WO2019002045A1 - Zéolite zsm-5 hiérarchique dotée d'une structure à pores ouverts - Google Patents

Zéolite zsm-5 hiérarchique dotée d'une structure à pores ouverts Download PDF

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Publication number
WO2019002045A1
WO2019002045A1 PCT/EP2018/066407 EP2018066407W WO2019002045A1 WO 2019002045 A1 WO2019002045 A1 WO 2019002045A1 EP 2018066407 W EP2018066407 W EP 2018066407W WO 2019002045 A1 WO2019002045 A1 WO 2019002045A1
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molecular sieve
zsm
mixture
range
mesopores
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PCT/EP2018/066407
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English (en)
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Junzhong LIN
Junliang Sun
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Stockholms Universitet Holding Ab
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
    • C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
    • C01B39/026—After-treatment
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
    • C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
    • C01B39/36—Pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
    • C01B39/38—Type ZSM-5
    • C01B39/40—Type ZSM-5 using at least one organic template directing agent
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/12—Surface area
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/14—Pore volume
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/16—Pore diameter

Definitions

  • the present invention relates to the field of molecular sieves, more
  • zeolite molecular sieves are widely used in the chemical industry today, especially for applications such as adsorption, separation, ion-exchange and catalysis.
  • Aluminosilicate zeolites such as Zeolite Socony Mobil-5 (ZSM-5)
  • ZSM-5 Zeolite Socony Mobil-5
  • ZSM-5 zeolite is an aluminosilicate zeolite belonging to the pentasil family of zeolites.
  • ZSM-5 contains a three-dimensional 10MR crossing pore structure, and relatively high thermal stability and hydrothermal stability.
  • ZSM-5 has a number of applications for catalysis in the petrochemical fields of paraffin cracking, isomerization of n-butylene, preparation of gasoline from synthesis gas and the like.
  • ZSM-5 molecular sieves used in the art today typically exhibits a microporous morphology. Such molecular sieves suffer from a number of drawbacks.
  • ZSM-5 molecular sieves are highly sensitive to deactivation and secondly, ZSM-5 molecular sieves used as catalysts are not well suited for the synthesis of bulky molecules.
  • Yet another object of the present invention is to provide a method for producing a crystalline molecular sieve having a uniform mesopore
  • the present invention provides a hierarchical
  • aluminosilicate ZSM-5 molecular sieve having a total pore volume of at least 0.85 cm 3 /g comprising mesopores having a diameter of 2-50 nm and micropores having a diameter of 0-2 nm. At least 50 percent of the
  • mesopores have an open pore structure.
  • the present invention is based on the realization that by introducing mesopores into a ZSM-5 molecular sieve, problems associated with conventional ZSM-5 molecular sieves can be alleviated.
  • the molecular sieve according to the present invention exhibits a uniform mesopore distribution which allows better mass transport for bulky molecules, during use of the molecular sieve as e.g. a catalyst.
  • the molecular sieve according to the invention will be less sensitive towards deactivation due to steric blockage by heavy secondary products.
  • the presence of mesopores further allows the hierarchical molecular sieve of the invention to be used as a catalyst in the synthesis of bulky molecules, as the introduction of mesopores allows for improved mass transport of larger molecules.
  • Hierarchical as referred to herein, should generally be understood as a property related to the porosity of the molecular sieve.
  • a hierarchical molecular sieve should be understood as a molecular sieve which comprises two or more different pore systems.
  • the hierarchical molecular sieve according to the present invention generally consists of two different pore systems having different pore size distribution.
  • the molecular sieve according to the present invention comprises mesopore type pores and micropore type pores. According to the definition provided by the International Union for Pure and Applied Chemistry (lUPAC) mesopores is defined as pores with intermediate size; i.e. those with widths in the range of 2-50 nm.
  • the definition of micropores, also according to lUPAC is pores with widths not exceeding about 2.0 nm.
  • a "molecular sieve” is intended to denote a porous solid with pores of molecular dimensions which permit the passage of molecules below a certain size.
  • Molecular sieves are typically used for drying gases and liquids and for separating molecules on the basis of their sizes and shapes. When two molecules are equally small and can enter the pores, separation is based on the polarity (charge separation) of the molecule, the more polar molecule being preferentially adsorbed. Other applications include catalytic applications.
  • the molecular sieve of the present invention is a zeolite molecular sieve, in particular a ZSM-5 molecular sieve.
  • the ZSM-5 (Zeolite Socony Mobil-5) zeolite is an aluminosilicate zeolite having the framework type MFI.
  • ZSM-5 zeolites are generally composed of several pentasil units linked together by oxygen bridges.
  • ZSM-5 zeolites comprise a three-dimensional 10MR crossing pores structure, and exhibit relatively high thermal and hydrothermal stability.
  • ZSM-5 molecular sieves are porous materials.
  • the term "total pore volume” as used herein denotes the total volume pore volume in the molecular sieve per unit mass molecular sieve, measured in the unit cm 3 /g.
  • ZSM-5 molecular sieves are porous materials. The total pore volume can be determined by use of a nitrogen gas adsorption measurements.
  • Nitrogen gas adsorption measurements are typically depicted as adsorption and desorption isotherms, wherein the quantity of absorbed nitrogen is plotted as a function of the relative pressure of nitrogen.
  • the total pore volume of the molecular sieve may be at least 0.85 cm 3 /g, such as at least 0.90 cm 3 /g, preferably about 0.91 cm 3 /g.
  • the total pore volume may be in the range of 0.85-1 .00 cm 3 /g, such as in the range of 0.85-0.95 cm 3 /g.
  • the total pore volume may also be at least 0.70 cm 3 /g, such as in the range of 0.70-1 .10 cm 3 /g.
  • the total pore volume may be at least 0.80 cm 3 /g.
  • the hierarchical aluminosilicate ZSM-5 molecular sieves according to the invention comprises mesopores having a diameter of 2-50 nm and
  • the volume of the micropores can also be determined using nitrogen gas adsorption.
  • the volume of the mesopores may be calculated as the difference between the total pore volume and the volume of the micropores.
  • the total pore volume may be determined using the method described above.
  • the volume of the micropores can be calculated by applying the t-plot method to the nitrogen gas adsorption isotherm.
  • the t-plot method is known to a person skilled in the art.
  • the t-plot method uses the nitrogen adsorption isotherm data in the region near the vertical uptake at lower relative pressures, after which the uptake plateaus.
  • the gas uptake volume at the plateau will be converted to a liquid volume which corresponds to the total volume of the micropores.
  • At least 50 percent of the total pore volume is made up by mesopores.
  • at least 70 percent of the total pore volume is made up by mesopores, such as at least 75 percent of the total volume, preferably about 78 percent of the total volume.
  • the mesopore volume may be below 90 percent of the total volume, such as below 80 percent of the total volume.
  • the mesopore volume is preferably in the range of 0.40-0.80 cm 3 /g, such as in the range of 0.65- 0.75 cm 3 /g, preferably about 0.71 cm 3 /g.
  • At least 50 percent of the mesopores have an open pore structure.
  • 50-90 percent of the mesopores may have an open pore structure, such as 50-80 percent, such as 50-70 percent.
  • 50-60 percent of the mesopores may have an open pore structure.
  • at least 60 percent of the mesopores have an open pore structure, such as at least 70 percent, preferably at least 80 percent, more preferably at least 90 percent.
  • the pores are classified into two categories based on their availability to an external fluid. Closed pores are defined as pores which are totally isolated from
  • Open pores are defined as pores which have a
  • open pores denote both pores which are open only at one end (generally denoted as e.g. blind pores, dead-end pores or saccate pores) and pores which are open at two ends (generally denoted as e.g. through pores).
  • the number of open pores may be estimated from transmission electron microscopy (TEM) images.
  • TEM transmission electron microscopy
  • a molecular sieve according to the some embodiments of the present invention wherein at least 50 percent of the mesopores have an open pore structure is advantageous for several reasons. Open pores improve the mass transport of molecules in the molecular sieve compared to closed pores. It allows for a faster mass transport and which is advantageous in applications such as separation and catalysis. Furthermore, an open pore structure provides less steric hindrance for bulky molecules.
  • the open mesopores of the present invention may be homogenously distributed both on the surface and in the molecular sieve particles.
  • the mesopores have a diameter in the range of 10-30 nm, such as about 15-25 nm.
  • the molecular sieve according to the present invention comprises uniformly distributed mesopores of a defined size in the range of 10-30 nm, such as about 15-25 nm.
  • terms such as “pore size” and “pore width” may be used interchangeably.
  • Mesopore size distribution may be estimated from nitrogen gas adsorption and calculated with the Barret-Joyner-Halenda (BJH) method known to a person skilled in the art.
  • the BJH method is based on the assumption that pores have a cylindrical shape and that pore radius is equal to the sum of the Kelvin radius and the thickness of the film adsorbed on the pore wall.
  • the adsorption and desorption branches can both be used to calculate pore size distribution
  • the amount of mesopores having a size in the range of 10-30 nm can also be estimated from TEM images.
  • 80 to 95 percent of the mesopores may have a diameter in the range of 10-30 nm.
  • 80- 90 percent of the mesopores may have a diameter in the range of 10-30 nm.
  • at least 60 percent of the mesopores may have a diameter in the range of 10-30 nm
  • the pores have an average wall thickness in the range of 20-50 nm, preferably in the range of 30-40 nm, such as about 34-36 nm.
  • the wall size is defined as the average distance between any two pores in the material.
  • the average wall size can be measured from TEM images using an appropriate software, such as Gatan DigitalMicrograph, known to a skilled person in the art.
  • the specific surface area is at least 400 m 2 /g, such as at least 500 m 2 /g, preferably 500-520 m 2 /g.
  • the specific surface area may be in the range of 450-550 m 2 /g.
  • the specific surface area may be in the range of 480-520 m 2 /g.
  • the specific surface is defined as the accessible area of solid surface per unit mass.
  • the specific surface can be derived from physisorption isotherm data (such as nitrogen adsorption data) by applying the Brunauer- Emmett-Teller (BET) method known to a skilled person in the art.
  • BET Brunauer- Emmett-Teller
  • a high specific surface area is preferred in applications such as catalysis.
  • a high specific surface area is believed to increase the number of sites at which a catalyzed reaction may take place.
  • the molecular sieve has a crystalline component of at least 70 weight percent as measured by X-ray diffraction.
  • the amount of crystalline component can be determined from the X-ray diffractogram using the PANalytical HighScores software.
  • the crystalline component is at least 80 weight percent, such as at least 90 weight percent.
  • the crystalline component is typically in the range of 90-100 weight percent.
  • the ZSM-5 molecular sieve of the present invention is preferably crystalline with a crystal size in the range of 1 -30 ⁇ , such as in the range of 5-20 ⁇ , preferably in the range of 5-15 ⁇ .
  • the crystals preferably have a MFI framework.
  • the mesopores are well distributed both on the surface and inside of the ZSM-5 crystals.
  • the molecular sieve may have an amorphous component.
  • a method for producing a hierarchical molecular sieve comprising the following steps:
  • the method according to the second aspect is advantageous in that a hierarchical ZSM-5 molecular sieve having homogenously distributed mesopores throughout the structure can be produced by treating a ZSM-5 zeolite with a post-treatment step.
  • the post-treatment step can be used to produce the molecular sieve disclosed in the first aspect of the invention.
  • One advantage with a post-treatment step according to the present invention is that it may be used to introduce mesoporosity into the ZSM-5 zeolite. Thus, it can be used to produce a hierarchical molecular sieve.
  • the post-treatment step according to the present invention furthermore provides a method for producing a molecular sieve which uses a mild hydrothermal re- crystallization, performed at a relatively low temperature for only a few hours. Furthermore, the method according to the present invention requires only a small amount of the alkali source. The hydrothermal recrystallization in step b) requires only a short period of time.
  • the method according to the second aspect of the invention is based on the realization that by post-treating a ZSM-5 molecular sieve with a structure directing agent, homogenously distributed mesopores can be introduced into the ZSM-5 molecular sieve.
  • a hierarchical ZSM-5 molecular sieve comprising mesopores and micropores can be formed.
  • Another advantage of the inventive method is that it may be used to produce a hierarchical molecular sieve having a high amount of crystalline material.
  • An advantage of the method of the present invention is that it allows for the introduction of homogenously distributed mesopores on the surface and inside the ZSM-5 crystals.
  • the structure directing agent of step a) may be a quaternary ammonium compound, such as tetrapropylammonium bromide or tetrapropylammonium hydroxide.
  • the structure directing agent is often added to the ZSM- 5 in the form of an aqueous solution.
  • the solution may have a concentration in the range of 0.05-0.15 M, such as about 1 M.
  • the step b) involves a hydrothermal reaction.
  • hydrothermal reaction is generally intended to denote a reaction wherein reactants are crystallized from aqueous solutions.
  • the hydrothermal reaction is preferably performed at a high vapor pressure, such as in the range of
  • the step b) may be performed in an autoclave, preferably a Teflon lined autoclave.
  • the autoclave may also be lined with any suitable material known to a person skilled in the art.
  • the hydrothermal reaction of step b) may be performed at temperature of 120-200 °C, such as 160-185 °C, preferably 175-185 °C.
  • the hydrothermal reaction is generally performed for 1 -6 hours, such as 1 -3 hours.
  • the step c) involves separating the solid product from the reacted mixture. During the hydrothermal reaction of step b) a solid product is formed. This solid product is separated from the reacted mixture by means known to a person skilled in the art, for example by filtering. The solid product is optionally dried after the step of separation. The step of drying may be performed at a moderate temperature in an oven.
  • the step d) involves a step of calcining the solid product.
  • Calcining, or calcination is supposed to denote a reaction performed at high temperature. Preferably, the reaction is performed in air or oxygen.
  • the calcining step may be used to drive off water vapour from the solid product.
  • Step d) produces a solid product, typically a powder, of the hierarchical molecular sieve.
  • the hierarchical molecular sieve may be in accordance with any one of the embodiments discussed in the first aspect.
  • the ZSM-zeolite used in step a) of the inventive method may be a ZSM-5 zeolite produced according to methods known in the art.
  • the aqueous phase may be water. It may also be a solution comprising water.
  • the method further comprises the following steps: a1 ) mixing an aluminum source, a silicon source, a structure directing agent and an alkali source to an aqueous phase to form a first mixture
  • the silicon source is selected from the group consisting of silica, fumed silica, carbon white, silica gel, sodium silicate or tetraethyl orthosilicate.
  • the silicon source may be provided as a powder. It may also be provided as a gel.
  • the aluminum source is preferably selected from the group consisting of sodium aluminate, aluminum silicate, aluminum
  • the structure directing agent is a quaternary
  • ammonium compound such as tetrapropylammonium bromide or
  • the same type of structure directing agent may be used in both step a1 ) and step a).
  • Structure directing agents are common in the art of synthesizing zeolites and known to a skilled person in the art.
  • the role of the structure directing agent in zeolite synthesis is generally to direct the aluminosilicate into the desired structure and framework.
  • the alkali source is sodium hydroxide (NaOH).
  • the alkali source may also be potassium hydroxide (KOH).
  • the molar ratio of Na + to silica (S1O2) in the first mixture of step a1 ) is in the range of 0.01 -0.4, preferably in the range of 0.01 -0.3.
  • the sodium ions are generally provided as part of the alkali source.
  • An advantage of the present invention is that the method can be performed using only a small amount of alkali source. The reaction of the present method does not require an excess of alkali source.
  • the molar ratio of S1O2 to AI2O3 in the first mixture of step a1 ) is in the range of 30-70, preferably 40-70. The molar ratio of S1O2 to AI2O3 is often used to describe zeolites.
  • the molar ratio of structure directing agent to S1O2 in the first mixture of step a1 is in the range of 0.1 -0.5, preferably 0.1 -0.4.
  • the molar ratio of water (H2O) to silica (S1O2) in step a) is in the range of 30-200, preferably 40-80.
  • the mixing of step a2) is performed by agitation at a temperature of 20 - 50 °C, preferably about 30 - 40 °C. The mixing is typically performed for 1 -24 hours.
  • the hydrothermal reaction of step a3) is performed at a temperature of 160-185 °C, such as 175-185 °C.
  • the hydrothermal reaction of step a3) is performed for 48-120 hours.
  • the steps a1 ) to a5) may be used to produce a microporous ZSM-5 zeolite. It is advantageous if the ZSM-5 zeolite has a well-defined, crystalline structure. It is furthermore an advantage if the ZSM-5 comprises micropores. In the present disclosure, it is advantageous if the ZSM-5 added in step a) has a large crystalline component.
  • the hierarchical molecular sieve produced by the method disclosed herein is a hierarchical aluminosilicate ZSM-5 molecular sieve having a total pore volume of at least 0.85 cm 3 /g comprising mesopores having a diameter of 2-50 nm and micropores having a diameter of 0-2 nm.
  • Figure 1 is a scanning electron micrograph at low magnification of the hierarchical ZSM-5 molecular sieve prepared according to Example 1 of the present invention.
  • Figure 2 is a scanning electron micrograph at high magnification of hierarchical ZSM-5 molecular sieve prepared according to Example 1 of the present invention.
  • Figure 3 is a transmission electron micrograph at low magnification of hierarchical ZSM-5 molecular sieve prepared according to Example 1 of the present invention.
  • Figure 4 is a transmission electron micrograph at high magnification of hierarchical ZSM-5 molecular sieve prepared according to Example 1 of the present invention.
  • Figure 5 is a nitrogen adsorption and desorption isotherm of hierarchical ZSM-5 prepared according to Example 1 of the present invention.
  • Figure 6 is a powder X-ray diffraction pattern of the hierarchical ZSM-5 molecular sieve prepared according to Example 1 of the present invention. Detailed description
  • tetrapropylammonium bromide was added to water, and stirred at a temperature of 30 °C for 18 hours to form a mixture.
  • the mixture was then transferred to a Teflon lined hydrothermal reactor.
  • the mixture was reacted in the reactor for 24 hours at 180 °C.
  • the reaction product was then removed from the reactor, cooled in cold deionized water, filtered and dried to obtain a white powder.
  • the white powder was then calcined at a temperature of 550 °C for 10 hours to obtain a ZSM-5 zeolite powder.
  • the ZSM-5 zeolite powder was then post-treated as follows.
  • the ZSM-5 zeolite powder was mixed with an aqueous solution of tetraprolylammonium bromide having a concentration of 0.1 M and stirred to form a mixture.
  • the mixture was then transferred to a Teflon lined hydrothermal reactor.
  • the mixture was reacted for 2 hours at 180 °C.
  • the reaction product was then removed from the reactor, cooled in cold deionized water, filtered and dried to obtain a second white powder.
  • the second white powder was then calcined at a temperature of 550 °C for 10 hours to obtain a hierarchical ZSM-5 molecular sieve (Sample 1 ).
  • Figure 1 shows a scanning electron microscope (SEM) image at a low magnification of the Sample 1 .
  • SEM scanning electron microscope
  • the SEM images herein was taken using a JSM-7401 F field emission scanning electron microscope using a cold cathode field emission gun, Gentle beam settings and low electron voltage to reveal more detail on the surface of the sample
  • the crystal of product is well crystallized, no obvious amorphous phase can be observed on the surface of ZSM-5 crystal after the re-crystallization post-treatment process.
  • the size of the crystal is in the range of 10-15 ⁇ .
  • Figure 2 shows a SEM image of the surface of the surface of hierarchical ZSM-5 Sample 1 at a higher magnification. Mesopores can be clearly seen on the surface of crystal. A network-like mesoporosity is formed inside the ZSM- 5 crystal, and the mesopores are dispersed homogeneously inside the crystal as it is seen from Figure 2. Transmission electron microscopy
  • TEM images of Sample 1 is shown in Figure 3 and 4.
  • the TEM images was taken using a JEM 2100, manufactured by JEOL Ltd., Japan.
  • the accelerating voltage used was 200 kV.
  • Figure 3 shows an image of Sample 1 at low magnification.
  • Figure 3 shows that the mesopores were not only formed on the surface of ZSM-5 crystal, but also on its inside, and the distribution of these mesopores are homogenous thorough the whole particle of ZSM-5 crystal.
  • Figure 4 shows a TEM image of Sample 1 at a higher magnification than in Figure 3.
  • the framework of the zeolite remains crystalline.
  • the lattice of ZSM-5 can be clearly observed, which proves that the wall of mesopores created during the post-treatment remains crystalline.
  • FIG. 5 shows a N2 adsorption/desorption isotherm for Sample 1 (upper curves) and for conventional ZSM-5 (lower curves).
  • the insert in Figure 5 shows the pore size distribution of the mesopores, as calculated by the Barret-Joyner- Halenda method, for Sample 1 (upper curve) and conventional ZSM-5 (lower curve).
  • the hierarchical ZSM-5 shows a significant amount of mesopores.
  • Sample 1 was further analyzed with powder x-ray diffraction and the diffraction pattern is shown in Figure 6.
  • the powder pattern clearly indicates the MFI framework of Sample 1 as well as a high amount of crystalline component.
  • the crystallinity was further analyzed using the PANalytical HighScores software.
  • the synthesized products were all well crystallized ZSM-5 molecular sieve crystals. This strengthens the observations from the SEM and TEM images with regard to the crystallinity of the product.

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Abstract

La présente invention concerne un tamis moléculaire ZSM-5 d'aluminosilicate hiérarchique présentant un volume total de pores d'au moins 0,85 cm3/g comprenant des mésopores ayant un diamètre de 2 à 50 nm et des micropores ayant un diamètre de 0 à 2 nm. Au moins 50 % des mésopores présentent une structure à pores ouverts.
PCT/EP2018/066407 2017-06-27 2018-06-20 Zéolite zsm-5 hiérarchique dotée d'une structure à pores ouverts WO2019002045A1 (fr)

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WO2023280630A1 (fr) 2021-07-08 2023-01-12 Basf Se Préparation d'amidoximes substituées
CN116062769A (zh) * 2021-10-29 2023-05-05 中国石油化工股份有限公司 氢型zsm-5分子筛及制备方法和二甲苯异构化催化剂及其制备方法

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CN111392744B (zh) * 2020-05-22 2022-09-13 江西师范大学 一种多级孔Fe-MFI分子筛的制备方法
CN114426293A (zh) * 2020-09-27 2022-05-03 中国石油化工股份有限公司 Scm-35分子筛、其制备方法和应用
CN114426293B (zh) * 2020-09-27 2023-09-29 中国石油化工股份有限公司 Scm-35分子筛、其制备方法和应用
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