CN112794338B - ZSM-5 molecular sieve and preparation method and application thereof - Google Patents
ZSM-5 molecular sieve and preparation method and application thereof Download PDFInfo
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- 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
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- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
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- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
- C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- C07C2529/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
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Abstract
The invention relates to the field of molecular sieve synthesis, and discloses a ZSM-5 molecular sieve, a preparation method and an application thereof, wherein the method comprises the following steps: (1) Mixing a silicon source, an alkali source, a template agent and water to obtain a gel precursor; (2) Adding an aqueous solution of an aluminum source into the gel precursor to obtain gel; (3) And crystallizing, drying and roasting the gel in sequence to obtain the ZSM-5 molecular sieve. The ZSM-5 molecular sieve prepared by the invention has the advantages of high crystallinity and high silicon source conversion rate, improves the utilization rate of raw materials, reduces the production cost, has higher silicon-aluminum ratio, specific surface area and pore volume, and has wider application range in the field of shape-selective catalysis. The ZSM-5 molecular sieve prepared by the invention is applied to the preparation of propylene from methanol, and has higher methanol conversion rate.
Description
Technical Field
The invention relates to the field of molecular sieve synthesis, in particular to a ZSM-5 molecular sieve and a preparation method and application thereof.
Background
Since the last 70 centuries ZSM-5 zeolite was invented by Mobil corporation, ZSM-5 molecular sieves were widely used in various fields. The ZSM-5 molecular sieve is a typical microporous molecular sieve, and a framework of the ZSM-5 molecular sieve contains two mutually crossed pore canal systems: the elliptical ten-membered ring straight channels and the circular zigzag-bent channels have pore diameters of about 0.51X 0.55nm and 0.53X 0.56nm, respectively. The unique three-dimensional cross pore channel structure of the ZSM-5 molecular sieve not only provides a space restriction effect for shape-selective catalysis, but also provides rich access channels for reactants and products. Therefore, the ZSM-5 molecular sieve can be used as a solid acid catalyst, a catalyst carrier, an adsorbent and an ion exchanger, and can also be applied to important industrial production of aromatic alkylation, catalytic cracking, light hydrocarbon aromatization, methanol-to-gasoline and the like.
There are many reports about the synthesis of ZSM-5 molecular sieve, and the hydrothermal method is mainly used in the laboratory synthesis and industrial production process. The template agents usually adopted for synthesizing the ZSM-5 molecular sieve by the hydrothermal method comprise organic template agents such as alcohol, amine, alcohol amine, quaternary ammonium salt, quaternary ammonium base and the like, wherein the organic template agents of the quaternary ammonium and the quaternary ammonium salt have high synthesis speed and controllable conditions, and the obtained ZSM-5 molecular sieve has good physical properties, thereby forming a hot spot of domestic and foreign research.
CN715186A discloses a preparation method of small crystal ZSM-5 zeolite, which comprises: mixing SiO 2 /Al 2 O 3 Mixing silica-alumina gel particles with the molar ratio of 20-600 and the granularity of 20-300 meshes with an aqueous solution of an organic template agent, then carrying out hydrothermal crystallization, filtering, drying and roasting to finally obtain the product. The method can prepare ZSM-5 zeolite with the mole ratio of silicon to aluminum of 15-200 and the primary grain diameter of 100-500 nm. The feeding mol ratio is SiO 2 /Al 2 O 3 ＝20-600，Na 2 O/SiO 2 ＝0.25-1，R/SiO 2 =0.01-0.2, water/SiO 2 And (5) 2-15, wherein R is a quaternary ammonium salt template agent.
CN1730391 discloses a microwave synthesis method of nano-sized silicate-based porous material, which comprises the following steps: firstly, adding tetrapropylammonium hydroxide and a silicon source into water, uniformly mixing, and then adding an aluminum source into the mixture under stirring to prepare an aluminosilicate solution; the reaction solution is directly synthesized by microwave for 3-180 minutes or crystallized for 1-3 days at 150-190 ℃ after being heated for 3-30 minutes by microwave; after crystallization, centrifugal separation or filtration, washing and drying are carried out to obtain the nano-scale ZSM-5 zeolite, the grain size of which can be adjusted within the range of 50-300nm, and the feeding molar ratio is (0-10) Al 2 O 3 /(20-30)SiO 2 /(100-1500) Water/(4-45) TPAOH, where TPAOH is tetrapropylammonium hydroxide.
CN104475150 discloses a one-step synthesis method of a B-EU-1/ZSM-5 composite molecular sieve, which comprises the following steps: according to Na 2 O/SiO 2 /Al 2 O 3 /B 2 O 3 The preparation method comprises the following steps of (1) adding sodium hydroxide, a silicon source, an aluminum source and a boron-containing compound into water together with a template agent according to a molar ratio of 1.5/(0.1-7)/(0.00-0.2)/(0.001-0.3)/(0.01-2.25)/(1-10), uniformly stirring to obtain a mixed gel, crystallizing at a constant temperature of 130-200 ℃, roasting at 350-650 ℃ to remove the template agent, performing ion exchange and washing with an acid solution, and keeping at 350-650 ℃ for 4 hours to obtain the B-EU-1/ZSM-5 hydrogen type composite molecular sieve, wherein the template agent is prepared by mixing tetrapropylammonium bromide and hexapotassium diammonium bromide. The method can quickly, simply and conveniently synthesize the composite molecular sieve which simultaneously contains an EUO structure and an MFI structure and is doped with the nonmetal element B.
CN107892308 discloses a ZSM-5 molecular sieve and a method for preparing the same, the method comprising: providing a silicon source, an aluminum source, a quaternary ammonium template, a phosphorus template, ethanol and water, and mixing to obtain mixed gel; siO in the mixed gel 2 With Al 2 O 3 The mol ratio of the quaternary ammonium template to the phosphate template is (20-200)/1, and the quaternary ammonium template, the phosphate template, the ethanol, the water and the SiO 2 The molar ratio of (0.001-0.5)/(0.001-0.5)/(1-50)/(0.2-50)/1; crystallizing the mixed gel at 100-200 deg.C for 6-72h to obtain reaction product,and obtaining the needed ZSM-5 molecular sieve from the reaction product. The preparation method of the ZSM-5 molecular sieve can prepare the ZSM-5 molecular sieve with the hierarchical pore structure simultaneously containing micropores and mesopores, and the ZSM-5 molecular sieve has the advantages of high stability and good catalytic performance.
However, in the above-disclosed method for preparing the ZSM-5 molecular sieve, the conversion rate of the raw material and the crystallinity are still further improved.
Disclosure of Invention
The invention aims to solve the problems of low conversion rate of raw materials and low crystallinity of a ZSM-5 molecular sieve in the prior art, and provides the ZSM-5 molecular sieve and the preparation method and the application thereof.
In order to achieve the above object, the present invention provides, in a first aspect, a method for preparing a ZSM-5 molecular sieve, the method comprising the steps of:
(1) Mixing a silicon source, an alkali source, a template agent and water to obtain a gel precursor;
(2) Adding an aqueous solution of an aluminum source into the gel precursor to obtain gel;
(3) And crystallizing, drying and roasting the gel in sequence to obtain the ZSM-5 molecular sieve.
In a second aspect, the present invention provides a ZSM-5 molecular sieve prepared by the above-described process.
The third aspect of the invention provides an application of the ZSM-5 molecular sieve in preparation of propylene from methanol.
Through the technical scheme, the invention has the following beneficial effects:
(1) According to the preparation method, a silicon source, an alkali source and a template agent are prepared into a gel precursor, an aluminum source is added into the gel precursor to obtain a gel, and the ZSM-5 molecular sieve is prepared through crystallization, drying and roasting.
(2) The ZSM-5 molecular sieve prepared by the invention has the advantages of high silicon source conversion rate and high crystallinity, improves the utilization rate of raw materials and reduces the production cost.
(3) The ZSM-5 molecular sieve prepared by the invention has higher specific surface area and pore volume and higher silica-alumina ratio, so that the ZSM-5 molecular sieve has a wider application range in the field of shape-selective catalysis.
(4) The ZSM-5 molecular sieve prepared by the invention is applied to the preparation of propylene from methanol, and has higher methanol conversion rate.
Drawings
FIG. 1 is an XRD spectrum of a ZSM-5 molecular sieve prepared in example 1 of the present invention;
FIG. 2 is an SEM electron micrograph of a ZSM-5 molecular sieve prepared in example 1 of the invention;
FIG. 3 is an SEM electron micrograph of a ZSM-5 molecular sieve prepared in example 8 of the invention.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and these ranges or values should be understood to encompass values close to these 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 a first aspect, the present invention provides a method for preparing a ZSM-5 molecular sieve, the method comprising the steps of:
(1) Mixing a silicon source, an alkali source, a template agent and water to obtain a gel precursor;
(2) Adding an aqueous solution of an aluminum source into the gel precursor to obtain gel;
(3) And crystallizing, drying and roasting the gel in sequence to obtain the ZSM-5 molecular sieve.
According to the present invention, preferably, the molar ratio of the aluminum source, the silicon source, the template, the alkali source and the water is 1: (100-300): (40-90): (10-35): (1200-4800) wherein the aluminum source is Al 2 O 3 The silicon source is SiO 2 Counting; further preferably, the aluminum source, the silicon source, the template, the alkali source and the water are added in amounts such that the obtained aluminum source, the silicon source, the template, the alkali source and the water are addedIn the gel, the ratio of aluminum source: silicon source: template agent: alkali source: the molar ratio of water is 1: (100-300): (40-90): (10-35): (1200-2000).
According to the present invention, the silicon source may be a substance capable of providing silicon element, which is generally known in the art, preferably, the silicon source is an organic silicon source and/or an inorganic silicon source, preferably, at least one of tetraethoxysilane, water glass (sodium silicate), silica sol and silica gel, and more preferably, at least one of tetraethoxysilane, silica sol and silica gel; further preferably, the silica gel is chromatographic silica gel, and the chromatographic silica gel can be 100-200 mesh granular chromatographic silica gel, 200-300 mesh granular chromatographic silica gel and 300-400 mesh granular chromatographic silica gel.
Note that, silica sol (mSiO) 2 ·nH 2 SiO in O) 2 The content of (B) is 25-40wt%; siO in chromatography silica gel 2 The content of (B) is more than or equal to 98wt%.
According to the present invention, the aluminum source may be a substance capable of providing aluminum element, which is generally known in the art, and preferably, the aluminum source is pseudoboehmite and/or an aluminum salt, preferably at least one of aluminum sulfate, aluminum nitrate and sodium aluminate, and more preferably sodium aluminate.
It is noted that Al in pseudo-boehmite 2 O 3 The content of (B) is more than or equal to 70wt%.
According to the present invention, preferably, the alkali source is an inorganic alkali, preferably at least one of sodium hydroxide, potassium hydroxide and ammonia.
According to the present invention, in order to further improve the silicon source conversion rate, crystallinity, silica-alumina ratio and specific surface area and pore volume of the ZSM-5 molecular sieve, the present invention uses two templates, preferably at least two templates selected from quaternary ammonium salts and quaternary ammonium bases, in preparing the gel precursor.
According to the present invention, the type of the quaternary ammonium salt is not particularly limited, and preferably, the quaternary ammonium salt is selected from tetraalkylammonium bromides.
According to the present invention, the kind of the quaternary ammonium hydroxide is not particularly limited, and preferably, the quaternary ammonium hydroxide is selected from tetraalkylammonium hydroxides.
In the present invention, the alkyl group in the tetraalkylammonium bromide and the tetraalkylammonium hydroxide may be a C1-C10 alkyl group, preferably a C1-C3 alkyl group.
According to the invention, in order to reduce the industrial application cost of the ZSM-5 molecular sieve, the invention selects the cheap template agent, preferably, the template agent is selected from at least two of tetramethyl ammonium hydroxide, tetramethyl ammonium bromide, tetrapropyl ammonium hydroxide, tetrapropyl ammonium bromide, tetraethyl ammonium hydroxide and tetraethyl ammonium bromide.
According to the present invention, in order to further improve the silicon source conversion rate, crystallinity, silicon-aluminum ratio, and specific surface area and pore volume of the ZSM-5 molecular sieve, in a particularly preferred case, the template is a combination of a quaternary ammonium salt and a quaternary ammonium base selected from at least one of tetramethylammonium hydroxide, tetrapropylammonium hydroxide, and tetraethylammonium hydroxide; the quaternary ammonium salt is at least one of tetramethylammonium bromide, tetrapropylammonium bromide and tetraethylammonium bromide; further preferably, the molar ratio of the quaternary ammonium hydroxide to the quaternary ammonium salt is 1: (0.2-1.1), more preferably 1: (0.8-1.1).
According to the present invention, the mixing conditions in step (1) are not particularly limited, and the silicon source, the alkali source and the template may be sequentially added to water and mixed, or the silicon source, the alkali source and the template may be mixed and then added to water, or the silicon source, the alkali source and the template may be separately added to water and then mixed. In order to better disperse the silicon source, alkali source and templating agent in water, the mixing conditions include: sequentially adding a silicon source, an alkali source and a template agent into water at the temperature of 20-100 ℃, and stirring and mixing.
According to the present invention, the method for preparing the gel precursor is not particularly limited, and the gel precursor is dispersed sufficiently to participate in the reaction. Preferably, the step (1) further comprises mixing the silicon source, the alkali source, the template and water, and then performing a first stirring, wherein the conditions of the first stirring include: the temperature is 20-100 deg.C (for example, 20 deg.C, 25 deg.C, 30 deg.C, 35 deg.C, 40 deg.C, 45 deg.C, 50 deg.C, 60 deg.C, 70 deg.C, 80 deg.C, 90 deg.C, 100 deg.C, and any two of the above ranges), preferably 25-50 deg.C; time of dayIs 0.1-24h (for example, can be 0.1h, 0.5h, 1h, 2h, 3h, 4h, 5h, 6h, 7h, 8h, 9h, 10h, 12h, 14h, 16h, 18h, 20h, 22h, 24h, and the range formed by any two of the above numerical values), and is preferably 1-12h; the stirring rate is 1-100r/min, preferably 20-50r/min, relative to 0.01mol of silicon source, which is SiO 2 And (6) counting.
According to the present invention, in order to increase the conversion rate of the silicon source, preferably, the step (2) further includes performing a second stirring after adding the aqueous solution of the aluminum source to the gel precursor, where the conditions of the second stirring include: the temperature is 20-100 deg.C (for example, 20 deg.C, 25 deg.C, 30 deg.C, 35 deg.C, 40 deg.C, 45 deg.C, 50 deg.C, 60 deg.C, 70 deg.C, 80 deg.C, 90 deg.C, 100 deg.C, and any two of the above ranges), preferably 20-40 deg.C; the time is 0.1-24h (for example, the time can be 0.1h, 0.5h, 1h, 2h, 3h, 4h, 5h, 6h, 7h, 8h, 9h, 10h, 12h, 14h, 16h, 18h, 20h, 22h, 24h, and the range formed by any two of the above numerical values), and is preferably 4-12h; the stirring rate is 1-100r/min, preferably 20-50r/min, relative to 0.01mol of silicon source, which is SiO 2 And (6) counting.
According to the present invention, in order to make the aluminum source dissolve in water better, the aqueous solution of the aluminum source may be preferably obtained by dissolving the aluminum source in water and then stirring at 20 to 100 ℃ for 0.1 to 12 hours.
According to the present invention, preferably, in the step (2), the molar ratio of water to the aluminum source in the aqueous solution of the aluminum source is 130 to 360, and the aluminum source is Al 2 O 3 And (6) counting.
According to the present invention, the rate of addition of the aqueous solution of the aluminum source to the gel precursor is not particularly limited, but the aluminum source is slowly added dropwise to the gel precursor in order for the aluminum source to sufficiently participate in the reaction. Preferably, in step (2), the aqueous solution of the aluminum source is added at a rate of 0.1 to 5mL/min, preferably 0.5 to 2mL/min, relative to 0.1mol of the silicon source.
According to the present invention, in order to create an environment for promoting the growth of ZSM-5 molecular sieve nuclei, it is preferable that the crystallization includes a first stage crystallization and a second stage crystallization.
According to the invention, an environment better suitable for the growth of ZSM-5 molecular sieve crystal nucleus is created, and the growth rate of crystal grains is controlled, so that the ZSM-5 molecular sieve with uniform particle size and smooth surface is obtained; preferably, the temperature of the second stage crystallization is 10 to 100 ℃ higher than the temperature of the first stage crystallization.
According to the present invention, the conditions for the first stage crystallization may be conventional crystallization conditions in the art, and preferably, the conditions for the first stage crystallization include: the temperature of the first stage crystallization is 100-150 ℃ (for example, 100 ℃, 110 ℃, 120 ℃,130 ℃, 140 ℃, 150 ℃, and any two of the above ranges), preferably 120-140 ℃, and the time of the first stage crystallization is 6-48h (for example, 6h, 7h, 8h, 9h, 10h, 12h, 14h, 16h, 18h, 20h, 22h, 24h, 30h, 34h, 36h, 38h, 40h, 42h, 48h, and any two of the above ranges), preferably 30-40h.
According to the present invention, the conditions for the crystallization of the second stage may be conventional crystallization conditions in the art, and preferably, the conditions for the crystallization of the second stage include: the temperature of the second stage crystallization is 150 to 220 ℃ (for example, may be 150 ℃, 155 ℃, 160 ℃, 165 ℃, 170 ℃, 180 ℃, 190 ℃, 200 ℃, 210 ℃, 220 ℃, and ranges of any two of the above numerical values), preferably 155 to 200 ℃, and the time of the second stage crystallization is 6 to 48h (for example, may be 6h, 7h, 8h, 9h, 10h, 12h, 14h, 16h, 18h, 20h, 22h, 24h, 30h, 34h, 36h, 38h, 40h, 42h, 48h, and ranges of any two of the above numerical values), preferably 12 to 36h.
According to the present invention, the conditions of the drying are not particularly required, and preferably, the conditions of the drying include: the drying temperature is 80-120 ℃, and the drying time is 8-12h.
According to the present invention, the conditions of the calcination are not particularly required, and preferably, the conditions of the calcination include: the roasting temperature is 350-600 ℃, and the roasting time is 6-12h.
In a second aspect, the present invention provides a ZSM-5 molecular sieve prepared by the above-described process.
According to the present invention, it is preferable that,the average pore diameter of the ZSM-5 molecular sieve is 2-6nm; wherein the specific surface area of the micropores is 300-500m 2 Per g, the specific surface area of the mesopores is 150 to 300m 2 (ii)/g; wherein the pore volume of the micropores is 0.01-0.30cm 3 Per g, the pore volume of the mesopores is 0.10-0.50cm 3 /g。
According to the invention, preferably, the silica to alumina ratio of the ZSM-5 molecular sieve is 100-300:1.
according to the present invention, preferably, the ZSM-5 molecular sieve has a crystallinity of 95 to 110%, preferably 100 to 110%.
The third aspect of the invention provides an application of the ZSM-5 molecular sieve in preparation of propylene from methanol.
According to the present invention, the methanol to propylene conditions may be conventional in the art, and preferably, the methanol to propylene conditions include: the temperature is 460-500 ℃, the pressure is 0-0.5MPa, and the mass space velocity of the methanol is 1-10h -1 The weight ratio of the raw material water to the raw material methanol is 1:0.5-1.
According to the invention, preferably, when the ZSM-5 molecular sieve is applied to the reaction of preparing propylene from methanol, the main products are ethylene, propylene, propane, C4 and C5 + Etc., wherein C4 includes a double bond-containing C4 ＝ Small amounts of methane and ethane may also be formed; dimethyl ether may also be formed as a by-product.
According to a particularly preferred embodiment of the present invention, the method of preparing a ZSM-5 molecular sieve comprises the steps of:
(1) Mixing a silicon source, an alkali source, quaternary ammonium salt, quaternary ammonium base and water, and then stirring for 1-12h at 25-50 ℃ to obtain a gel precursor;
(2) Mixing an aluminum source with water, and then stirring for 1-8h at 25-50 ℃ to obtain an aqueous solution of the aluminum source;
(3) Dropwise adding an aluminum source water solution into the gel precursor, and then stirring for 4-12h at 20-40 ℃ to obtain gel;
(4) Sequentially carrying out first-stage crystallization and second-stage crystallization on the gel, and then carrying out solid-liquid separation, washing, drying and roasting to obtain the ZSM-5 molecular sieve;
wherein the content of the first and second substances,the molar ratio of the aluminum source to the silicon source to the quaternary ammonium hydroxide to the quaternary ammonium salt to the alkali source to water is 1: (100-300): (20-40): (20-32): (10-35): (1200-2000), wherein the aluminum source is Al 2 O 3 The silicon source is SiO 2 Counting; preferably, the molar ratio of quaternary ammonium base to quaternary ammonium salt is 1: (0.8-1.1);
wherein the crystallization temperature of the second section is 10-100 ℃ higher than that of the first section;
wherein the conditions for the first stage crystallization include: the temperature of the first stage of crystallization is 120-140 ℃, and the time of the first stage of crystallization is 30-40h;
wherein the second crystallization condition comprises: the temperature of the second stage crystallization is 155-200 ℃, and the time of the first stage crystallization is 12-36h.
The present invention will be described in detail below by way of examples. In the following examples of the present invention, the following examples,
the pore structure and the specific surface area of the ZSM-5 molecular sieve are completed on an ASAP2420 surface analyzer, the desorption area of the sample after adsorbing nitrogen at the liquid nitrogen temperature is determined and recorded by using a chemical pulse adsorption method, and the sample is pretreated for 8 hours at 350 ℃ before the determination. The specific surface area and the pore volume of the ZSM-5 molecular sieve are simulated and calculated by adopting a t-plot model, and the pore size distribution of the ZSM-5 molecular sieve is calculated by adopting a BJH model.
X-ray diffraction (XRD): the method adopts a Dutch Pasnake X' pert3 powder, the working voltage is 40kV, the tube current is 40mA, a copper target, a 1-dimensional semiconductor PIXcel1D matrix detector, and the scanning mode is as follows: θ/θ, minimum step size: 0.0001;
SEM electron microscope: the method is carried out on a Dutch Helna Phenom-Pro scanning electron microscope, and a sample is subjected to surface metal spraying treatment after being fully ground, and the accelerating voltage is 10kV.
The analysis of the raw materials and the products in the reaction process of preparing propylene from methanol adopts a four-channel micro-reverse evaluation device produced by Beijing Sixin communication manufacturers to carry out the test, and the test conditions are as follows:
(1) An experimental instrument: four-channel micro-return evaluation device
(2) The experimental conditions are as follows: the loading of the catalyst is 2.0g, and the particle size of the catalyst is 10-20 meshes.
Steaming: at the temperature of 480 ℃, normal pressure and the mass space velocity of water vapor of 0.5h -1 Treating the ZSM-5 molecular sieve for 48 hours by using water vapor under the condition of (1).
Reaction: methanol and water vapor (the weight ratio of the raw material water to the raw material methanol is 1: 0.7) at the temperature of 480 ℃, the normal pressure and the mass space velocity of the methanol of 2h -1 The run was stopped until there was a significant decrease in methanol conversion.
(3) Experiment raw materials: chromatographic methanol, north union fine chemical development ltd, tianjin; pure water, ultrapure water (resistivity not less than 18 M.OMEGA.cm).
(4) And (3) product analysis: the product composition distribution adopts a gas chromatograph GC9860 III, online sampling full-component analysis is carried out, and the product distribution unit is mol%;
the calculation formula of the silicon source conversion rate is as follows: c (Si)% = (the amount of a silicon source substance in the ZSM-5 molecular sieve/the amount of a silicon source charging substance in the preparation of the ZSM-5 molecular sieve) × 100%, wherein the silicon source is SiO 2 Counting;
the silicon-aluminum ratio refers to SiO in a ZSM-5 molecular sieve 2 With Al 2 O 3 The molar ratio therebetween;
the conversion of methanol is calculated by the formula:
wherein x is MEOH Represents the amount of unreacted methanol in the product, x DME Which represents the amount of the by-product dimethyl ether,
representing the sum of the amounts of the components in the product;
the chromatography silica gel is a commercial product with a trade name of 201103X from Qingdao Bangkai high and new technology materials Co Ltd, and SiO in the chromatography silica gel 2 The content of (A) is more than or equal to 98wt%;
the silica sol is a commercial product with trade name of S-830 from Huihe Yongcheng nanometer science and technology Limited, and SiO is contained in the silica sol 2 The content of (B) is 40wt%.
Example 1
(1) 0.541g of sodium hydroxide, 4.711g of tetrapropylammonium hydroxide, 5.0g of tetrapropylammonium bromide and 10.925g of chromatographic silica gel are sequentially dissolved in 15g of deionized water, and then the mixture is stirred in a closed reaction kettle at the temperature of 25 ℃ for 1 hour at the speed of 450r/min to obtain a gel precursor.
(2) 0.0988g of sodium aluminate (NaAlO) 2 ) Uniformly mixing the aluminum source and 5g of deionized water, and stirring for 1h at 25 ℃ to obtain an aqueous solution of an aluminum source; then slowly dropwise adding an aqueous solution of an aluminum source into the gel precursor at a rate of 1mL/min, and continuously stirring at a speed of 450r/min for 4h at a temperature of 20 ℃ to obtain the gel.
(3) Transferring the gel into a hydrothermal reaction kettle, and performing two-stage crystallization, wherein the first-stage crystallization conditions comprise: the temperature is 120 ℃, and the time is 36h; the conditions for the second stage crystallization include: the temperature is 160 ℃ and the time is 24h. And after crystallization is finished, carrying out solid-liquid separation and washing, drying at 100 ℃ for 10h, and roasting at 550 ℃ for 6h to obtain the ZSM-5 molecular sieve. The silicon to aluminum ratio was 295. The XRD diffractogram is shown in FIG. 1. The BET characterization and the silicon source conversion are shown in table 1.
As can be seen from the analysis of the XRD diffractogram of fig. 1, characteristic diffraction peaks of the ZSM-5 molecular sieve appear at positions of 2 θ =7.98 °, 8.49 °, 13.10 °, 13.83 °, 23.11 ° and 23.91 °, which proves that the molecular sieve prepared in example 1 is the ZSM-5 molecular sieve; the XRD diffractogram of the ZSM-5 molecular sieve prepared in example 1 was compared with the XRD diffractogram of the standard ZSM-5 molecular sieve, resulting in a relative crystallinity of 110% for the ZSM-5 molecular sieve prepared in example 1.
As can be seen from the SEM image of FIG. 2, the ZSM-5 molecular sieve is in the form of cross-shaped spherical particles with relatively uniform size and smooth surface.
Example 2
(1) 0.541g of sodium hydroxide, 4g of tetrapropylammonium hydroxide, 5.711g of tetrapropylammonium bromide and 12g of chromatographic silica gel are sequentially dissolved in 15g of deionized water, and then stirred in a closed reaction kettle at the temperature of 30 ℃ for 2 hours at the speed of 400r/min to obtain a gel precursor.
(2) 0.147g of sodium aluminate (NaAlO) 2 ) Uniformly mixing the aluminum source and 5g of deionized water, and stirring for 2 hours at the temperature of 30 ℃ to obtain an aqueous solution of an aluminum source;then, slowly dropwise adding the aqueous solution of the aluminum source into the gel precursor at the speed of 2mL/min, and continuously stirring at the speed of 400r/min for 6h at the temperature of 30 ℃ to obtain the gel.
(3) Transferring the gel into a hydrothermal reaction kettle, and performing two-stage crystallization, wherein the first-stage crystallization conditions comprise: the temperature is 130 ℃, and the time is 30h; the conditions for the second stage crystallization include: the temperature is 180 ℃ and the time is 20h. After crystallization, solid-liquid separation and washing are carried out, then drying is carried out for 10h at 100 ℃, and then roasting is carried out for 6h at 550 ℃, so that the ZSM-5 molecular sieve is obtained, the XRD diffraction pattern of the ZSM-5 molecular sieve is similar to that of figure 1 and is not shown, and the relative crystallinity of the obtained ZSM-5 molecular sieve is 105%. The BET characterization and the silicon source conversion are shown in table 1.
Example 3
(1) 0.541g of sodium hydroxide, 4.8g of tetrapropylammonium hydroxide, 5.33g of tetrapropylammonium bromide and 10.925g of chromatographic silica gel are sequentially dissolved in 22g of deionized water, and then the mixture is stirred in a closed reaction kettle at 40 ℃ for 12 hours at the speed of 450r/min to obtain a gel precursor.
(2) 0.123g of sodium aluminate (NaAlO) 2 ) Uniformly mixing the aluminum source and 5g of deionized water, and stirring for 8 hours at 50 ℃ to obtain an aluminum source water solution; then slowly dripping the aqueous solution of the aluminum source into the gel precursor at the speed of 1mL/min, and continuously stirring for 5 hours at the speed of 450r/min at the temperature of 40 ℃ to obtain the gel.
(3) Transferring the gel into a hydrothermal reaction kettle, and performing two-stage crystallization, wherein the first-stage crystallization conditions comprise: the temperature is 120 ℃, and the time is 40h; the conditions for the second stage crystallization include: the temperature is 200 ℃ and the time is 12h. After crystallization, solid-liquid separation and washing are carried out, then drying is carried out for 10h at 100 ℃, and then roasting is carried out for 6h at 550 ℃, so that the ZSM-5 molecular sieve is obtained, the XRD diffraction pattern of the ZSM-5 molecular sieve is similar to that of figure 1 and is not shown, and the relative crystallinity of the obtained ZSM-5 molecular sieve is 105%. The BET characterization and the silicon source conversion are shown in table 1.
Example 4
(1) 0.541g of sodium hydroxide, 4.0g of tetrapropylammonium hydroxide, 5.711g of tetrapropylammonium bromide and 12g of chromatographic silica gel are sequentially dissolved in 15g of deionized water, and then stirred for 5 hours at the speed of 400r/min in a closed reaction kettle at the temperature of 50 ℃ to obtain a gel precursor.
(2) 0.1147g of sodium aluminate (NaAlO) 2 ) Uniformly mixing the aluminum source and 5g of deionized water, and stirring for 6 hours at 35 ℃ to obtain an aqueous solution of an aluminum source; then slowly dropwise adding an aqueous solution of an aluminum source into the gel precursor at a rate of 1mL/min, and continuously stirring at a speed of 400r/min at 25 ℃ for 12h to obtain the gel.
(3) Transferring the gel into a hydrothermal reaction kettle, and performing two-stage crystallization, wherein the first-stage crystallization conditions comprise: the temperature is 140 ℃, and the time is 35h; the conditions for the second stage crystallization include: the temperature was 155 ℃ and the time was 36h. After crystallization is finished, solid-liquid separation and washing are carried out, then the ZSM-5 molecular sieve is obtained after drying for 8 hours at 90 ℃ and roasting for 8 hours at 550 ℃, the XRD diffraction pattern of the ZSM-5 molecular sieve is similar to that of figure 1 and is not shown, and the relative crystallinity of the obtained ZSM-5 molecular sieve is 103%. The BET characterization and the silicon source conversion are shown in table 1.
Example 5
(1) 0.541g of sodium hydroxide, 4.8g of tetrapropylammonium hydroxide, 5.33g of tetrapropylammonium bromide and 12g of chromatographic silica gel are sequentially dissolved in 22g of deionized water, and then stirred in a closed reaction kettle at the temperature of 45 ℃ at the speed of 400r/min for 6 hours to obtain a gel precursor.
(2) 0.163g of sodium aluminate (NaAlO) 2 ) Uniformly mixing the aluminum source and 5g of deionized water, and stirring for 6 hours at 35 ℃ to obtain an aluminum source water solution; then, slowly dropwise adding the aqueous solution of the aluminum source into the gel precursor at the speed of 2mL/min, and continuously stirring at the speed of 400r/min for 10h at the temperature of 30 ℃ to obtain the gel.
(3) Transferring the gel into a hydrothermal reaction kettle, and performing two-stage crystallization, wherein the first-stage crystallization conditions comprise: the temperature is 120 ℃, and the time is 32h; the conditions for the second stage crystallization include: the temperature is 170 ℃ and the time is 30h. After crystallization, solid-liquid separation and washing are carried out, then drying is carried out for 10h at 100 ℃, and then roasting is carried out for 8h at 550 ℃, so that the ZSM-5 molecular sieve is obtained, the XRD diffraction pattern of the ZSM-5 molecular sieve is similar to that of figure 1 and is not shown, and the relative crystallinity of the obtained ZSM-5 molecular sieve is 104%. The BET characterization and the silicon source conversion are shown in table 1.
Example 6
(1) 0.541g of sodium hydroxide, 1.97g of tetrapropylammonium hydroxide, 2.6g of tetrapropylammonium bromide and 12g of silica sol are sequentially dissolved in 28.8g of deionized water, and then stirred in a closed reaction kettle at the temperature of 20 ℃ for 24 hours at the speed of 400r/min to obtain a gel precursor.
(2) 0.065g of sodium aluminate (NaAlO) 2 ) Uniformly mixing the aluminum source and 5g of deionized water, and stirring for 0.1h at 100 ℃ to obtain an aluminum source aqueous solution; then, slowly dropwise adding the aqueous solution of the aluminum source into the gel precursor at the speed of 2mL/min, and continuously stirring at the speed of 400r/min for 24h at the temperature of 50 ℃ to obtain the gel.
(3) Transferring the gel into a hydrothermal reaction kettle, and performing two-stage crystallization, wherein the first-stage crystallization conditions comprise: the temperature is 150 ℃, and the time is 6h; the conditions for the second stage crystallization include: the temperature is 220 ℃ and the time is 6h. After crystallization is finished, solid-liquid separation and washing are carried out, then the ZSM-5 molecular sieve is obtained after drying for 8 hours at 110 ℃ and roasting for 10 hours at 550 ℃, the XRD diffraction pattern of the ZSM-5 molecular sieve is similar to that of figure 1 and is not shown, and the relative crystallinity of the obtained ZSM-5 molecular sieve is 100%. The BET characterization and the silicon source conversion are shown in table 1.
Example 7
(1) 0.541g of sodium hydroxide, 6.988g of tetrapropylammonium hydroxide, 2.633g of tetrapropylammonium bromide and 12g of tetraethoxysilane are sequentially dissolved in 16.6g of deionized water, and then stirred in a closed reaction kettle at 100 ℃ at a speed of 400r/min for 0.1h to obtain a gel precursor.
(2) 0.088g of sodium aluminate (NaAlO) 2 ) Uniformly mixing the aluminum source and 5g of deionized water, and stirring for 12 hours at 20 ℃ to obtain an aqueous solution of an aluminum source; then, slowly dropwise adding the aqueous solution of the aluminum source into the gel precursor at the speed of 2mL/min, and continuously stirring at the temperature of 100 ℃ at the speed of 400r/min for 0.1h to obtain the gel.
(3) Transferring the gel into a hydrothermal reaction kettle, and performing two-stage crystallization, wherein the first-stage crystallization conditions comprise: the temperature is 100 ℃, and the time is 48h; the conditions for the second stage crystallization include: the temperature is 150 ℃ and the time is 48h. After crystallization, solid-liquid separation and washing are carried out, then drying is carried out for 10h at 100 ℃, and then roasting is carried out for 8h at 550 ℃, so that the ZSM-5 molecular sieve is obtained, the XRD diffraction pattern of the ZSM-5 molecular sieve is similar to that of figure 1 and is not shown, and the relative crystallinity of the obtained ZSM-5 molecular sieve is 99%. The BET characterization and the silicon source conversion are shown in table 1.
Example 8
The preparation of the ZSM-5 molecular sieve was performed as in example 1, except that tetrapropylammonium hydroxide was replaced with tetrapropylammonium bromide in the preparation of the gel precursor. The XRD diffraction pattern is similar to that of figure 1 and is not shown, and the obtained ZSM-5 molecular sieve has the relative crystallinity of 96%. The silicon to aluminum ratio was 260. The BET characterization and the silicon source conversion are shown in table 1.
As can be seen from the SEM image in FIG. 3, the ZSM-5 molecular sieves are spherical with different sizes and are irregular amorphous substances, which affects the crystallinity.
Example 9
ZSM-5 molecular sieves were prepared as in example 1, except that the amount of tetrapropylammonium hydroxide added was 2.428g and the amount of tetrapropylammonium bromide added was 7.283g in the preparation of the gel precursor. The XRD diffraction pattern is similar to that of figure 1 and no longer shows that the ZSM-5 molecular sieve obtained has the relative crystallinity of 98 percent. The silicon to aluminum ratio was 275. The BET characterization and the silicon source conversion are shown in table 1.
Example 10
The preparation of the ZSM-5 molecular sieve was carried out in the same manner as in example 1, except that the temperature for the second-stage crystallization in step (3) was the same as that for the first-stage crystallization. The XRD diffraction pattern is similar to that of figure 1 and no longer shows that the ZSM-5 molecular sieve obtained has the relative crystallinity of 98 percent. The silicon to aluminum ratio was 275. The BET characterization and the silicon source conversion are shown in table 1.
Example 11
The preparation of the ZSM-5 molecular sieve was carried out according to the method of example 1, except that the conditions for the first stage crystallization in step (3) included: the temperature is 160 ℃, and the time is 24 hours; the conditions for the second stage crystallization include: the temperature is 120 ℃ and the time is 36h. The XRD diffraction pattern is similar to that of figure 1 and no longer shows that the ZSM-5 molecular sieve obtained has the relative crystallinity of 97 percent. The silicon to aluminum ratio was 270. The BET characterization and the silicon source conversion are shown in table 1.
Example 12
The preparation of the ZSM-5 molecular sieve was performed according to the method of example 1, except that the aqueous solution of the aluminum source was slowly dropped into the gel precursor at 10mL/min in step (2). The XRD diffraction pattern is similar to that of figure 1 and is not shown, and the obtained ZSM-5 molecular sieve has the relative crystallinity of 98%. The silicon to aluminum ratio was 264. The BET characterization and the silicon source conversion are shown in table 1.
Comparative example 1
0.541g of sodium hydroxide, 4.711g of tetrapropylammonium hydroxide, 5.0g of tetrapropylammonium bromide, 0.0988g of sodium aluminate (NaAlO) 2 ) And 10.925g of chromatographic silica gel are sequentially dissolved in 20g of deionized water to obtain a mixture, and then the mixture is transferred into a hydrothermal reaction kettle for crystallization, wherein the crystallization conditions comprise that: the temperature is 120 ℃ and the time is 36h. And after crystallization is finished, carrying out solid-liquid separation and washing, drying at 100 ℃ for 8h, and roasting at 550 ℃ for 6h to obtain the ZSM-5 molecular sieve. The XRD diffraction pattern is similar to that of figure 1 and is not shown, and the obtained ZSM-5 molecular sieve has the relative crystallinity of 96%. The silicon to aluminum ratio was 245. The BET characterization and the silicon source conversion are shown in table 1.
Comparative example 2
The molecular sieve was prepared according to the method of comparative example 1 except that tetrapropylammonium hydroxide was replaced with tetrapropylammonium bromide. The XRD diffraction pattern is similar to that of figure 1 and is not shown, and the obtained ZSM-5 molecular sieve has the relative crystallinity of 96%. The silicon to aluminum ratio was 240. The BET characterization and the silicon source conversion are shown in table 1.
TABLE 1
Test example 1
The ZSM-5 molecular sieves prepared in the examples 1-12 and the comparative examples 1-2 are applied to the reaction of preparing propylene from methanol under the conditions that the temperature is 460-480 ℃, the pressure is normal pressure, the loading amount of the ZSM-5 molecular sieve is 2g, and the mass space velocity of the methanol is 2h -1 The weight ratio of the raw material water to the raw material methanol is 1:0.7, the reaction results are shown in Table 2.
TABLE 2
The results in table 2 show that the ZSM-5 molecular sieve prepared by the method of the present invention has a high methanol conversion rate and a high propylene selectivity when applied to a reaction of producing propylene from methanol. The ZSM-5 molecular sieve prepared in the embodiments 1-5 of the invention is applied to the reaction of preparing propylene from methanol, the conversion rate of methanol is higher than 99.95%, the selectivity of propylene is higher than 47.36%, and the catalyst has better catalytic performance.
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 (11)
1. A method of preparing a ZSM-5 molecular sieve, the method comprising the steps of:
(1) Mixing a silicon source, an alkali source, a template agent and water to obtain a gel precursor;
(2) Adding an aqueous solution of an aluminum source into the gel precursor to obtain gel;
(3) Crystallizing, drying and roasting the gel in sequence to obtain the ZSM-5 molecular sieve;
the template agent is selected from the combination of quaternary ammonium salt and quaternary ammonium base, the quaternary ammonium base is selected from at least one of tetramethyl ammonium hydroxide, tetrapropyl ammonium hydroxide and tetraethyl ammonium hydroxide, the quaternary ammonium salt is selected from at least one of tetramethyl ammonium bromide, tetrapropyl ammonium bromide and tetraethyl ammonium bromide, and the molar ratio of the quaternary ammonium base to the quaternary ammonium salt is 1: (0.2-1.1);
the molar ratio of the aluminum source to the silicon source to the template agent to the alkali source to the water is 1: (100-300): (40-90): (10-35): (1200-4800) wherein the aluminum source is Al 2 O 3 The silicon source is SiO 2 Counting;
the crystallization comprises a first section of crystallization and a second section of crystallization, and the temperature of the second section of crystallization is 10-100 ℃ higher than that of the first section of crystallization.
2. The method of claim 1, wherein the silicon source is an organic silicon source and/or an inorganic silicon source; the aluminum source is pseudoboehmite and/or aluminum salt; the alkali source is inorganic alkali.
3. The method of claim 1, wherein the silicon source is at least one of tetraethoxysilane, water glass, silica sol and silica gel; the aluminum source is at least one of aluminum sulfate, aluminum nitrate and sodium aluminate; the alkali source is at least one of sodium hydroxide, potassium hydroxide and ammonia.
4. The method of claim 1, wherein the silicon source is at least one of tetraethoxysilane, silica sol, and silica gel; the aluminum source is sodium aluminate.
5. The method of any one of claims 1 to 4, wherein in step (2), the aqueous solution of the aluminum source is added at a rate of 0.1 to 5mL/min of SiO source relative to 0.1mol of the silicon source 2 Counting;
in the step (2), in the aqueous solution of the aluminum source, the molar ratio of water to the aluminum source is 130-360, wherein the aluminum source is Al 2 O 3 And (6) counting.
6. The method of any one of claims 1 to 4, wherein the aqueous solution of aluminum source is added at a rate of 0.5 to 2mL/min relative to 0.1mol of the silicon source, which is SiO 2 And (6) counting.
7. The method of any one of claims 1-4, wherein the conditions for the first stage crystallization comprise: the temperature of the first stage of crystallization is 100-150 ℃, and the time of the first stage of crystallization is 6-48h.
8. The method of any one of claims 1-4, wherein the conditions for the second crystallization comprise: the temperature of the second section crystallization is 150-220 ℃, and the time of the second section crystallization is 6-48h.
9. The method of any of claims 1-4, wherein the drying conditions comprise: the drying temperature is 80-120 ℃, and the drying time is 10-15h;
the roasting conditions comprise: the roasting temperature is 350-600 ℃, and the roasting time is 6-12h.
10. A ZSM-5 molecular sieve produced by the process of any of claims 1-9.
11. Use of the ZSM-5 molecular sieve as described in claim 10 in the preparation of propylene from methanol.
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