical problem to be solved, and make up for the problem of the current technological means for synthesizing the nanometer hierarchical pore MOR/MTW eutectic molecular sieve. The technical scheme adopted by the invention is as follows:
the preparation method of the nanometer hierarchical pore MOR/MTW eutectic molecular sieve is carried out according to an ordered synthesis method and comprises the following steps:
1) preparation of seed solution a containing MOR: mixing a substance at least containing an MOR type molecular sieve with an organic template agent, proportioning the MOR molecular sieve, the template agent and water as raw materials, and stirring to obtain a seed crystal solution A containing MOR;
2) preparation of mixed solution B: sequentially using a template agent, water, an aluminum source, a silicon source and a surfactant as raw materials according to the proportion of Al2O3∶SiO2Template agent and H2Mixing O and a surfactant in a molar ratio of 1 to (20-220) to (9.8-60) to (1-2000) to (1-3) to prepare a mixed solution B;
3) preparing a nanometer hierarchical pore MOR/MTW eutectic molecular sieve: fully and uniformly stirring the seed crystal solution A and the mixed solution B according to the mass ratio of 1: 0.1-10, putting the mixture into a reaction kettle, crystallizing for 0.01-1200 h at 120-190 ℃, filtering and washing the obtained solid matter, drying at 50-300 ℃, and roasting the dried sample at 300-800 ℃ to obtain the nano hierarchical pore MOR/MTW eutectic molecular sieve.
Preferably, the silicon source used in the raw material at least contains one of silica sol, tetraethyl orthosilicate, water glass, white carbon black, fly ash, kaolin, montmorillonite and attapulgite; the aluminum source is at least one of metaaluminate, pseudo-boehmite, aluminum sulfate, aluminum nitrate, aluminum chloride, aluminum hydroxide, fly ash, kaolin, montmorillonite, alumina, aluminum-containing spinel and the like; the template agent at least contains one of tetraethyl ammonium ion, methyl triethyl bromide ion, ammonium ion and the like; the surfactant used contains at least one of polyethylene, cetyl ammonium bromide, nonionic copolymer, octadecyl dimethyl trimethyl ammonium trimethicone chloride, etc.
The further scheme is that in the step 1), the MOR molecular sieve, the organic template and water are mixed according to the molar ratio of 1 to (1-5) to (1-3), and the mixing and stirring time is 1-24 hours;
the further proposal is that the specific surface area of the MOR type molecular sieve used in the step 1) is 50-1000 m2A pore diameter of 0.001 to 0.89cm3(iv)/g, the average particle diameter is 0.001 to 45 μm, and the Si/Al atomic ratio is 9000 to 1.0.
The invention also provides application of the nanometer hierarchical pore MOR/MTW eutectic molecular sieve, which is used as a catalyst for producing 2, 6-dimethylnaphthalene, producing dimethylbenzene and selectively hydrogenating acetylene.
The method for producing the molecular sieve of the 2, 6-dimethylnaphthalene by using the nano hierarchical pore MOR/MTW eutectic molecular sieve as the catalyst has the advantages of high conversion rate of raw materials, high 2.6-site selectivity and good stability; overcomes the defects of low conversion rate of raw materials, low selectivity, poor stability and the like in the prior art for producing 2, 6-dimethylnaphthalene. The method specifically comprises the following steps: the nanometer hierarchical pore MOR/MTW eutectic molecular sieve is used as a catalyst, a substance containing naphthalene or alkyl naphthalene is used as a main raw material, and C is used9 +Monocyclic aromatic hydrocarbon or methanolThe alkylation reagent is used for alkylation reaction at the reaction temperature of 240-600 ℃, the reaction pressure of 0.1-5.5 MPa and the weight space velocity of 0.3-6h-1Under the condition of (1), the raw material is contacted with a catalyst bed layer and reacts to generate a product containing 2, 6-dimethylnaphthalene.
Wherein, the method for producing the molecular sieve of the dimethylbenzene by using the nanometer hierarchical pore MOR/MTW eutectic molecular sieve as a catalyst. Has the advantages of high conversion rate of raw materials, high para-selectivity and good stability; overcomes the defects of low conversion rate of raw materials, low para-selectivity, poor stability and the like in the prior xylene production technology. The method specifically comprises the following steps: the nanometer hierarchical pore MOR/MTW eutectic molecular sieve is used as a catalyst, a substance containing benzene or toluene is used as a raw material, and C is used9 +Monocyclic aromatic hydrocarbon or methanol is taken as an alkylating reagent, the reaction temperature is 230-600 ℃, the reaction pressure is 0.1-6 MPa, and the weight space velocity is 0.2-7 h-1Under the conditions of (1) contacting the feedstock with a catalyst bed, reacting to produce a product containing xylene.
The method for preparing the ethylene by selective hydrogenation of the acetylene by using the nanometer hierarchical pore MOR/MTW eutectic molecular sieve as the catalyst has the advantages of high conversion rate of raw materials, high selectivity and good stability; overcomes the defect that the prior art can not directly prepare the ethylene by selectively hydrogenating the acetylene. The method specifically comprises the following steps: the nanometer hierarchical pore MOR/MTW eutectic molecular sieve is used as a catalyst, a substance containing hydrogen and acetylene is used as a raw material, the reaction temperature is 30-400 ℃, the reaction pressure is 0.05-3.0 MPa, and the airspeed is 300-450000 h-1The feedstock is contacted with a catalyst bed and reacted to produce a product comprising ethylene.
Compared with the prior art, the invention has the beneficial effects that:
(1) the specific surface area of the eutectic material of the nanometer hierarchical pore eutectic molecular sieve prepared by the method is 100-900 m2Per g, pore volume of 0.01-0.93 cm3The particle size of the molecular sieve is 20-1000 nm, and the ratio of the mesoporous volume to the microporous volume is about 1.0-10.0: 1. The content of at least the MTW molecular sieve in the eutectic material is 5-96 percent, the mass percentage content of the alumina is 1-45 percent, and the MOR/MTW co-porous nano-grade can be accurately regulated and controlledThe crystal molecular sieve is a component molecular sieve.
(2) The invention provides a method for preparing a nanometer hierarchical pore MOR/MTW eutectic molecular sieve, which solves the problem that the prior art can not prepare and provide the nanometer hierarchical pore MOR/MTW eutectic molecular sieve.
Drawings
FIG. 1 is an XRD diagram of a nano hierarchical pore MOR/MTW eutectic molecular sieve obtained by the preparation method of example 1 of the present invention.
FIG. 2 is an SEM image of a nano hierarchical pore MOR/MTW eutectic molecular sieve obtained by the preparation method of example 1 of the invention.
The invention is further explained with reference to the drawings and the embodiments.
Detailed Description
The preparation methods and the use conditions used in the following examples are conventional methods unless otherwise specified; reagents, gases, materials and the like used in the following examples are commercially available unless otherwise specified.
[ example 1 ]
Preparing a nano multi-level pore MOR/MTW eutectic molecular sieve by using a self-made MOR type molecular sieve:
1. taking 73g of tetraethylammonium hydroxide, 5g of sodium metaaluminate and 2.5g of sodium fluoride, sequentially adding the tetraethylammonium hydroxide, the sodium metaaluminate and the sodium fluoride into a polytetrafluoroethylene lining under the stirring of a magnetic stirrer, stirring to dissolve the tetraethylammonium hydroxide, slowly adding 75g of silica sol by using a dropping funnel, stirring strongly until the solution is uniform, continuing stirring for 30min, placing the polytetrafluoroethylene lining filled with the solution into a stainless steel kettle, sealing, placing the stainless steel kettle in an oven at 178 ℃ for crystallization for 4d, washing for 30min by cold water after the crystallization is finished, and stirring for 30min at room temperature by using the magnetic stirrer to obtain an MOR type molecular sieve solution;
2. mixing 35g of MOR type molecular sieve solution with 30g of TEAOH solution, and stirring for 12 hours at room temperature by using a magnetic stirrer to obtain MOR type seed crystal solution;
3. weighing 41g of tetraethylammonium hydroxide, 28g of deionized water, 1.1g of sodium metaaluminate and 1g of polyethylene, sequentially adding the materials into a polytetrafluoroethylene lining under the stirring of a magnetic stirrer, stirring to dissolve the materials, slowly adding 66g of silica sol by using a dropping funnel, stirring strongly until the solution is uniform, continuing stirring for 30min, placing the polytetrafluoroethylene lining filled with the solution into a stainless steel kettle, sealing, placing the stainless steel kettle in an oven at 160 ℃ for crystallization for 6d, after the crystallization is finished, washing, filtering, stirring and drying, and roasting at 550 ℃ for 6h to finally obtain the nano multilevel pore MOR/MTW eutectic molecular sieve. The sample was analyzed by XRD and SEM and the spectra were similar to those of FIGS. 1 and 2.
The specific surface area of the obtained nanometer hierarchical pore MOR/MTW eutectic molecular sieve is 220m2Per g, pore volume 0.25cm3The value of mesoporous volume/microporous volume is 2.5, and the particle size of the molecular sieve is 150 nm.
[ example 2 ]
Using a specific surface area of 256m2(ii)/g, total pore volume 0.24cm3Preparing a nanometer multilevel-pore MOR/MTW eutectic molecular sieve by using the MOR type molecular sieve with the particle size of 5-10 mu m and the Si/Al atomic ratio of 10:
1. mixing 15g of MOR type molecular sieve with 30g of TEAOH solution, and stirring for 12 hours at room temperature by using a magnetic stirrer to obtain MOR type seed crystal solution;
2. weighing 40g of tetraethylammonium hydroxide, 18g of deionized water, 0.35g of sodium metaaluminate and 1.2g of hexadecylammonium bromide, sequentially adding the tetraethylammonium hydroxide, the deionized water and the sodium metaaluminate into a polytetrafluoroethylene lining under the stirring of a magnetic rotor, stirring to dissolve the tetraethylammonium hydroxide, slowly adding 43g of silica sol by using a dropping funnel, stirring strongly until the solution is uniform, continuing stirring for 30min, placing the polytetrafluoroethylene lining filled with the solution into a stainless steel kettle, sealing, placing the stainless steel kettle in an oven at 160 ℃ for crystallization for 6d, after the crystallization is finished, washing with cold water, filtering, stirring, drying, and roasting at 550 ℃ for 6h to finally obtain the nano hierarchical pore MOR/MTW eutectic molecular sieve. The sample was analyzed by XRD and SEM and the spectra were similar to those of FIGS. 1 and 2.
The specific surface area of the obtained nanometer hierarchical pore MOR/MTW eutectic molecular sieve is 240m2Per g, pore volume 0.24cm3The value of mesoporous volume/microporous volume is 3.3, and the particle size of the molecular sieve is 350 nm.
[ example 3 ]
Preparing a nano hierarchical pore MOR/MTW eutectic molecular sieve by using a suction filtration liquid of a self-made MOR type molecular sieve:
1. mixing the 20g of the extract of the MOR molecular sieve in the example 1 with 35g of TEAOH solution, and stirring for 12h at room temperature by using a magnetic rotor to obtain MOR type seed crystal solution;
2. weighing 10g of tetraethylammonium hydroxide, 21g of deionized water, 0.23g of sodium metaaluminate and 1.5g of octadecyl dimethyl trimethyl silica propyl ammonium chloride, sequentially adding the tetraethylammonium hydroxide, the deionized water and the sodium metaaluminate into a polytetrafluoroethylene lining under the stirring of a magnetic stirrer, stirring to dissolve the tetraethylammonium hydroxide, slowly adding 53g of silica sol by using a dropping funnel, strongly stirring until the solution is uniform, continuously stirring for 30min, placing the polytetrafluoroethylene lining filled with the solution into a stainless steel kettle for sealing, placing the stainless steel kettle for crystallization for 6d in an oven at 160 ℃, washing the polytetrafluoroethylene lining with cold water after the crystallization is finished, filtering, stirring, drying, and roasting at 550 ℃ for 6h to finally obtain the nano hierarchical pore MOR/MTW eutectic molecular sieve. The sample was analyzed by XRD and SEM and the spectra were similar to those of FIGS. 1 and 2.
The specific surface area of the obtained nanometer hierarchical pore MOR/MTW eutectic molecular sieve is 210m2Per g, pore volume 0.22cm3The value of mesoporous volume/microporous volume is 4.8, and the particle size of the molecular sieve is 500 nm.
[ examples 4 to 27 ]
The preparation method comprises the following steps of operating the raw materials such as water, an aluminum source, a silicon source, an organic template agent, a surfactant and the like according to the preparation conditions shown in the table 1 and implementing the steps 1 to 3 to obtain the nano hierarchical pore MOR/MTW eutectic molecular sieve.
TABLE 1 reaction conditions and resulting molecular Sieve Properties for examples 4-27
Figure BDA0003318127120000071
Figure BDA0003318127120000081
Figure BDA0003318127120000091
Figure BDA0003318127120000101
[ examples 28 to 77 ]
The nanometer hierarchical pore MOR/MTW eutectic molecular sieve is used for producing 2, 6-dimethylnaphthalene.
Using substance containing naphthalene or alkyl naphthalene as main raw material and C9 +Monocyclic aromatic hydrocarbon or methanol is used as an alkylating agent, and the nanometer multilevel pore MOR/MTW eutectic molecular sieve obtained in examples 1-27 is adopted to evaluate the performance of the catalyst according to the reaction conditions in the following table, so that a product rich in 2, 6-dimethylnaphthalene can be obtained.
TABLE 2 reaction conditions and products of examples 28-77
Figure BDA0003318127120000102
Figure BDA0003318127120000111
Figure BDA0003318127120000121
Examples 78 to 104
The nanometer hierarchical pore MOR/MTW eutectic molecular sieve is used for producing dimethylbenzene.
Using substance containing benzene or toluene as raw material and C9 +Monocyclic aromatic hydrocarbon or methanol is used as an alkylating agent, and the performance of the catalyst is evaluated by adopting the nano multilevel pore MOR/MTW eutectic molecular sieve obtained in the examples 1 to 27 according to the reaction conditions shown in the following table, so that a product rich in xylene can be obtained.
TABLE 3 reaction conditions and products of examples 78-104
Figure BDA0003318127120000122
Figure BDA0003318127120000131
Example 105-131
The nanometer hierarchical pore MOR/MTW eutectic molecular sieve is used for acetylene selective hydrogenation reaction.
Substances containing hydrogen and acetylene are used as raw materials, the nanometer hierarchical pore MOR/MTW eutectic molecular sieve prepared in examples 1-27 is adopted, and the performance of the catalyst is evaluated according to the reaction conditions in the following table, so that a product rich in ethylene can be obtained.
TABLE 4 reaction conditions and products of example 105-131
Figure BDA0003318127120000141
Figure BDA0003318127120000151
The above description is only a preferred embodiment of the present invention and should not be taken as limiting, and it will be understood by those skilled in the art that various changes and modifications may be made in the invention and any alterations, equivalents, improvements and the like made within the spirit and principle of the present invention should be included in the scope of the present invention.

Claims (10)

1. A nanometer hierarchical pore MOR/MTW eutectic molecular sieve is characterized in that:
1) the nanometer hierarchical pore MOR/MTW eutectic molecular sieve has a pore structure and a crystal structure of MOR and MTW;
2) the material comprises 1.0 to 99.99 percent of MTW structural material by mass percentage, and the rest at least comprises MOR structural molecular sieve;
3) the Si/Al atomic ratio in the nanometer hierarchical pore MOR/MTW eutectic molecular sieve is 1-7000: 1;
4) the grain size of the nanometer hierarchical pore MOR/MTW eutectic molecular sieve is 20-1000 nm;
5) the value of medium pore volume/micropore volume of the nanometer hierarchical pore MOR/MTW eutectic molecular sieve is 1.0-10.0: 1.
2. The nanomicelle MOR/MTW eutectic molecular sieve of claim 1, wherein: the specific surface area of the nanometer hierarchical pore MOR/MTW eutectic molecular sieve is 50-1000 m2(ii) a total pore volume of 0.001 to 0.93cm3The acid content is 0.0001-18.5 mmol/g.
3. The nanomicelle MOR/MTW eutectic molecular sieve of claim 1, wherein: the content of the MTW molecular sieve in the nanometer hierarchical pore MOR/MTW eutectic molecular sieve is 5-96%; the mass percentage of alumina in the nanometer hierarchical pore MOR/MTW eutectic molecular sieve is 1-45%.
4. The preparation method of the nanometer hierarchical pore MOR/MTW eutectic molecular sieve as claimed in any one of claims 1 to 3, wherein the synthesis is carried out according to an ordered synthesis method, comprising the following steps:
1) preparation of seed solution a containing MOR: mixing a substance at least containing an MOR type molecular sieve with a template agent, proportioning the MOR molecular sieve, the template agent and water as raw materials, and stirring to obtain a seed crystal solution A containing MOR;
2) preparation of mixed solution B: sequentially using a template agent, water, an aluminum source, a silicon source and a surfactant as raw materials according to Al2O3∶SiO2Template agent and H2Mixing O and a surfactant in a molar ratio of 1 to (20-220) to (9.8-60) to (1-2000) to (1-3) to prepare a mixed solution B;
3) preparing a nanometer hierarchical pore MOR/MTW eutectic molecular sieve: fully and uniformly stirring the seed crystal solution A and the mixed solution B according to the mass ratio of 1: 0.1-10, putting the mixture into a reaction kettle, crystallizing for 0.01-1200 h at 110-300 ℃, filtering and washing the obtained solid matter, drying at 50-300 ℃, and roasting the dried sample at 350-800 ℃ to obtain the nano hierarchical pore MOR/MTW eutectic molecular sieve.
5. The method for preparing nano hierarchical pore MOR/MTW eutectic molecular sieve according to claim 4, wherein: the specific surface area of the MOR type molecular sieve used in the step 1) is 50-1000 m2The total pore volume is 0.01-0.89 cm3(iii)/g, the particle diameter is 0.001 to 45 μm, and the Si/Al atomic ratio is 9000 to 1.0.
6. The method for preparing nano hierarchical pore MOR/MTW eutectic molecular sieve according to claim 4, wherein: in the step 1), the MOR molecular sieve, the template agent and the water are mixed according to the molar ratio of 1 to (1-5) to (1-3); the mixing and stirring time is 1-24 h.
7. The use of a nanomultipore MOR/MTW eutectic molecular sieve according to any one of claims 1 to 3, wherein: the application of the nanometer hierarchical pore MOR/MTW eutectic molecular sieve in a catalyst is used for producing 2, 6-dimethylnaphthalene, producing dimethylbenzene and selectively hydrogenating acetylene.
8. The use of the nanomultipore MOR/MTW eutectic molecular sieve according to claim 7, wherein the method for producing 2, 6-dimethylnaphthalene is specifically:
the nanometer hierarchical pore MOR/MTW eutectic molecular sieve is used as a catalyst, a substance containing naphthalene or alkyl naphthalene is used as a main raw material, and C is used9 +Monocyclic aromatic hydrocarbon or methanol is taken as an alkylating reagent, the reaction temperature is 240-600 ℃, the reaction pressure is 0.1-5.5 MPa, and the weight space velocity is 0.3-6h-1Under the condition of (1), the raw material is contacted with a catalyst bed layer and reacts to generate a product containing 2, 6-dimethylnaphthalene.
9. Use of a nanomultipore MOR/MTW eutectic molecular sieve according to claim 7, wherein said method for producing xylene is specifically:
the nanometer hierarchical pore MOR/MTW eutectic molecular sieve is used as a catalyst, a substance containing benzene or toluene is used as a raw material, and C is used9 +Monocyclic aromatic hydrocarbon or methanol is taken as an alkylating reagent, the reaction temperature is 230-600 ℃, the reaction pressure is 0.1-6 MPa, and the weight space velocity is 0.2-7 h-1Under the conditions of (1) contacting the feedstock with a catalyst bed, reacting to produce a product containing xylene.
10. The use of the nanomultipore MOR/MTW eutectic molecular sieve according to claim 7, wherein the selective hydrogenation of acetylene is specifically:
the nanometer hierarchical pore MOR/MTW eutectic molecular sieve is used as a catalyst, a substance containing hydrogen and acetylene is used as a raw material, the reaction temperature is 30-400 ℃, the reaction pressure is 0.05-3.0 MPa, and the airspeed is 300-450000 h-1The feedstock is contacted with a catalyst bed and reacted to produce a product comprising ethylene.
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