CN111484035A - Preparation method and application of ZSM-5 molecular sieve precursor - Google Patents

Preparation method and application of ZSM-5 molecular sieve precursor Download PDF

Info

Publication number
CN111484035A
CN111484035A CN202010258814.0A CN202010258814A CN111484035A CN 111484035 A CN111484035 A CN 111484035A CN 202010258814 A CN202010258814 A CN 202010258814A CN 111484035 A CN111484035 A CN 111484035A
Authority
CN
China
Prior art keywords
molecular sieve
zsm
source
organic amine
silicon source
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN202010258814.0A
Other languages
Chinese (zh)
Other versions
CN111484035B (en
Inventor
周升
舒歌平
杨葛灵
章序文
高山松
王洪学
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
China Shenhua Coal to Liquid Chemical Co Ltd
Shanghai Research Institute of China Shenhua Coal to Liquid Chemical Co Ltd
Original Assignee
China Shenhua Coal to Liquid Chemical Co Ltd
Shanghai Research Institute of China Shenhua Coal to Liquid Chemical Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by China Shenhua Coal to Liquid Chemical Co Ltd, Shanghai Research Institute of China Shenhua Coal to Liquid Chemical Co Ltd filed Critical China Shenhua Coal to Liquid Chemical Co Ltd
Priority to CN202010258814.0A priority Critical patent/CN111484035B/en
Publication of CN111484035A publication Critical patent/CN111484035A/en
Application granted granted Critical
Publication of CN111484035B publication Critical patent/CN111484035B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • 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
    • 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

Abstract

The invention relates to the field of molecular sieve preparation, and discloses a preparation method and application of a ZSM-5 molecular sieve precursor. The method comprises the following steps: carrying out crystallization reaction on an organic amine template, water, a silicon source and an optional aluminum source; wherein SiO is used for 2g2The silicon source is counted, and the using amount of the water is 0.05-0.5 g. The method has simple synthesis steps, and the organic amine template can be recycled.

Description

Preparation method and application of ZSM-5 molecular sieve precursor
Technical Field
The invention relates to the field of molecular sieve preparation, in particular to a preparation method and application of a ZSM-5 molecular sieve precursor.
Background
Molecular sieves, also known as zeolites, are porous materials that can be either obtained from nature or synthesized artificially. After the petrochemical energy is applied in a large scale, the zeolite molecular sieve serving as a catalyst and a catalyst carrier is developed greatly, and is widely applied in various fields, in particular to the fields of catalytic cracking, hydrocracking, alkylation reaction, synthesis of low-carbon olefins and low-carbon alcohols in the coal chemical industry and the like. The synthesis and application technology of molecular sieve has gradually become the core technology in the fields of petroleum industry, oil refining technology and coal chemical industry.
The ZSM-5 molecular sieve is one of the most important zeolite molecular sieve catalytic materials at present, and is widely applied to the catalytic fields of petroleum processing, coal chemical industry, fine organic synthesis, separation and the like. With the research and application of the ZSM-5 molecular sieve technology for many years, the catalyst material has higher selectivity and activity, and can be compounded with other molecular sieves, transition metals and catalysts to become a research hotspot, for example, the catalyst material is modified on the surface structure of the original molecular sieve, is compounded with the molecular sieves with other pore structures on the original performance of one molecular sieve, and introduces transition metal elements to enter pore passages of the molecular sieve, attach to the surface of the molecular sieve or replace skeleton atoms of the original molecular sieve on the basis of the original performance of the molecular sieve, and the performance of the molecular sieve is controllably adjusted after introducing inorganic heteroatoms.
Currently, the synthesis technology of ZSM-5 molecular sieves mainly includes a liquid phase synthesis method (solid-liquid system), a solid phase synthesis method (solid-solid system), a vapor phase synthesis method, and the like. The hydrothermal synthesis method/solvothermal synthesis method takes nitrogen-containing organic matters as a template agent, the template agent, a silicon source and an aluminum source need to be dissolved in water, the whole synthesis process is completed in a water phase or a solvent phase, the template agent is expensive and can not be reused, and the template agent is discharged along with mother liquor, so that the raw material consumption is high, the cost is high, and the method can be strictly monitored by environmental protection regulations; the solid-phase synthesis method relates to physical mixing and high-temperature roasting processes of a silicon source, an aluminum source and an alkali source, and a further organic alkali treatment crystallization process after roasting is finished, and has large pre-treatment energy consumption and complex steps; in the steam synthesis process, a silicon source, an aluminum source and sodium hydroxide are stirred to obtain dry gel, and then steam is introduced for crystallization, so that the use of solvent water is avoided in the whole synthesis process, but the discharge of sodium hydroxide after conversion and post-treatment cleaning is irreversible.
Disclosure of Invention
The invention aims to solve the problems of irreversible consumption of a template agent and environmental pollution in the hydrothermal synthesis/solvothermal synthesis process, energy consumption caused by multi-step roasting in the solid-phase synthesis process and salt solution discharge caused by post-treatment washing in the steam synthesis process in the conventional molecular sieve synthesis process, and provides a method for synthesizing a ZSM-5 molecular sieve precursor and a molecular sieve by using an organic amine steam phase.
The inventor of the invention carries out intensive research on the existing ZSM-5 molecular sieve synthesis process and finds that a ZSM-5 molecular sieve precursor can be simply and quickly synthesized by adopting organic amine as a template agent and utilizing a vapor phase synthesis mode, and the composition can also be adjusted to directly synthesize the ZSM-5 molecular sieve. In addition, the inventors have surprisingly found that the surface structure of the synthesized ZSM-5 molecular sieve can be further improved and the surface defects of the molecular sieve can be increased by adding a small amount of water in the vapor phase synthesis process. The synthesis method does not need the dissolving and gelling processes of a silicon source, an aluminum source and the like, has simple synthesis steps, can recycle and reuse the organic amine template, improves the utilization rate of the template, reduces the cost for synthesizing the ZSM-5 molecular sieve, does not discharge waste liquid, and is an environment-friendly synthesis technology.
In order to achieve the above object, the present invention provides a method for preparing a ZSM-5 molecular sieve precursor, the method comprising: carrying out crystallization reaction on an organic amine template, water, a silicon source and an optional aluminum source; wherein SiO is used for 2g2The silicon source is counted, and the using amount of the water is 0.05-0.5 g.
Preferably, the crystallization reaction comprises: the vapor and water vapor of the organic amine templating agent are contacted with a silicon source and optionally an aluminum source.
Preferably, the organic amine template is one or more of ethylamine, ethylenediamine, diethylamine and triethylamine; more preferably, the organic amine templating agent is ethylene diamine.
Preferably, the silicon source is white carbon black and/or fumed silica.
Preferably, the aluminium source is one or more of aluminium sulphate, aluminium isopropoxide, aluminium nitrate and sodium metaaluminate.
Preferably, where the aluminium source is used, the silicon and aluminium sources are sources of silica and aluminium, the sources of silica and aluminium being one or more of the kaolinite group, the smectite group, the mica group, the pyrophyllite, the illite, the vermiculite or the chlorite.
Preferably, SiO is used relative to 2g2The dosage of the silicon source and the organic amine template is 2-50ml, preferably 10-50ml, and more preferably 15-30 ml.
Preferably, SiO is used relative to 2g2The silicon source is counted, and the using amount of the water is 0.1-0.2 g.
Preferably, as opposed to SiO2The silicon source is calculated as Al2O3The dosage of the aluminum source satisfies the silicon-aluminum ratio SiO2：Al2O3＞100。
Preferably, the temperature of the crystallization is 150-300 ℃, preferably 160-240 ℃.
Preferably, the crystallization time is 24-200h, preferably 24-120 h.
Preferably, the method further comprises: and carrying out heat treatment on the product of the crystallization reaction.
More preferably, the temperature of the heat treatment is 500-700 ℃, preferably 550-600 ℃.
More preferably, the heat treatment time is 3 to 50 hours, preferably 3 to 20 hours, more preferably 4 to 6 hours.
More preferably, the temperature rise rate of the heat treatment is 2-10 ℃/min.
Preferably, the method further comprises recovering the organic amine template and reusing the organic amine template for the crystallization reaction.
The second aspect of the present invention provides an application of the preparation method of the present invention in pretreatment of surface modification or surface metal element loading of a molecular sieve.
The ZSM-5 molecular sieve precursor and the ZSM-5 molecular sieve synthesized by the preparation method have smaller crystal grains. In the gas phase crystallization process, the crystal growth is slow, and the formation of polycrystal is avoided; the surface structure of the formed crystal grain is rich, and an excellent precursor is provided for further preparing a ZSM-5 molecular sieve product with a high specific surface; in the preparation of molecular sieve products with other structures, the crystal seeds are used, and the combination of various molecular sieve crystals provides a foundation.
In addition, the preparation method of the present invention can be used for increasing the specific surface area and the surface active sites of the bulk material, and thus is preferably used for surface structure modification and loading pretreatment of the molecular sieve.
Drawings
FIG. 1 shows the raw material gas phase SiO2X-ray diffraction pattern (XRD).
FIG. 2 shows the raw material gas phase SiO2Scanning Electron Micrograph (SEM).
FIG. 3 is an X-ray diffraction pattern (XRD) of a ZSM-5 molecular sieve precursor prepared in example 1.
FIG. 4 is a Scanning Electron Micrograph (SEM) of a ZSM-5 molecular sieve precursor prepared in example 1.
FIG. 5 is a Scanning Electron Micrograph (SEM) of a ZSM-5 molecular sieve precursor prepared in example 1.
FIG. 6 is an X-ray diffraction pattern (XRD) of a ZSM-5 molecular sieve precursor prepared in example 2.
FIG. 7 is a Scanning Electron Micrograph (SEM) of a ZSM-5 molecular sieve precursor prepared in example 2.
FIG. 8 is a Scanning Electron Micrograph (SEM) of a ZSM-5 molecular sieve precursor prepared in example 2.
FIG. 9 is an X-ray diffraction pattern (XRD) of a ZSM-5 molecular sieve precursor prepared in example 3.
FIG. 10 is a Scanning Electron Micrograph (SEM) of a ZSM-5 molecular sieve precursor prepared in example 3.
FIG. 11 is a Scanning Electron Micrograph (SEM) of a ZSM-5 molecular sieve precursor prepared in example 3.
FIG. 12 is an X-ray diffraction pattern (XRD) of a ZSM-5 molecular sieve precursor prepared in example 4.
FIG. 13 is a Scanning Electron Micrograph (SEM) of a ZSM-5 molecular sieve precursor prepared in example 4.
FIG. 14 is a Scanning Electron Micrograph (SEM) of a ZSM-5 molecular sieve precursor prepared in example 4.
FIG. 15 is an X-ray diffraction pattern (XRD) of a ZSM-5 molecular sieve precursor prepared in example 5.
FIG. 16 is a Scanning Electron Micrograph (SEM) of a ZSM-5 molecular sieve precursor prepared in example 5.
FIG. 17 is a Scanning Electron Micrograph (SEM) of a ZSM-5 molecular sieve precursor prepared in example 5.
FIG. 18 is an X-ray diffraction pattern (XRD) of a ZSM-5 molecular sieve precursor prepared in example 6.
FIG. 19 is a Scanning Electron Micrograph (SEM) of a ZSM-5 molecular sieve precursor prepared in example 6.
FIG. 20 is a Scanning Electron Micrograph (SEM) of a ZSM-5 molecular sieve precursor prepared in example 6.
FIG. 21 is an X-ray diffraction pattern (XRD) of a ZSM-5 molecular sieve precursor prepared in example 7.
FIG. 22 is a Scanning Electron Micrograph (SEM) of a ZSM-5 molecular sieve precursor prepared in example 7.
FIG. 23 is a Scanning Electron Micrograph (SEM) of a ZSM-5 molecular sieve precursor prepared in example 7.
FIG. 24 is an X-ray diffraction pattern (XRD) of a ZSM-5 molecular sieve precursor prepared in example 8.
FIG. 25 is a Scanning Electron Micrograph (SEM) of a ZSM-5 molecular sieve precursor prepared in example 8.
FIG. 26 is a Scanning Electron Micrograph (SEM) of a ZSM-5 molecular sieve precursor prepared in example 8.
FIG. 27 is an X-ray diffraction pattern (XRD) of a ZSM-5 molecular sieve precursor of example 9.
FIG. 28 is a Scanning Electron Micrograph (SEM) of a ZSM-5 molecular sieve precursor prepared in example 9.
FIG. 29 is a Scanning Electron Micrograph (SEM) of a ZSM-5 molecular sieve precursor prepared in example 9.
FIG. 30 is an X-ray diffraction pattern (XRD) of a ZSM-5 molecular sieve precursor prepared in example 10.
FIG. 31 is a Scanning Electron Micrograph (SEM) of a ZSM-5 molecular sieve precursor prepared in example 10.
FIG. 32 is a Scanning Electron Micrograph (SEM) of a ZSM-5 molecular sieve precursor prepared in example 10.
FIG. 33 is an X-ray diffraction pattern (XRD) of a ZSM-5 molecular sieve precursor of example 11.
FIG. 34 is a Scanning Electron Micrograph (SEM) of a ZSM-5 molecular sieve precursor prepared in example 11.
FIG. 35 is a Scanning Electron Micrograph (SEM) of a ZSM-5 molecular sieve precursor prepared in example 11.
FIG. 36 is an X-ray diffraction pattern (XRD) of the ZSM-5 molecular sieve prepared in comparative example 1.
FIG. 37 is a Scanning Electron Micrograph (SEM) of the ZSM-5 molecular sieve prepared in comparative example 1.
FIG. 38 is a Scanning Electron Micrograph (SEM) of the ZSM-5 molecular sieve prepared in comparative example 1.
FIG. 39 is an X-ray diffraction pattern (XRD) of the ZSM-5 molecular sieve prepared in comparative example 2.
FIG. 40 is a Scanning Electron Micrograph (SEM) of the ZSM-5 molecular sieve prepared in comparative example 2.
FIG. 41 is a Scanning Electron Micrograph (SEM) of the ZSM-5 molecular sieve prepared in comparative example 2.
FIG. 42 is an X-ray diffraction pattern (XRD) of the product prepared in comparative example 3.
Fig. 43 is a Scanning Electron Micrograph (SEM) of the product prepared in comparative example 3.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
In the method, the prepared ZSM-5 molecular sieve precursor can also be directly used as the ZSM-5 molecular sieve according to the requirement.
The invention providesA method for preparing a ZSM-5 molecular sieve precursor, the method comprising: carrying out crystallization reaction on an organic amine template, water, a silicon source and an optional aluminum source; wherein SiO is used for 2g2The silicon source is counted, and the using amount of the water is 0.05-0.5 g.
In the invention, the water is used as a wetting agent, the dosage of the water needs to be accurately controlled, and the dosage of the water is controlled within the range, so that the crystallization reaction is not influenced, the formation of the surface microstructure of the ZSM-5 molecular sieve is facilitated, and the ZSM-5 molecular sieve with larger specific surface area is prepared. More preferably, SiO is used relative to 2g2The amount of the water used is 0.05 to 0.5g, more preferably 0.1 to 0.2g, based on the silicon source.
In a preferred embodiment of the present invention, the crystallization reaction comprises: the vapor and water vapor of the organoamine templating agent are contacted with a silicon source and optionally an aluminum source. That is, the present invention preferably employs a gas phase crystallization method. Specifically, in the crystallization reaction of the present invention, it is preferable that the organic amine templating agent and water in a liquid state are not contacted with the silicon source and optionally the aluminum source, and the vapor phase crystallization is performed only by contacting the vapor and water vapor of the organic amine templating agent with the silicon source and optionally the aluminum source.
In the present invention, in order to perform the crystallization reaction, it is necessary to use an organic amine template. For the crystallization reaction of the present invention, the organic amine template may be one or more of ethylamine, ethylenediamine, diethylamine and triethylamine. From the standpoint of complexing with water, the organic amine templating agent is most preferably ethylene diamine. Relative to 2g as SiO2The amount of the silicon source and the organic amine template used is preferably 2 to 50ml, more preferably 10 to 50ml, and still more preferably 15 to 30 ml. In addition, the organic amine template is used in a volume ratio of 1/50-1/300, preferably 1/150-1/250, for example 1/200, relative to 0.1g of water.
In the present invention, it is preferable that the silicon source and the aluminum source are added in a solid form. In addition, from the viewpoint of promoting the crystallization reaction, the particle diameters of the silicon source and the aluminum source are preferably in the range of 10 to 200nm, and preferably 20 to 100 nm. When the aluminum source is used, it is preferable to mix the source and the aluminum source and then perform the crystallization reaction.
In the present invention, the types of the silicon source and the aluminum source are not particularly limited, and any silicon source or aluminum source that can be used for preparing a ZSM-5 molecular sieve may be used. The method does not need pretreatment such as solution homogenization, xerogel preparation and the like on the silicon source and the aluminum source, simplifies the preparation process, and does not influence the crystallization reaction.
Specifically, the silicon source may be white carbon black and/or fumed silica, or other silicon source precursors that may be used to prepare the molecular sieve. The aluminium source may be one or more of aluminium sulphate, aluminium isopropoxide, aluminium nitrate and sodium metaaluminate. In the case of using the aluminum source, a silica-aluminum source may be used as the silicon source and the aluminum source, and a specific silica-aluminum source may be one or more of kaolinite group, smectite group, mica group, pyrophyllite, illite, ammonium illite, vermiculite or chlorite. The amounts of the silicon source and the aluminum source may be selected according to the molecular sieve component to be formed, and are preferably SiO relative to 2g2The silicon source is calculated as Al2O3The dosage of the aluminum source satisfies the silicon-aluminum ratio SiO2：Al2O3> 100, preferably SiO2：Al2O3Is more than 150, for example 150-.
The crystallization reaction of the invention can be carried out in any reaction vessel capable of providing crystallization reaction conditions. Preferably, a screen is arranged in the reaction kettle, and the screen is used for placing the silicon source and the optional aluminum source (the silicon source and the aluminum source are solid), so that the silicon source and the optional aluminum source are not contacted with the liquid organic amine template and water at the bottom of the reaction kettle, and the screen holes can be used for contacting organic amine template steam and water vapor with the silicon source and the optional aluminum source, so as to perform crystallization reaction. The pore size of the mesh can be selected according to the particle size of the silicon source and optional aluminum source, and the material can be stainless steel, for example.
The crystallization reaction conditions of the invention are not particularly limited, and in order to improve the surface performance of the prepared ZSM-5 molecular sieve precursor or ZSM-5 molecular sieve, the crystallization temperature is preferably 150-300 ℃, more preferably 160-240 ℃, further preferably 160-220 ℃, and further preferably 160-200 ℃; more preferably, the crystallization time is 24-200h, preferably 24-120 h.
According to the invention, by using the crystallization method, the organic amine template and water can be recovered and reused for the crystallization reaction after the crystallization reaction is finished, and the ZSM-5 molecular sieve can be repeatedly prepared without influencing the use effect.
According to a preferred embodiment of the invention, the method further comprises: and carrying out heat treatment on the product of the crystallization reaction. The temperature of the heat treatment may be 500-700 ℃, preferably 550-600 ℃. The heat treatment time may be 1 to 50 hours, preferably 3 to 20 hours, more preferably 4 to 6 hours. The heating rate of the heat treatment can be 1-15 ℃/min, preferably 2-10 ℃/min. By carrying out the heat treatment under the above conditions, the surface properties of the ZSM-5 molecular sieve precursor or ZSM-5 molecular sieve prepared can be further improved.
The invention also provides the ZSM-5 molecular sieve prepared by the preparation method.
The invention also provides the application of the preparation method in the pretreatment of surface modification or surface metal element loading of the molecular sieve.
Alternatively, the preparation method of the invention can be used for further forming the ZSM-5 molecular sieve on the surface of the molecular sieve, so that the specific surface area of the overall material can be increased.
Optionally, the preparation method of the invention can carry out pretreatment on the molecular sieve before carrying out surface metal element loading on the molecular sieve, thereby increasing the surface active sites of the material and improving the surface loading amount of the metal elements.
Alternatively, the preparation method of the invention can also be used for surface modification of other catalysts and carrier materials thereof which can be corroded by the surfaces of organic amine and water vapor, such as the surface functionalization treatment of traditional zeolite molecular sieves of FAU, MFI, BEA and the like and novel mesoporous materials of SBA-15, MCM-41, KIT-6 and the like.
The present invention will be described in detail below by way of examples. In the following examples of the present invention,irradiating a sample by using an XRD-6000 diffractometer of Shimadzu Japan, analyzing the diffraction pattern of the sample, and obtaining sample information such as a crystal structure and the like, wherein the specific experimental conditions are that Cu K α rays are used
Figure BDA0002438492650000081
And a Ni filter, 30mA tube current, 40kV tube pressure, 5-85 scanning angle and 4 DEG/min scanning speed. The morphology and the micro-area composition of the sample are analyzed by using a FEI Quanta200F type field emission environment scanning electron microscope (FE-SEM). The experimental conditions are as follows: acceleration voltage: 200V-30kV, resolution: less than 1.2nm, magnification: 25-200 k.
Example 1
Directly weighing 20ml of ethylenediamine in a 100ml polytetrafluoroethylene reaction kettle lining, and dripping 0.1g of distilled water into the ethylenediamine to form a solution; fixing a stainless steel screen support and a stainless steel screen on the top of the inner liner of the reaction kettle; weighing gas phase SiO22g of solid (as shown in figure 1-2), slowly spreading on the plane of a stainless steel screen; screwing the inner cover and the outer cover of the reaction kettle, putting the reaction kettle into an oven, and crystallizing for 72 hours at the temperature of 180 ℃; after the reaction is finished, taking out the product on the screen, putting the product into a muffle furnace, heating to 580 ℃ at the heating rate of 5 ℃/min in the air atmosphere, and keeping the temperature for 5 hours; and cooling the product to room temperature to obtain a crystallization product ZSM-5 molecular sieve precursor A1 at 180 ℃ for 72 hours.
As shown in FIGS. 3-5, the ZSM-5 molecular sieve precursor A1 shows a certain diffraction peak structure in an XRD diffraction pattern, and the intensity is weak; a large number of white columnar particles are observed in a low-resolution SEM picture through a field emission scanning electron microscope; and continuously amplifying the selected area, and in a high-resolution SEM picture, the white particles are in a hexagonal prism shape with the size of 4-5 mu m, the columnar surface has rich etching structures, the edge structure is incomplete, and the appearance is shown as a stripping appearance.
Example 2
A ZSM-5 molecular sieve precursor was prepared as in example 1, except that the crystallization temperature was 160 ℃. Finally obtaining a crystallization product ZSM-5 molecular sieve precursor A2 with the temperature of 160 ℃ and the time of 72 hours.
As shown in FIGS. 6-8, the ZSM-5 molecular sieve precursor A2 shows a certain diffraction peak structure in an XRD diffraction pattern, and the intensity is weak; by means of a field emission scanning electron microscope, no products with a regular structure are found in the SEM picture.
Example 3
A ZSM-5 molecular sieve precursor was prepared as in example 1, except that the crystallization temperature was 170 ℃. Finally obtaining a crystallization product ZSM-5 molecular sieve precursor A3 with the temperature of 170 ℃ and the time of 72 hours.
As shown in FIGS. 9-11, the ZSM-5 molecular sieve precursor A3 shows a certain diffraction peak structure in an XRD diffraction pattern, and the intensity is weak; a small amount of white particles are observed in a low-resolution SEM picture through a field emission scanning electron microscope; the selected area is further enlarged and the white particles appear as columnar structures in the high resolution SEM picture.
Example 4
A ZSM-5 molecular sieve precursor was prepared as in example 1, except that the crystallization temperature was 190 ℃. Finally obtaining a crystallization product ZSM-5 molecular sieve precursor A4 with the temperature of 190 ℃ and the time of 72 hours.
As shown in FIGS. 12-14, the ZSM-5 molecular sieve precursor A4 shows a certain diffraction peak structure in an XRD diffraction pattern, and the intensity is weak; a large number of white particles were observed in a low-resolution SEM photograph by a field emission scanning electron microscope; and continuously enlarging the selected area, wherein in the high-resolution SEM picture, the white particles are in a 4-5 mu m columnar structure, the edges of the columnar particles are incomplete, and the surface is not smooth.
Example 5
A ZSM-5 molecular sieve precursor was prepared as in example 1, except that the crystallization temperature was 200 ℃. Finally obtaining a crystallization product ZSM-5 molecular sieve precursor A5 with the temperature of 200 ℃ and the time of 72 hours.
As shown in fig. 15-17, the morphology of the ZSM-5 molecular sieve precursor a5 is similar to that of example 4, and the precursor shows a certain diffraction peak structure and is weaker in intensity in an XRD diffractogram; a large number of white particles were observed in a low-resolution SEM photograph by a field emission scanning electron microscope; and continuously enlarging the selected area, wherein in the high-resolution SEM picture, the white particles are in a 4-5 mu m columnar structure, the edges of the columnar particles are incomplete, and the surface is not smooth.
Example 6
A ZSM-5 molecular sieve precursor was prepared as in example 1, except that the crystallization time was 24 h. Finally obtaining a crystallization product ZSM-5 molecular sieve precursor A6 with the temperature of 180 ℃ and the time of 24 hours.
As shown in FIGS. 18-20, the ZSM-5 molecular sieve precursor A6 shows a certain diffraction peak structure in an XRD diffraction pattern, and the intensity is weak; a large number of white particles were observed in a low-resolution SEM photograph by a field emission scanning electron microscope; and continuously enlarging the selected area, wherein in the high-resolution SEM picture, the white particles are in a 4-5 mu m columnar structure, the edges of the columnar particles are incomplete, and the surface is not smooth.
Example 7
A ZSM-5 molecular sieve precursor was prepared as in example 1, except that the crystallization time was 48 h. Finally obtaining a crystallization product ZSM-5 molecular sieve precursor A7 with the temperature of 180 ℃ and the time of 48 hours.
As shown in FIGS. 21-23, the ZSM-5 molecular sieve precursor A7 shows a certain diffraction peak structure in an XRD diffraction pattern, and the intensity is weak; a large number of white particles were observed in a low-resolution SEM photograph by a field emission scanning electron microscope; and continuously enlarging the selected area, wherein in the high-resolution SEM picture, the white particles are in a 4-5 mu m columnar structure, the edges of the columnar particles are incomplete, and the surface is not smooth.
Example 8
A ZSM-5 molecular sieve precursor was prepared as in example 1, except that the crystallization time was 96 h. Finally obtaining a crystallization product ZSM-5 molecular sieve precursor A8 with the temperature of 180 ℃ and the time of 96 hours.
As shown in FIGS. 24-26, the ZSM-5 molecular sieve precursor A8 shows a certain diffraction peak structure in an XRD diffraction pattern, and the intensity is weak; a large number of white particles were observed in a low-resolution SEM photograph by a field emission scanning electron microscope; and continuously enlarging the selected area, wherein in the high-resolution SEM picture, the white particles are in a 4-5 mu m columnar structure, the edges of the columnar particles are incomplete, and the surface is not smooth.
Example 9
A ZSM-5 molecular sieve precursor was prepared as in example 1, except that the crystallization time was 120 h. Finally obtaining a crystallization product ZSM-5 molecular sieve precursor A9 with the temperature of 180 ℃ and the time of 120 h.
As shown in FIGS. 27-29, the ZSM-5 molecular sieve precursor A9 shows a certain diffraction peak structure in an XRD diffraction pattern, and the intensity is weak; a large number of white particles were observed in a low-resolution SEM photograph by a field emission scanning electron microscope; and continuously enlarging the selected area, wherein in the high-resolution SEM picture, the white particles are in a 4-5 mu m columnar structure, the edges of the columnar particles are incomplete, and the surface is not smooth.
Example 10
A ZSM-5 molecular sieve precursor was prepared as in example 1, except that 10ml of ethylenediamine was used in the crystallization reaction; after the reaction is finished, taking out the product on the screen, putting the product into a muffle furnace, heating to 580 ℃ at a heating rate of 2 ℃/min in the air atmosphere, and keeping the temperature for 4 hours; and cooling the product to room temperature to obtain a ZSM-5 molecular sieve precursor A10.
As shown in FIGS. 30-32, the ZSM-5 molecular sieve precursor A10 shows a certain diffraction peak structure in an XRD diffraction pattern, and has weaker intensity; a large number of white particles were observed in a low-resolution SEM photograph by a field emission scanning electron microscope; and continuously enlarging the selected area, wherein in the high-resolution SEM picture, the white particles are in a 4-5 mu m columnar structure, the edges of the columnar particles are incomplete, the surface is not smooth, and an etched structure exists.
Example 11
A ZSM-5 molecular sieve precursor was prepared as in example 1, except that 50ml of ethylenediamine was used in the crystallization reaction; after the reaction is finished, taking out the product on the screen, putting the product into a muffle furnace, heating to 580 ℃ at a heating rate of 10 ℃/min in the air atmosphere, and keeping the temperature for 6 hours; and cooling the product to room temperature to obtain a ZSM-5 molecular sieve precursor A11.
As shown in FIGS. 33-35, the ZSM-5 molecular sieve precursor A11 shows a certain diffraction peak structure in an XRD diffraction pattern, and the intensity is weak; a large number of white particles were observed in a low-resolution SEM photograph by a field emission scanning electron microscope; and continuously enlarging the selected area, wherein in the high-resolution SEM picture, the white particles are in a 4-5 mu m columnar structure, the edges of the columnar particles are incomplete, the surface is not smooth, and an etched structure exists.
Comparative example 1
A ZSM-5 molecular sieve was prepared as in example 1, except that 1g of distilled water was added (i.e., the amount of water was increased by 10 times). Finally obtaining the ZSM-5 molecular sieve DA 1.
As shown in FIGS. 36-38, the ZSM-5 molecular sieve DA1 shows clear ZSM-5 molecular sieve characteristic diffraction peaks in XRD diffractogram, the peaks are sharp, and the peak intensity is high; a large number of hexagonal prism crystals are observed in a low-resolution SEM picture through a field emission scanning electron microscope; and continuously amplifying the selected area, wherein in a high-resolution SEM picture, the size of the formed prism is 4-5 mu m, the edge is clear, the crystal form is complete, and the surface has a defect structure.
Comparative example 2
A ZSM-5 molecular sieve was prepared as in example 1, except that 10g of distilled water was added (i.e., the amount of water was increased by 100 times). Finally obtaining the ZSM-5 molecular sieve DA 2.
As shown in FIGS. 39-41, the ZSM-5 molecular sieve DA2 shows clear ZSM-5 molecular sieve characteristic diffraction peaks in XRD diffractogram, and has sharp peak shape and high peak intensity; observing a large amount of hexagonal prism crystals with uneven sizes in a low-resolution SEM picture through a field emission scanning electron microscope; and continuously amplifying the selected area, wherein in a high-resolution SEM picture, the size of the formed prism is 2-5 mu m, the edge is clear, and the crystal form is complete.
Comparative example 3
A ZSM-5 molecular sieve precursor was prepared according to the method of example 1, except that distilled water was not added. The product DA3 is finally obtained.
As shown in FIGS. 42-43, the product was designated DA3 and showed an amorphous broad peak in the XRD diffractogram with low peak intensity, comparable to SiO in FIG. 12Diffraction peaks are close; by a field emission scanning electron microscope, no regular crystal is observed to be generated in a low-resolution SEM picture, and the overall product appearance is similar to that of SiO in figure 22The morphology was similar, and it is presumed that SiO, the raw material in comparative example 32No crystallization reaction occurred.
The experimental conditions and the drawings in examples 1 to 11 and comparative examples 1 to 3 were collated and shown in Table 1.
TABLE 1
Examples Ethylenediamine (ml) Water (g) SiO2(g) Crystallization temperature (. degree. C.) Crystallization time (h) Corresponding figures
A1
20 0.1 2 180 72 3-5
A2 20 0.1 2 160 72 6-8
A3 20 0.1 2 170 72 9-11
A4 20 0.1 2 190 72 12-14
A5 20 0.1 2 200 72 15-17
A6 20 0.1 2 180 24 18-20
A7 20 0.1 2 180 48 21-23
A8 20 0.1 2 180 96 24-26
A9 20 0.1 2 180 120 27-29
A10 10 0.1 2 180 72 30-32
A11 50 0.1 2 180 72 33-35
DA1 2 1 2 180 72 36-38
DA2 2 10 2 180 72 39-41
DA3 2 0 2 180 72 42-43
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.

Claims (10)

1. A preparation method of a ZSM-5 molecular sieve precursor is characterized by comprising the following steps: carrying out crystallization reaction on an organic amine template, water, a silicon source and an optional aluminum source;
wherein SiO is used for 2g2The silicon source is counted, and the using amount of the water is 0.05-0.5 g.
2. The method of claim 1, wherein the crystallization reaction comprises: the vapor and water vapor of the organic amine templating agent are contacted with a silicon source and optionally an aluminum source.
3. The preparation method according to claim 1, wherein the organic amine template is one or more of ethylamine, ethylenediamine, diethylamine and triethylamine;
preferably, the organic amine templating agent is ethylene diamine.
4. The preparation method according to claim 1, wherein the silicon source is white carbon black and/or fumed silica;
preferably, the aluminum source is one or more of aluminum sulfate, aluminum isopropoxide, aluminum nitrate and sodium metaaluminate;
preferably, where the aluminium source is used, the silicon and aluminium sources are sources of silica and aluminium, the sources of silica and aluminium being one or more of the kaolinite group, the smectite group, the mica group, the pyrophyllite, the illite, the vermiculite or the chlorite.
5. The production method according to claim 1, wherein SiO is used for 2g2The dosage of the silicon source and the organic amine template is 2-50ml, preferably 10-50ml, and more preferably 15-30 ml.
6. The production method according to claim 1, wherein SiO is used for 2g2The silicon source is counted, and the using amount of the water is 0.1-0.2 g;
preferably, as opposed to SiO2The silicon source is calculated as Al2O3The dosage of the aluminum source satisfies the silicon-aluminum ratio SiO2：Al2O3＞100。
7. The preparation method according to any one of claims 1 to 6, wherein the crystallization temperature is 150-300 ℃, preferably 160-240 ℃;
preferably, the crystallization time is 24-200h, preferably 24-120 h.
8. The production method according to any one of claims 1 to 6, wherein the method further comprises: carrying out heat treatment on the product of the crystallization reaction;
preferably, the temperature of the heat treatment is 500-700 ℃, preferably 550-600 ℃;
preferably, the time of the heat treatment is 1 to 50 hours, preferably 3 to 20 hours, more preferably 4 to 6 hours;
preferably, the heating rate of the heat treatment is 2-10 ℃/min.
9. The method of any one of claims 1-6, wherein the method further comprises recovering the organic amine templating agent and reusing it in the crystallization reaction.
10. Use of the preparation method of any one of claims 1 to 9 in a pretreatment for surface modification or surface metal element loading of a molecular sieve.
CN202010258814.0A 2020-04-03 2020-04-03 Preparation method and application of ZSM-5 molecular sieve precursor Active CN111484035B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202010258814.0A CN111484035B (en) 2020-04-03 2020-04-03 Preparation method and application of ZSM-5 molecular sieve precursor

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202010258814.0A CN111484035B (en) 2020-04-03 2020-04-03 Preparation method and application of ZSM-5 molecular sieve precursor

Publications (2)

Publication Number Publication Date
CN111484035A true CN111484035A (en) 2020-08-04
CN111484035B CN111484035B (en) 2023-08-15

Family

ID=71811657

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202010258814.0A Active CN111484035B (en) 2020-04-03 2020-04-03 Preparation method and application of ZSM-5 molecular sieve precursor

Country Status (1)

Country Link
CN (1) CN111484035B (en)

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4952385A (en) * 1987-03-02 1990-08-28 Georgia Tech Research Corp. Ferrisilicate molecular sieve and use as a catalyst
CN101348262A (en) * 2007-07-18 2009-01-21 中国石油化工股份有限公司 Preparation of zeolite binderless ZSM-5
CN104843740A (en) * 2014-02-13 2015-08-19 中国科学院过程工程研究所 ZSM-5 molecular sieve and preparation method thereof
CN104843739A (en) * 2014-02-13 2015-08-19 中国科学院过程工程研究所 Preparation method of ZSM-5 molecular sieve
CN109012740A (en) * 2018-08-22 2018-12-18 国家能源投资集团有限责任公司 Molecular sieve catalyst, preparation method and application for microwave catalysis oxidation processing organic wastewater
CN110028080A (en) * 2019-05-30 2019-07-19 天津金玺科技发展有限公司 A kind of method of the rapid crystallization synthesis mesoporous ZSM-5 molecular sieve of high-crystallinity

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4952385A (en) * 1987-03-02 1990-08-28 Georgia Tech Research Corp. Ferrisilicate molecular sieve and use as a catalyst
CN101348262A (en) * 2007-07-18 2009-01-21 中国石油化工股份有限公司 Preparation of zeolite binderless ZSM-5
CN104843740A (en) * 2014-02-13 2015-08-19 中国科学院过程工程研究所 ZSM-5 molecular sieve and preparation method thereof
CN104843739A (en) * 2014-02-13 2015-08-19 中国科学院过程工程研究所 Preparation method of ZSM-5 molecular sieve
CN109012740A (en) * 2018-08-22 2018-12-18 国家能源投资集团有限责任公司 Molecular sieve catalyst, preparation method and application for microwave catalysis oxidation processing organic wastewater
CN110028080A (en) * 2019-05-30 2019-07-19 天津金玺科技发展有限公司 A kind of method of the rapid crystallization synthesis mesoporous ZSM-5 molecular sieve of high-crystallinity

Also Published As

Publication number Publication date
CN111484035B (en) 2023-08-15

Similar Documents

Publication Publication Date Title
WO2019010815A1 (en) Cu-sapo-34 molecular sieve synthesis method, and synthesized cu-sapo molecular sieve and application thereof
CN1311757A (en) Process for mfg. molecular sieves
CN108529642A (en) A kind of preparation method of Cu-SSZ-13 molecular sieves
CN110615444A (en) Mordenite molecular sieve, and preparation method and application thereof
CN109201109B (en) Catalyst for preparing olefin from methanol and preparation method thereof
CN114436279B (en) ZSM-22 molecular sieve, preparation method and application thereof, and n-dodecane isomerization reaction
US10287172B2 (en) Preparation method for beta zeolite
CN108439427A (en) A kind of method that fabricated in situ is rich in mesoporous NaY molecular sieve
CN112661166B (en) Hierarchical pore Y-type molecular sieve and preparation method and application thereof
CN114751426A (en) Preparation method and application of B-Al-ZSM-5 molecular sieve
CN111484035A (en) Preparation method and application of ZSM-5 molecular sieve precursor
CN109694086B (en) Preparation method of nano ZSM-5 zeolite molecular sieve aggregate
CN110856819B (en) Surface aluminum-rich molecular sieve, preparation method and application thereof, isomerization reaction catalyst and application thereof
WO2022148416A1 (en) Zsm-23 molecular sieve and preparation method therefor
US9387465B2 (en) Process for producing molecular sieve materials
CN114644345B (en) ZSM-48 molecular sieve, preparation method and hydroisomerization catalyst
CN112661168B (en) Lamellar ZSM-5 molecular sieve and preparation method and application thereof
CN109516471B (en) Synthesis method of ZSM-23 molecular sieve with aluminum-rich surface
CN106809850A (en) A kind of synthetic method of little crystal grain FER molecular sieve
CN111410207B (en) Normal-pressure synthesis method of SAPO-11 molecular sieve
CN108238615B (en) Preparation method of boron-containing NU-87 molecular sieve
CN103274428A (en) Method of synthesizing nano Nu-10 molecular sieve by recycling mother solution
CN115140746B (en) ZSM-5 molecular sieve with cascade hole distribution and preparation method thereof
CN114433223A (en) Bifunctional catalyst containing hierarchical pore SAPO-34 molecular sieve, preparation method and application thereof
CN116515528A (en) Production method of isoparaffin solvent oil

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant