CN111924856B - ZSM-57 molecular sieve and preparation method thereof - Google Patents

ZSM-57 molecular sieve and preparation method thereof Download PDF

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CN111924856B
CN111924856B CN201910393482.4A CN201910393482A CN111924856B CN 111924856 B CN111924856 B CN 111924856B CN 201910393482 A CN201910393482 A CN 201910393482A CN 111924856 B CN111924856 B CN 111924856B
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郭鹏
王磊
田鹏
刘中民
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Abstract

The application discloses a ZSM-57 molecular sieve, wherein the ZSM-57 molecular sieve is a regular sheet with stacked nano crystal grains. The ZSM-57 molecular sieve not only has regular pore channel arrangement, but also has shorter diffusion path, extremely high crystallinity and more abundant contact area, thereby improving the utilization efficiency of the zeolite.

Description

ZSM-57 molecular sieve and preparation method thereof
Technical Field
The invention belongs to the technical field of inorganic materials, and particularly relates to a preparation method of a ZSM-57 molecular sieve single crystal sheet.
Background
ZSM-57 zeolite is a microporous crystalline zeolite having a two-dimensional ten-membered ring and eight-membered ring channel structure. Meanwhile, the ZSM-57 zeolite also has higher thermal stability, hydrothermal stability and adjustable acidity. Therefore, ZSM-57 zeolites have shown high utility in small molecule shape selective catalysis, aromatic alkylation, toluene disproportionation, and long paraffin isomerization.
The ZSM-57 zeolite reported at present has irregular appearance and nonuniform grain size, so that the ten-membered ring channel structure is in disordered stacking arrangement and often has higher mass transfer resistance. The preparation of regular shape and uniform nano zeolite crystal grain is one of the effective approaches to solve the above problems. Compared with conventional disordered ZSM-57 zeolite crystal grains, the ZSM-57 zeolite with regular pore channel arrangement and single crystal disc sheet shape has the advantages of wider mass transfer orientation, high activity, high mechanical strength and the like, so the application of the ZSM-57 zeolite in the chemical industry is increasingly wide.
Usually, more additives, such as amino acids or polyhydroxy high molecular polymers, are required to be introduced to adjust the structure and morphology of the zeolite, which increases the cost and pollutes the environment.
Disclosure of Invention
According to one aspect of the present application, there is provided a ZSM-57 molecular sieve characterized in that,
the ZSM-57 molecular sieve is a regular sheet with stacked nano crystal grains.
Optionally, the ZSM-57 molecular sieve morphology is a pentagonal star-like regular single crystal disc.
Optionally, the particle size of the zsm-57 molecular sieve is 0.2-1 μm.
Optionally, the length-diameter ratio of the ZSM-57 molecular sieve is 1-100; the thickness of the ZSM-57 molecular sieve is 20-300 nm.
Alternatively, the ZSM-57 molecular sieve pore channels are oriented.
Optionally, the ZSM-57 molecular sieve has a silicon-aluminum atomic ratio of 15-40.
Optionally, the XRD pattern of the ZSM-57 molecular sieve contains diffraction peaks at the following positions:
Figure BDA0002057373680000021
Figure BDA0002057373680000022
Figure BDA0002057373680000023
Figure BDA0002057373680000024
Figure BDA0002057373680000025
Figure BDA0002057373680000026
Figure BDA0002057373680000027
Figure BDA0002057373680000028
Figure BDA0002057373680000029
Figure BDA00020573736800000210
optionally, the specific surface area of the ZSM-57 molecular sieve is 400-500 m2/g；
The specific surface area of the micropores of the ZSM-57 molecular sieve is 300-400 m2/g；
The micropore volume of the ZSM-57 molecular sieve is 0.1-0.5 m3/g。
According to one aspect of the application, a preparation method of a directional pore channel arranged ZSM-57 molecular sieve sheet single crystal with low pollution and high efficiency is provided. The preparation method is simple, high in efficiency, convenient to operate, low in pollution and suitable for industrial production.
The method for preparing the ZSM-57 molecular sieve is characterized by comprising the following steps of:
(1) the method comprises the steps of providing a source containing T element, a source containing A element and an alkali source OH-Mixing the raw materials of the organic template agent R and water to obtain an initial mixture;
(2) carrying out hydrothermal crystallization on the initial mixture obtained in the step (1) to obtain the ZSM-57 molecular sieve;
wherein the T element source is selected from at least one of group IV A elements;
the A element source is selected from at least one of group IIIA elements;
the alkali source OH-Is a source of an alkali metal and/or a source of an alkaline earth metal;
the organic template R is selected from at least one of compounds with a chemical structural formula shown in formula I:
Figure BDA0002057373680000031
in the formula I, n is 3-10; r1，R2，R3，R4，R5，R6Independently selected from C1～C6At least one of the hydrocarbon groups of (a); x1 -、X2 -Independently selected from OH-And a halogen element anion.
Alternatively, R1，R2，R3，R4，R5，R6Independently selected from C1～C6At least one of alkyl groups of (a).
Alternatively, R1，R2，R3，R4，R5，R6Independently selected from C1～C6At least one of linear alkyl groups of (a).
Alternatively, R1，R2，R3，R4，R5，R6Independently selected from C1～C6At least one of the alkyl groups having a branch.
Alternatively, R1，R2，R3，R4，R5，R6Independently selected from C1～C5At least one of alkyl groups of (a).
Alternatively, R1，R2，R3，R4，R5，R6Independently selected from C1～C5At least one of linear alkyl groups of (a).
Alternatively, R1，R2，R3，R4，R5，R6Independently selected from C1～C5At least one of the alkyl groups having a branch.
Optionally, the lower limit of the hydrothermal crystallization temperature is selected from 140 ℃, 145 ℃, 150 ℃, 155 ℃. 160 ℃, 165 ℃, 170 ℃, 175 ℃, 180 ℃, 185 ℃, 190 ℃ or 195 ℃; the upper limit is selected from 145 deg.C, 150 deg.C, 155 deg.C. 160 ℃, 165 ℃, 170 ℃, 175 ℃, 180 ℃, 185 ℃, 190 ℃, 195 ℃ or 200 ℃.
Optionally, the lower limit of the hydrothermal crystallization time is selected from 24 hours, 48 hours, 72 hours, 96 hours, 120 hours, 144 hours, 168 hours, 192 hours, 216 hours, 240 hours, 264 hours, 288 hours, 312 hours, 336 hours, 360 hours, 384 hours, 408 hours, 432 hours, or 456 hours; the upper limit is selected from 48 hours, 72 hours, 96 hours, 120 hours, 144 hours, 168 hours, 192 hours, 216 hours, 240 hours, 264 hours, 288 hours, 312 hours, 336 hours, 360 hours, 384 hours, 408 hours, 432 hours, 456 hours, or 480 hours.
Specifically, the method comprises the following steps:
(1) TO is a tetravalent oxide2Of a trivalent oxide A2O3OH as a source of alkali-Mixing an organic template agent R and water to obtain an initial mixture;
(2) placing the mixture obtained in the step (1) at 140-200 ℃ for hydrothermal crystallization for 24-480 hours to obtain the ZSM-57 molecular sieve with the directional pore channel arrangement;
wherein TO in the initial mixture2、A2O3OH as a source of alkali-R and H2The molar ratio of O is: TO2/Y2O3Is in the range of 10 to 999,
OH-/TO2is in the range of 0.01 to 1.0,
H2O/TO2is in the range of 10 to 120,
R/TO20.05 to 1.0;
r is selected from at least one of the compounds with the chemical structural formula shown in the formula I:
Figure BDA0002057373680000041
wherein n is 3-10.
Optionally, a source of T element, a source of A element, a source of an alkali OH in the initial mixture-Organic templating agents R and H2The molar ratio of O is:
TO2/A2O3is in the range of 10 to 999,
OH-/TO2is in the range of 0.01 to 1.0,
H2O/TO2is in the range of 10 to 120,
R/TO20.05 to 1.0;
wherein, T element is sourced from TO2Based on the mole number of the element A, the source of the element A is A2O3Based on the mole number of the alkali source OH-With OH contained therein-In moles of the organic template R, H in moles of the organic template R itself2O is in moles on its own.
Optionally, R/TO in the initial mixture2The lower limit of the molar ratio range of (a) is selected from 0.06: 1. 0.07: 1. 0.08: 1. 0.09: 1. 0.1: 1 or 0.12: 1, upper limit selected from 0.15: 1. 0.2: 1. 0.3: 1. 0.4: 1. 0.5: 1. 0.6: 1. 0.7: 1. 0.8: 1. 0.9: 1 or 1.0: 1.
optionally, R/TO in the initial mixture2The molar ratio of (A) to (B) is: 0.08-0.8: 1.
optionally, OH in the initial mixture-/TO2The lower limit of the molar ratio range of (a) is selected from 0.01: 1. 0.02: 0.03, 0.04: 1. 0.045: 1 or 0.05: 1, upper limit selected from 0.5: 1. 0.6: 1. 0.65: 1. 0.7: 1 or 0.8: 1.
optionally, TO in the initial mixture2/A2O3The lower limit of the molar ratio range of (a) is selected from 10, 20, 25, 30, 40, 50, 60, 70, 80, 90, 100, 120, 150, 180, 200, 250, 300, 400, 500, 600, 700, 800 or 900; the upper limit is selected from 20, 25, 30, 40, 50, 60, 70, 80, 90, 100, 120, 150, 180, 200, 250, 300, 400, 500, 600, 700, 800, 900, or 999.
Alternatively, H in the initial mixture2O/TO2The lower limit of the molar ratio range of (a) is selected from 10, 20, 30, 40, 50, 60, 70, 80, 90, 100 or 110; the upper limit is selected from 20, 30, 40, 50, 60, 70, 80, 90, 100, 110, or 120.
Optionally, the T element source is selected from at least one of a silicon source, a germanium source and a tin source;
the A element source is at least one selected from aluminum source, boron source and gallium source;
the alkali source OH-At least one selected from alkali metal hydroxides and alkaline earth metal hydroxides.
Optionally, the silicon source is selected from at least one of tetraethoxysilane, silica gel, silicic acid, white carbon black, silica sol, water glass and diatomite;
the germanium source is germanium oxide;
the tin source is at least one of tin oxide and tin chloride;
the aluminum source is selected from at least one of aluminum isopropoxide, sodium aluminate, aluminum foil, aluminum sulfate, aluminum chloride, aluminum nitrate, aluminum hydroxide and pseudo-boehmite;
the boron source is at least one of boric acid, sodium borate and boron oxide;
the gallium source is selected from at least one of gallium nitrate and gallium trichloride;
the alkali source OH-At least one selected from sodium hydroxide, potassium hydroxide and cesium hydroxide.
Alternatively, in formula I, n ═ 3-7; r1，R2，R3，R4，R5，R6Independently selected from C1～C3At least one of alkyl groups of (a).
Optionally, the organic template agent R is 1, 5-hexaethyl pentanediammonium bromide.
Optionally, step (1) comprises: to A element source and alkali source OH-And adding a T element source into the mixture of the organic template agent R and the water, and mixing to obtain an initial mixture.
Optionally, step (1) comprises: to A element source and alkali source OH-And adding a T element source into the mixture of the organic template agent R and the water, and mixing to obtain an initial mixture.
Optionally, step (2) comprises: and (2) carrying out hydrothermal crystallization on the initial mixture obtained in the step (1) at the temperature of 140-200 ℃ for 24-480 hours, and separating, washing and drying the obtained product to obtain the ZSM-57 molecular sieve.
Based on the principle of zeolite preparation, framework four connecting atoms in zeolite can be replaced by other metals (germanium source, tin source, aluminum source and gallium source) or non-metal atoms (silicon source and boron source) and the framework structure of zeolite crystal is kept the same.
All conditions in this application that relate to a numerical range can be independently selected from any point within the numerical range.
In this application "C1～C6"and the like refer to the number of carbon atoms which a group contains.
In the present application, an "alkyl group" is a group formed by losing any one hydrogen atom on the molecule of an alkane compound.
In this application, a "hydrocarbyl group" is a group formed by the loss of one hydrogen atom on a carbon atom in a hydrocarbon molecule. The hydrocarbon is a carbohydrate, for example, the alkane, alkene, alkyne are all hydrocarbons.
The beneficial effects that this application can produce include:
1) according to the method provided by the application, the prepared ZSM-57 has a regular appearance and a directionally distributed zeolite pore channel structure;
2) according to the method provided by the application, the prepared ZSM-57 has extremely high crystallinity and relatively abundant contact area, so that the sieving utilization efficiency of the zeolite is improved;
3) the ZSM-57 prepared by the method has extremely high length-diameter ratio and shorter diffusion path, thereby improving the film forming efficiency of the zeolite sheets.
Drawings
Figure 1 is an XRD spectrum of the sample of example 1.
FIG. 2 is a SEM photograph of a sample of example 1.
FIG. 3 is a transmission electron micrograph of a selected area of the sample of example 1.
FIG. 4 is a scanning electron micrograph of a sample of comparative example 1.
Detailed Description
The invention is illustrated by the following examples, which are not intended to limit the scope of the invention. The starting materials, templating agents and solvents in the examples of the present invention were all purchased commercially, unless otherwise specified.
The molar ratio of Si to Al in the product is Si/Al atomic ratio in the examples.
The analysis method in the examples of the present invention is as follows:
x-ray powder diffraction phase analysis (XRD) was performed using X' Pert PRO X-ray diffractometer [ Cu target, ka radiation source (λ ═ 0.15418nm), voltage 40kV, current 40mA ], of pananace (PANalytical), netherlands.
SEM topography analysis was performed using a Hitachi (SU8020) scanning electron microscope.
Selective electron diffraction analysis was performed using a JEOL (2100) type transmission electron microscope.
Example 1
The initial gel was formulated in the following molar ratios: SiO 22/Al2O3＝100，OH-/SiO2＝0.4，R/SiO2＝0.2，H2O/SiO2Sodium aluminate, potassium hydroxide and 1, 5-hexaethyl pentanediammonium bromide are respectively dissolved in deionized water, and then white carbon black is added under the condition of continuous stirring. Then the mixture is put into a 100ml crystallization kettle to react for 168 hours at 160 ℃.
And (3) placing the cooled reaction liquid into a water bath, standing for 5 hours to generate obvious layering, wherein beige solid at the lower layer is ZSM-57 zeolite, separating, washing, drying and roasting (the roasting temperature is 550 ℃ and the roasting time is 8 hours) to obtain a sample, wherein the number of the sample is ZSM-57-1, and the yield of the ZSM-57-1 is 91% based on the weight of the added silicon dioxide.
XRD analysis (XRD spectrogram is shown in figure 1) shows that the sample is ZSM-57 zeolite, and the molar ratio of silicon to aluminum is 21; SEM characterization (the SEM image is shown in FIG. 2) confirmed that the sample morphology is pentagonal disk-shaped with nano-small crystal grain stacking, the particle size is 2 μm, and the thickness is about 20 nm.
Examples 2 to 5
The specific compounding ratio and crystallization conditions are shown in table 1, and the specific compounding process is the same as that of example 1.
XRD analysis is carried out on the prepared sample, the data result is similar to that of the sample shown in the table 2, namely, the position and the shape of the peak are the same, and the relative kurtosis of the peak fluctuates within the range of +/-10% according to the change of the preparation conditions, which shows that the prepared product has the characteristics of a ZSM-57 structure.
TABLE 1 ingredient and crystallization conditions for molecular sieve preparation
Figure BDA0002057373680000071
Figure BDA0002057373680000081
Table 2 XRD results for the sample of example 1
Figure BDA0002057373680000082
Comparative example 1
Mixing sodium hydroxide, 1, 5-hexaethyl pentanediammonium bromide, sodium aluminate, water and white carbon black, and preparing according to the following molar ratio: SiO 22/Al2O3＝60，OH-/SiO2＝0.6，R/SiO2＝0.15，H2O/SiO 240. The mixture was then stirred in a 50 ℃ water bath to a homogeneous gel and aged for 12 hours while stirring. And transferring the gel into a hydrothermal crystallization kettle, heating to 160 ℃, carrying out hydrothermal crystallization for 168 hours, then naturally cooling, filtering and drying to obtain zeolite raw powder, and marking the zeolite raw powder as a sample ZSM-57-D1. XRD tests prove that the ZSM-57-D1 sample is ZSM-57 zeolite, small-grain aggregates are observed in a low-power SEM, and a ZSM-57 pentagonal disc with a regular surface is not formed, as shown in figure 4. The yield of ZSM-57 was 86% based on the weight of silica charged. Comparative example description: the aging of the gel affects the morphology of the ZSM-57 molecular sieve, and the obtained ZSM-57 sample does not form a regular single crystal disc and only presents a small particle aggregation state with the same crystal orientation.
Experimental example 6
The sample obtained in example 1 is calcined at 550 ℃ for 8 hours by introducing air to remove the template agent, and then the specific surface area and the pore volume of the sample are tested, wherein the sample has high BET specific surface area of 456m2The specific surface area and the volume of each micropore calculated according to the t-plot method are 316m2G and 0.16cm3/g。
The samples prepared in examples 2 to 5 have similar BET specific surface areas to those tested for the sample of example 1.
Experimental example 7
And (3) introducing air into the sample obtained in the example 1 at 550 ℃ to roast for 8 hours to remove the template agent, and then testing the crystal plane orientation of the sample by adopting a transmission electron microscope. From the selected area electron diffraction pattern (FIG. 3), it can be found that the zeolite sheet orientation of ZSM-57 is [100], i.e. the ten-member ring channel orientation of the zeolite.
The samples prepared in examples 2-5 were similar to the transmission electron mirror image obtained from the sample testing of example 1.
Although the present application has been described with reference to a few embodiments, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the application as defined by the appended claims.

Claims (8)

1. The ZSM-57 molecular sieve is characterized in that the ZSM-57 molecular sieve is a pentagram-shaped regular sheet with stacked nano crystal grains, the direction of the sheet is [100], and the length-diameter ratio of the ZSM-57 molecular sieve is 1-100; the thickness of the ZSM-57 molecular sieve is 20-300 nm.
2. The ZSM-57 molecular sieve of claim 1, wherein the ZSM-57 molecular sieve has a particle size of 0.2 to 1 μm.
3. The ZSM-57 molecular sieve of claim 1, wherein the ZSM-57 molecular sieve has a specific surface area of 400-500 m2/g；
The specific surface area of the micropores of the ZSM-57 molecular sieve is 300-400 m2/g；
The micropore volume of the ZSM-57 molecular sieve is 0.1-0.5 m3/g。
4. A method of preparing the ZSM-57 molecular sieve of any of claims 1 to 3, comprising the steps of:
(1) will contain T elementSource, source of element A, source of base OH-Mixing the raw materials of the organic template agent R and water to obtain an initial mixture;
(2) carrying out hydrothermal crystallization on the initial mixture obtained in the step (1) to obtain the ZSM-57 molecular sieve;
wherein a step of gel aging is not included between the steps (1) and (2);
wherein the T element source is selected from at least one of group IV A elements;
the A element source is selected from at least one of group IIIA elements;
the alkali source OH-Is a source of an alkali metal and/or a source of an alkaline earth metal;
the organic template agent R is 1, 5-hexaethyl pentanediammonium bromide;
a source of T element, a source of A element, and a source of alkalinity OH in the initial mixture-Organic templating agents R and H2The molar ratio of O is:
TO2/A2O3＝10～999，
OH-/TO2＝0.01～1.0，
H2O/TO2＝10～120，
R/TO2＝0.05～1.0；
wherein the mole number of the T element source is TO2In moles of the source of element A as A2O3Based on the mole number of the alkali source OH-In terms of the number of moles of OH it contains-In moles of organic template R, H2The number of moles of O is in terms of its own number of moles.
5. The method of claim 4, wherein the T element source is selected from at least one of a silicon source, a germanium source, and a tin source;
the A element source is at least one selected from aluminum source, boron source and gallium source;
the alkali source OH-At least one selected from alkali metal hydroxides and alkaline earth metal hydroxides.
6. The method according to claim 5, wherein the silicon source is at least one selected from the group consisting of tetraethoxysilane, silica gel, silicic acid, silica white, silica sol, water glass, and diatomaceous earth;
the germanium source is germanium oxide;
the tin source is at least one of tin oxide and tin chloride;
the aluminum source is selected from at least one of aluminum isopropoxide, sodium aluminate, aluminum foil, aluminum sulfate, aluminum chloride, aluminum nitrate, aluminum hydroxide and pseudo-boehmite;
the boron source is at least one of boric acid, sodium borate and boron oxide;
the gallium source is selected from at least one of gallium nitrate and gallium trichloride;
the alkali source OH-At least one selected from sodium hydroxide, potassium hydroxide and cesium hydroxide.
7. The method of claim 4, wherein step (1) comprises: to A element source and alkali source OH-And adding a T element source into the mixture of the organic template agent R and the water, and mixing to obtain an initial mixture.
8. The method according to claim 4, wherein the conditions of the hydrothermal crystallization are: hydrothermal crystallization is carried out for 24-480 hours at 140-200 ℃.
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CN101384361A (en) * 2006-02-14 2009-03-11 埃克森美孚化学专利公司 Process for manufacturing molecular sieve of mfs framework type and its use
SG178331A1 (en) * 2009-08-28 2012-03-29 Exxonmobil Chem Patents Inc Method of making and use of molecular sieve of mfs framework type with controllable average size
CA2913033A1 (en) * 2013-06-10 2014-12-18 Exxonmobil Chemical Patents Inc. A process for making molecular sieves
CN105692643B (en) * 2016-01-21 2018-02-27 嘉兴学院 The method for synthesizing other structures zeolite crystal using the template effect of the zeolite seed crystals of ZSM 57

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