CN109694085B - Template-free synthesis method of ammonium type ZSM-5 nanosheet - Google Patents
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Abstract
The invention relates to a template-free synthesis method of ammonium ZSM-5 nanosheets, which mainly solves the problems that flaky nano ZSM-5 is difficult to obtain in the synthesis process of the conventional nano ZSM-5 molecular sieve without using an organic template or inorganic alkali or salt containing alkali metal or alkaline earth metal, the aftertreatment needs 2-3 times of ammonium nitrate exchange, the material consumption and the energy consumption are high, and the like. The invention adopts a novel method for synthesizing the ammonium ZSM-5 nanosheet molecular sieve, no alkali metal or alkaline earth metal ions are introduced in the process, and the used micromolecule alkali has less pollution and low toxicity, so that the serious environmental protection pressure is not caused. Can be used in the industrial production of ammonium type ZSM-5 nanosheets.
Description
Technical Field
The invention relates to a template-free synthesis method of an ammonium ZSM-5 nanosheet.
Background
The molecular sieves synthesized by conventional methods used in industry generally have a crystal size of greater than 1 μm. The molecular sieve crystal contains 400-1000 molecular sieve unit cells in one dimension direction. The molecular sieve prepared by the improved method has the common crystal with the submicron size of 0.1-1 mu m, and the nano molecular sieve with the grain size smaller than 0.1 mu m is difficult to synthesize. After the particle size of the molecular sieve is reduced from micron level to nanometer level, some physical and chemical properties, such as catalytic performance, thermal stability, reaction performance, etc., can be greatly changed, so that the molecular sieve has different special performances.
Generally, molecular sieves are synthesized by hydrothermal treatment of a silica-alumina gel at a certain time and temperature. Parameters such as stirring speed, seed, crystallization temperature, gel composition, pH, silica to alumina ratio, and template concentration all control the size of the crystallites.
Electrolyte such as NaOH, NaCl and other dispersing agents are adsorbed on the surfaces of the particles, so that on one hand, the absolute value of the surface potential of the particles is remarkably improved, and therefore, a strong double-layer electrostatic repulsion effect is generated, and meanwhile, the electrolyte can also enhance the wetting degree of the surfaces of the particles on water, so that the agglomeration of the particles in the water is effectively prevented, and the particle size of the nano zeolite can be effectively controlled. When ZSM-5 nano zeolite is synthesized, the content of NaCl is increased to reduce the crystal grain to about 70nm (XRD). When ZSM-5 nano zeolite is synthesized, a proper amount of NaCl is added into the system to reduce the crystal grain to about 60nm (TEM). Further research results show that the addition of sodium chloride has obvious influence on crystallization speed and crystal grain shape, and the addition of a proper amount of sodium chloride can not only accelerate the crystallization process, but also inhibit the growth of crystal grains. When small grains are obtained, the ratio of sodium chloride to aluminum chloride is controlled to be between 30 and 60, and the superfine grains of the ZSM-5 molecular sieve cannot be obtained when the ratio is higher than or lower than 15.
In the synthesis of the nano ZSM-5 zeolite, tetrapropylammonium hydroxide is mostly used as an alkali source and tetraethoxysilane is used as a silicon source in order to obtain uniform and transparent sol, and the existence of alkali metal ions in the system can make the silicon-aluminum sol unstable and aggregate. Therefore, it must be synthesized in the absence of alkali metal ions. Synthesizing 10-100 nm (TEM) ZSM-5 zeolite under a supersaturated gelling ratio hydrothermal condition (443K), and performing systematic research on influence synthesis factors to find that the formation of small-grain zeolite is facilitated by taking aluminum isopropoxide as an aluminum source, long aging time, high alkalinity and low sodium content; the presence of sodium ions reduces the crystallization rate of the ZSM-5 zeolite, resulting in a significant increase in the crystallite size. The low temperature (373K) system without alkali metal ions is not beneficial to aluminum entering a zeolite framework, and only a high-silicon or pure-silicon molecular sieve (silicalite-1) can be synthesized with the participation of an organic template.
In the past reports, NaOH, NaCl, KCl or the like is generally adopted as an alkalinity adjusting reagent or a mineralizing agent, and the methods are easy to synthesize the nano ZSM-5, but the treatment of the filtered waste liquid and the exchange of the molecular sieve cause environmental problems and increase the synthesis cost.
The synthesis of nano pure silicon ZSM-5(silicalite-1) is simpler, but can be generally synthesized under the environment of TEOS and TPA template agent (CN 102602959B). In addition, TPAOH or TPABr is also used as a template agent as a main means for synthesizing the nano ZSM-5. CN 105668586A adopts a sectional crystallization method, and TPAOH is used as a template agent to synthesize a molecular sieve with the particle size of 50-200 nm; CN 105712378A uses template agent and surface active agent to reduce the particle size of molecular sieve. CN 103787367A uses template agent and seed crystal to prepare nanometer molecular sieve shaped body; CN 102502696A uses acid, alkali and organic amine to prepare nano molecular sieve; CN 105565340A also used TPAOH as a template agent to synthesize a nano molecular sieve; CN 102001680B and CN 101643219B use NaOH to replace an organic template as an alkali source, but part of the molecular sieve is dissolved in a strong alkaline environment, so that the yield of the molecular sieve is reduced, and ion exchange sodium removal treatment is required.
Seeding is also one of the effective methods for synthesizing nano molecular sieve, but TPAOH or Na ion synthesis systems (CN 102666385 a, CN 101983921 a, CN 102874843B) are used, which all cause the yield of the molecular sieve to decrease.
CN 104085899A and CN 104525246A adopt a template-free and seed-crystal-free system to synthesize the nano ZSM-5, but NaOH components are required to promote crystallization, the synthesized sodium type molecular sieve can be used only after sodium removal treatment, and a certain amount of molecular sieve is lost in the process.
Disclosure of Invention
The invention aims to solve the technical problems that in the prior art, a macromolecular organic template agent or inorganic alkali containing alkali metal or alkaline earth metal and salt are not used in the synthesis process of the nano ZSM-5 molecular sieve, the flaky nano ZSM-5 is difficult to obtain, the aftertreatment needs 2-3 times of ammonium nitrate exchange, the material consumption and the energy consumption are high, and the like. A novel method for synthesizing the ammonium ZSM-5 nanosheets is adopted, no alkali metal or alkaline earth metal ions are introduced in the process, and the used micromolecule alkali is less in pollution and toxicity and cannot cause serious environmental protection pressure.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
a template-free synthesis method of an ammonium ZSM-5 nanosheet comprises the following steps: a) dissolving an aluminum source and water, and adding micromolecular alkali M1 containing 0-3 carbon atoms to form solution A; b) uniformly mixing a silicon source and water, adding a solution A, and adding ZSM-5 seed crystals after the solution A is added; c) adding micromolecular alkali M2 containing 0-3 carbon atoms into the alkaline synthetic solution again, wherein the molar ratio of the final synthetic solution is as follows: h2O/SiO2＝3～ 150，SiO2/Al2O3＝20～∞，(M1+M2)/SiO20.2-5; d) crystallizing the mixed solution; e) and after crystallization is finished, filtering, washing and drying to obtain the ammonium ZSM-5 nanosheet.
In the above technical solutions, the number of carbon atoms of the small molecule base M1 or M2 is preferably 0, 1, or 2.
In the above technical solution, preferably, (M1+ M2)/SiO2＝0.2-1。
In the above technical scheme, preferably, in the step a), the amount of the small molecular alkali M1 containing 0-3 carbon atoms is added in the amount of M1/SiO2＝0.05-1。
In the above technical scheme, preferably, in the step c), the amount of the small molecular alkali M2 containing 0-3 carbon atoms is added into the mixture, and the small molecular alkali M2/SiO2＝0.15～4。
In the above technical solution, preferably, the crystallization temperature is 100 to 200 ℃, and the crystallization time is 0.5 to 240 hours. More preferably, 130 ℃ and 180 ℃ for 24-72 hours.
In the above technical scheme, the silicon source is selected from at least one of silicon oxide, silica sol, white carbon black, ethyl orthosilicate and activated clay.
In the above technical solution, the aluminum source is at least one selected from aluminum isopropoxide, aluminum oxide, aluminum hydroxide, metallic aluminum, aluminum sol, aluminum sulfate, aluminum nitrate or aluminum chloride. In order to synthesize the ammonium type nano ZSM-5 with a better appearance, Aluminum Isopropoxide (AIP) is mostly adopted in the prior literature, although the product size is smaller, the yield is not high, generally not higher than 50%, the raw material cost is high, a large amount of organic template is used, the pressure is higher in the synthesis process, and certain risks exist.
In the technical scheme, the small molecular sieve base M1 and M2 containing 0-3 carbon atoms are selected from at least one of ethylamine, diethylamine, ethylenediamine, triethylamine, ammonia water, urea and n-propylamine.
In the technical scheme, the adding amount of the ZSM-5 seed crystal is 0.5 to 5 percent of the weight of the synthetic liquid; more preferably, the ZSM-5 seed crystal is added in an amount of 1-2% of the weight of the synthesis solution.
The molecular sieve product does not contain alkali metal or alkaline earth metal ions; the solid amount after roasting is more than 90% of the added solid amount.
The template-free synthesis method of the ammonium ZSM-5 nanosheet adopts micromolecule alkali, and in the synthesis process, part of the micromolecule alkali is mixed with an aluminum source, seed crystals are added, and part of the micromolecule alkali is added after the seed crystals are added, so that the nanosheet ZSM-5 molecular sieve can be obtained. The technical scheme adopts common inorganic raw materials, does not use alkali metal or alkaline earth metal, does not need subsequent exchange treatment, uses micromolecule alkali to replace an organic template agent, has low toxicity, easy volatilization and simple treatment, can save mass production cost, and achieves the aims of high yield, low cost and environmental protection.
Drawings
FIG. 1 is the XRD spectrum of the product of example 5;
FIG. 2 is an SEM of the product of example 5.
The invention is further illustrated by the following examples, but is not limited thereto.
Detailed Description
In the examples, the raw materials used in the synthesis were all chemically pure reagents.
[ example 1 ]
Stirring and dissolving 2 g of aluminum nitrate, 5 g of ethylamine (M1) and 30 g of water to obtain a solution A, mixing 40 g of tetraethyl orthosilicate and 50 g of deionized water, stirring at room temperature for 5 hours to obtain a solution B, slowly adding the solution B into the solution A, stirring strongly for 2 hours, adding 1 wt% of ZSM-5 seed crystal, stirring for 1 hour, adding 15 g of ammonia water (M2), transferring the mixed system into a stainless steel crystallization kettle, and crystallizing at 150 ℃ for 72 hours. The XRD pattern of the obtained sample has the characteristic diffraction peak of the ZSM-5 zeolite molecular sieve, and the thickness of the sheet-shaped molecular sieve in the SEM pattern is about 80 nm. Product SiO2/Al2O3The molar ratio is 63, Na+The content is 0.02%, and the yield of the molecular sieve is 96%.
[ example 2 ]
1.5 g of aluminium sulphate, 2 g of diethylamine (M1) and 30 g of water are dissolved by stirring to form a solution A, 50 g of silica sol (40%) is mixed with 10 g of deionized waterMixing, stirring at room temperature for 0.5 hr to obtain solution B, slowly adding solution B into solution A, stirring under strong force for 2 hr, adding 2 wt% ZSM-5 seed crystal, stirring for 1 hr, adding 5 g ethylamine (M2) solution, transferring the mixed system into stainless steel crystallization kettle, and crystallizing at 170 deg.C for 24 hr. The XRD pattern of the obtained sample has characteristic diffraction peaks of a ZSM-5 zeolite molecular sieve, and the thickness of a sheet-shaped molecular sieve in the SEM pattern is about 50 nm. Product SiO2/Al2O3The molar ratio is 147, Na+The content is 0.01 percent, and the yield of the molecular sieve is 98 percent
[ example 3]
5 g of aluminum nitrate, 2 g of ethylenediamine (M1) and 30 g of deionized water are stirred and dissolved to form a solution A,40 g of white carbon black is added with 50 g of water and is continuously stirred uniformly to obtain a solution B, the solution B is slowly added into the solution A and is stirred strongly for 2 hours, 0.5 wt% of ZSM-5 seed crystal is added and is stirred for 1 hour, finally 8 g of ammonia water (M2) is added and is mixed uniformly, and the mixture is transferred into a stainless steel crystallization kettle and crystallized for 72 hours at the temperature of 130 ℃. The XRD pattern of the obtained sample has characteristic diffraction peaks of a ZSM-5 zeolite molecular sieve, and the thickness of a sheet-shaped molecular sieve in the SEM pattern is about 30 nm. Product SiO2/Al2O3The molar ratio is 98, Na+The content is 0.01 percent, and the yield of the molecular sieve is 97 percent
[ example 4 ]
0.31 g of aluminum hydroxide, 20g of ammonia water (M1) and 50 g of deionized water are sealed, stirred and dissolved for 1 hour to form A, 104 g of silica sol (40%) and 32 g of deionized water are mixed, the solution B is slowly added into the solution A, stirred for 2 hours with strong force, added with 1 wt% of ZSM-5 seed crystal and stirred for 1 hour, added with 16 g of ammonia water (M2) solution, then the mixed system is moved into a stainless steel crystallization kettle and crystallized for 12 hours at 170 ℃. The XRD pattern of the obtained sample has characteristic diffraction peaks of a ZSM-5 zeolite molecular sieve, and the thickness of a sheet-shaped molecular sieve in the SEM pattern is about 100 nm. Product SiO2/Al2O3The molar ratio is 350 and Na+The content is 0.02%, and the yield of the molecular sieve is 99%.
[ example 5 ]
1.5 g of alumina sol (30%), 3 g of n-propylamine (M1) and 32 g of deionized water were dissolved with stirring to form solution A, 25 g of tetraethyl orthosilicate and 20g of deionized waterMixing, stirring at room temperature for 5 hours to form a solution B, slowly adding the solution B into the solution A, strongly stirring for 2 hours, adding 5 wt% ZSM-5 seed crystal, stirring for 1 hour, finally adding 20g diethylamine (M2), uniformly mixing, transferring into a stainless steel crystallization kettle, and crystallizing at 180 ℃ for 36 hours. The XRD pattern of the obtained sample has characteristic diffraction peaks of a ZSM-5 zeolite molecular sieve, and the thickness of a sheet-shaped molecular sieve in the SEM pattern is about 120 nm. Product SiO2/Al2O3The molar ratio is 24, Na+The content is 0.01%, and the yield of the molecular sieve is 93%.
Comparative example 1
According to the formula of the document (chem. Mater.2005,17, 2494-2513),
9TPAOH:0.16Na2O:1Al2O3:50Si:300-495H20/100EtOH (S), crystallizing at 165 ℃ for 24h, filtering and washing to obtain spherical ZSM-5 with the particle size of 50nm and the molecular sieve yield of only 60 percent, and performing acid cross-linking, ammonium cross-linking and other steps to obtain the hydrogen type molecular sieve, wherein the final yield is about 45 percent and a large amount of materials are lost.
Comparative example 2
1g of aluminium nitrate and 25ml of a 1mol/L sodium hydroxide solution are mixed and stirred by the method of patent CN 104525246A. Then 20g of silica sol is added, stirred for 10 hours and then moved into a stainless steel crystallization kettle, and crystallized for 48 hours at 170 ℃, wherein the crystallized product is cylindrical ZSM-5 with the grain diameter of 3-5 mu m, but not a nano molecular sieve.
Comparative example 3
Dissolving 4KgNaOH and 1.64KgNaAlO2 in 1.46L of deionized water by adopting a method of a patent CN 104085899A, adding 83.8L of silica sol, stirring, aging for 12h, crystallizing at 130 ℃ for 0.5h, crystallizing at 170 ℃ for 9h, filtering, washing and drying to obtain spherical particles with small crystal grain ZSM-5 of 0.5 mu m, wherein the yield of the molecular sieve is 75%; the yield of the ammonium type ZSM-5 molecular sieve obtained after the exchange of the ammonium nitrate solution is reduced to 60 percent.
Comparative example 4
The experimental procedure is the same as that of example 1, except that no 1 wt% ZSM-5 seed crystal is added in the gelling process, the XRD spectrogram of the product after crystallization, washing and drying is amorphous, and the SEM spectrogram is irregular particles.
Comparative example 5
The experimental process is the same as that of example 1, except that no ethylamine is added in the process of forming the solution A, 20g of ammonia water is added before the solution A is transferred into a stainless steel crystallization kettle, the XRD spectrogram of the product after crystallization, washing and drying is ZSM-5, and the product SiO is SiO2/Al2O3The molar ratio was also 63, but the nanoplatelets and the nanospheres were present in the SEM spectra.
Comparative example 6
The experimental process is the same as that of example 1, except that 0.2 wt% of ZSM-5 seed crystal is added in the gelling process, and the XRD spectrogram of the product after crystallization, washing and drying is ZSM-5, but the diffraction peak intensity is not high; the coexistence of the nano-sheets and the irregular spherical particles in the SEM spectrogram indicates that amorphous substances exist; the calcination weighing results indicated that the yield of the molecular sieve was 67%.
Claims (6)
1. A template-free synthesis method of an ammonium ZSM-5 nanosheet comprises the following steps:
a) dissolving an aluminum source and water, and adding micromolecular alkali M1 containing 0-3 carbon atoms to form solution A;
b) uniformly mixing a silicon source and water, adding a solution A, and adding ZSM-5 seed crystals after the solution A is added;
c) adding micromolecular alkali M2 containing 0-3 carbon atoms into the alkaline synthetic solution again, wherein the molar ratio of the final synthetic solution is as follows: h2O/SiO2＝3～150，SiO2/Al2O3＝20～∞，(M1+M2)/SiO2＝0.2～5；
d) Crystallizing the mixed solution;
e) filtering, washing and drying after crystallization to obtain an ammonium type ZSM-5 nanosheet;
in the step a), adding a micromolecular alkali M1 with the carbon atom number of 0-3, wherein the molar weight of the micromolecular alkali M1/SiO2＝0.05-1；
In the step c), adding the micromolecular alkali M2 with the carbon atom number of 0-3, wherein the molar weight of the micromolecular alkali M2/SiO2＝0.15～4；
The micromolecular alkali with carbon atom number of 0-3 comprises at least one of ethylamine, ethylenediamine, ammonia water, urea and n-propylamine;
the adding amount of the ZSM-5 seed crystal is 0.5 to 5 percent of the weight of the synthetic liquid.
2. The templatedess synthesis method of ammonium-type ZSM-5 nanosheets of claim 1, wherein the source of aluminum is selected from at least one of aluminum isopropoxide, aluminum oxide, aluminum hydroxide, metallic aluminum, aluminum sol, aluminum sulfate, aluminum nitrate, or aluminum chloride.
3. The template-free synthesis method of ammonium-type ZSM-5 nanosheets of claim 1, wherein the silicon source is selected from at least one of silica, silica sol, white carbon black, ethyl orthosilicate, or activated clay.
4. The templatederless synthesis of ammonium ZSM-5 nanosheets of claim 1, characterized by the absence of alkali or alkaline earth metal ions in the product of step e).
5. The template-free synthesis method of ammonium-type ZSM-5 nanosheets of claim 1, wherein the amount of solids after calcination of the product of step e) is greater than 90% of the amount of added solids.
6. The template-free synthesis method of ammonium ZSM-5 nanosheets according to claim 1, wherein in step d), the crystallization temperature is 100 to 200 ℃ and the crystallization time is 0.5 to 240 hours.
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| CN103086399B (en) * | 2011-10-31 | 2014-12-10 | 华东师范大学 | Small-grain NH4-ZSM-5 zeolite and its one-step synthetic method |
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