CN112794338A - 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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- 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
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- 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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- 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 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 th century, the company Mobil invented ZSM-5 zeolite, the ZSM-5 molecular sieve has been widely used in various fields. The ZSM-5 molecular sieve is a typical microporous molecular sieve, and a ZSM-5 molecular sieve framework contains two mutually crossed pore channel systems: the diameter of the oval ten-membered ring straight channel and the round zigzag curved channel is 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 a small-grain ZSM-5 zeolite, which comprises the following steps: mixing SiO2/Al2O3Mixing 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 molar ratio is SiO2/Al2O3＝20-600，Na2O/SiO2＝0.25-1，R/SiO20.01-0.2, water/SiO22-15, wherein R is a quaternary ammonium salt templating 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 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 the temperature of 150-190 ℃ after being heated by microwave for 3-30 minutes; 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) Al2O3/(20-30)SiO2(100-1500) Water/(4-45) TPAOH, wherein 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 Na2O/SiO2/Al2O3/B2O3The molar ratio of the template agent/water is 1.5/(0.1-7)/(0.00-0.2)/(0.001-0.3)/(0.01-2.25)/(1-10), sodium hydroxide, silicon source, aluminum source, boron-containing compound and the template agent are added into water and stirred evenly to obtain mixed gel, the mixed gel is crystallized at constant temperature of 130-200 ℃, the template agent is removed by roasting at 350-650 ℃ to remove the template agentAnd (3) carrying out ion exchange and washing on the acid solution, and keeping the acid solution at the temperature of 350-650 ℃ for 4 hours to obtain the B-EU-1/ZSM-5 hydrogen type composite molecular sieve, wherein the template agent is formed by mixing tetrapropylammonium bromide and hexapotassium bromide diammonium. 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 non-metallic element B.
CN107892308 discloses a ZSM-5 molecular sieve and its preparation method, which comprises: 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 gel2With Al2O3The mol ratio of the components is (20-200)/1, the quaternary ammonium template agent, the phosphorus template agent, the ethanol, the water and the SiO2The molar ratio of (0.001-0.5)/(0.001-0.5)/(1-50)/(0.2-50)/1; and crystallizing the mixed gel at the temperature of 100-200 ℃ for 6-72h to obtain a 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 invention, 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 by 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 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 a first aspect, the present invention provides a process for preparing a ZSM-5 molecular sieve, the process 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) in which the aluminum source is Al2O3The silicon source is SiO2Counting; further preferably, the aluminum source, the silicon source, the templating agent, the alkali source, and the water are added in amounts such that, in the resulting 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 a chromatography silica gel, and the chromatography silica gel can be a chromatography silica gel of 100-200 mesh particles, a chromatography silica gel of 200-300 mesh particles and a chromatography silica gel of 300-400 mesh particles.
Note that, silica sol (mSiO)2·nH2SiO in O)2The content of (B) is 25-40 wt%; chromatography of SiO in silica gel2The content of (B) is more than or equal to 98 wt%.
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 should be noted that Al in pseudo-boehmite2O3Of (1) containsThe amount is more than or equal to 70 wt%.
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, silicon-aluminum ratio and specific surface area and pore volume of the ZSM-5 molecular sieve, two templates, preferably at least two templates selected from quaternary ammonium salt and quaternary ammonium base, are used in the preparation of 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 quaternary ammonium base to 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 the water, the conditions of mixing 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; 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 preferably 1-12 h; the stirring rate is 1-100r/min, preferably 20-50r/min, relative to 0.01mol of silicon source, which is SiO2And (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 4-12 h; the stirring rate is 1-100r/min, preferably 20-50r/min, relative to 0.01mol of silicon source, which is SiO2And (6) counting.
According to the present invention, in order to better dissolve the aluminum source in water, 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 aluminum source in the aqueous solution of aluminum source is 130-2O3And (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 crystallization conditions of the first stage may be conventional crystallization conditions in the art, and preferably, the crystallization conditions of the first stage include: the temperature of the first stage crystallization is 100-.
According to the present invention, the conditions for the second stage crystallization may be conventional in the art, and preferably, the conditions for the second stage crystallization include: the temperature of the second-stage crystallization is 150-.
According to the present invention, the drying conditions are not particularly required, and preferably, the drying conditions include: the drying temperature is 80-120 deg.C, and the drying time is 8-12 h.
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 6-12 h.
In a second aspect, the present invention provides a ZSM-5 molecular sieve prepared by the above-described process.
According to the present invention, preferably, the ZSM-5 molecular sieve has an average pore size of 2-6 nm; wherein the specific surface area of the micropores is 300-500m2The specific surface area of the mesopores is 150-300m2(ii)/g; wherein the pore volume of the micropores is 0.01-0.30cm3The pore volume of the mesopores is 0.10-0.50cm3/g。
According to the present invention, preferably, the ZSM-5 molecular sieve has a silica-alumina ratio of 100-: 1.
according to the present invention, the ZSM-5 molecular sieve preferably has a crystallinity of 95-110%, preferably 100-110%.
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 ℃ and 500 ℃, the pressure is 0-0.5MPa, and the mass space velocity of the methanol is 1-10h-1The 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 C4 containing a double bond＝Small amounts of methane may also be formedAnd ethane; dimethyl ether may also be formed as a by-product.
According to a particularly preferred embodiment of the present invention, the process for 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 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 the water is 1: (100-300): (20-40): (20-32): (10-35): (1200-2000), wherein the aluminum source is Al2O3The silicon source is SiO2Counting; 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 first stage crystallization conditions include: the temperature of the first section of crystallization is 120-;
wherein the second crystallization condition comprises: the temperature of the second section of crystallization is 155-.
The present invention will be described in detail below by way of examples. In the following examples of the present invention,
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 10 kV.
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 water vapor mass space velocity of 0.5h-1Treating 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-1The run was stopped until there was a significant decrease in methanol conversion.
(3) Experiment raw materials: chromatographic methanol, north-linked fine chemicals 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)% (amount of silicon source material in ZSM-5 molecular sieve/amount of silicon source charged in preparation of ZSM-5 molecular sieve) × 100%, wherein the silicon source is SiO ═ si2Counting;
the silicon-aluminum ratio refers to SiO in the ZSM-5 molecular sieve2With Al2O3The molar ratio therebetween;
the formula for calculating the conversion of methanol is:
wherein xMEOHRepresents the amount of unreacted methanol in the product, xDMEWhich represents the amount of the by-product dimethyl ether,
represents the sum of the amounts of the components in the product;
the chromatography silica gel is prepared from a commercial product of Qingdao Bangkai high and new technology materials GmbH with a trademark of 201103X, and SiO in the chromatography silica gel2The content of (A) is more than or equal to 98 wt%;
the silica sol is a commercial product with trade name of S-830 from Huihe and Yongcheng nanometer science and technology Limited, and SiO is contained in the silica sol2The content of (B) is 40 wt%.
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 dripping the aqueous solution of the aluminum source into the gel precursor at the speed of 1mL/min, and continuously stirring for 4 hours at the speed of 450r/min at the 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 36 h; the conditions for the second stage crystallization include: the temperature is 160 ℃ and the time is 24 h. And after crystallization is finished, carrying out solid-liquid separation and washing, then 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 XRD diffractogram analysis of fig. 1, characteristic diffraction peaks of the ZSM-5 molecular sieve appear at positions such as 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; comparing the XRD diffraction pattern of the ZSM-5 molecular sieve prepared in example 1 with the XRD diffraction pattern of a standard ZSM-5 molecular sieve, the relative crystallinity of the ZSM-5 molecular sieve prepared in example 1 was 110%.
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 the mixture is 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 30 h; the conditions for the second stage crystallization include: the temperature is 180 ℃ and the time is 20 h. 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 aqueous solution of an aluminum source; then slowly dripping 1mL/min aqueous solution of aluminum source into the gel precursor, and collecting the gel precursor at the temperature of 40 ℃ at 450 r-Stirring is continued for 5h at min to obtain a 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 40 h; the conditions for the second stage crystallization include: the temperature is 200 ℃ and the time is 12 h. 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 the mixture is stirred in a closed reaction kettle at the temperature of 50 ℃ for 5 hours at the speed of 400r/min 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 dripping the aqueous solution of the aluminum source into the gel precursor at the speed of 1mL/min, and continuously stirring at the speed of 400r/min for 12h at the temperature of 25 ℃ 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 35 h; the conditions for the second stage crystallization include: the temperature was 155 ℃ and the time was 36 h. After crystallization, solid-liquid separation and washing are carried out, then drying is carried out for 8h at 90 ℃, 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 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 ℃ for 6 hours at the speed of 400r/min 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 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 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 32 h; the conditions for the second stage crystallization include: the temperature is 170 ℃ and the time is 30 h. 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 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 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 6 h; the conditions for the second stage crystallization include: the temperature was 220 ℃ and the time was 6 h. After crystallization, solid-liquid separation and washing are carried out, then drying is carried out for 8h at 110 ℃, and then roasting is carried out for 10h 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 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 ethyl orthosilicate are sequentially dissolved in 16.6g of deionized water, and then the mixture is stirred in a closed reaction kettle at 100 ℃ for 0.1h at the speed of 400r/min 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 48 h; the conditions for the second stage crystallization include: the temperature is 150 ℃ and the time is 48 h. 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 36 h. 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 no longer shows that the ZSM-5 molecular sieve obtained has the relative crystallinity of 98 percent. 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: the temperature is 120 ℃ and the time is 36 h. 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
Molecular sieves were prepared according to the procedure 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 and 480 ℃, the pressure is normal pressure, the filling amount of the ZSM-5 molecular sieve is 2g, and the mass space velocity of the methanol is 2h-1The 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 higher methanol conversion rate and a higher propylene selectivity when applied to the reaction of preparing 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 molecular sieve 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 (10)
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) and crystallizing, drying and roasting the gel in sequence to obtain the ZSM-5 molecular sieve.
2. The method of claim 1, wherein the aluminum source, the silicon source, the templating agent, the alkali source, and the water are present in a molar ratio of 1: (100-300): (40-90): (10-35): (1200-4800) in which the aluminum source is Al2O3The silicon source is SiO2And (6) counting.
3. The method according to claim 1 or 2, wherein the silicon source is an organic silicon source and/or an inorganic silicon source, preferably at least one of ethyl orthosilicate, water glass, silica sol and silica gel, more preferably at least one of ethyl orthosilicate, silica sol and silica gel;
and/or the aluminium source is pseudoboehmite and/or an aluminium salt, preferably at least one of aluminium sulphate, aluminium nitrate and sodium aluminate, more preferably sodium aluminate;
and/or the alkali source is an inorganic alkali, preferably at least one of sodium hydroxide, potassium hydroxide and ammonia.
4. The method of any one of claims 1-3, wherein the templating agent is selected from at least two of quaternary ammonium salts and quaternary ammonium bases;
preferably, the quaternary ammonium salt is selected from tetraalkylammonium bromides;
preferably, the quaternary ammonium base is selected from tetraalkylammonium hydroxides;
more preferably, the templating agent is selected from at least two of tetramethylammonium hydroxide, tetramethylammonium bromide, tetrapropylammonium hydroxide, tetrapropylammonium bromide, tetraethylammonium hydroxide, and tetraethylammonium bromide.
5. The method of claim 4, wherein the templating agent is a combination of quaternary ammonium salt and 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;
preferably, the molar ratio of the quaternary ammonium base to the quaternary ammonium salt is 1: (0.2-1.1).
6. The process according to any one of claims 1 to 5, wherein 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, which is SiO2Counting;
preferably, in the step (2), the molar ratio of water to aluminum source in the aqueous solution of aluminum source is 130-360:1, and the aluminum source is Al2O3And (6) counting.
7. The method of any of claims 1-6, wherein the crystallizing comprises a first stage crystallizing and a second stage crystallizing;
preferably, the crystallization temperature of the second section is 10-100 ℃ higher than that of the first section;
preferably, the conditions for the first stage crystallization include: the temperature of the first section of crystallization is 100-;
preferably, the conditions for the second crystallization include: the temperature of the second-stage crystallization is 150-.
8. The method of any one of claims 1-7, wherein the drying conditions comprise: the drying temperature is 80-120 ℃, and the drying time is 10-15 h;
and/or, the roasting conditions include: the roasting temperature is 350-600 ℃, and the roasting time is 6-12 h.
9. A ZSM-5 molecular sieve, prepared by the process of any of claims 1-8.
10. Use of the ZSM-5 molecular sieve as claimed in claim 9 in the preparation of propylene from methanol.
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