CN108467048B - Acidity adjusting method for MFI type molecular sieve - Google Patents
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Abstract
The application belongs to the technical field of molecular sieve modification, and particularly relates to an acidity adjusting method for an MFI type molecular sieve. The acidity adjusting method provided by the invention comprises the following steps: heating the laminar MFI type molecular sieve subjected to ammonium ion exchange to a roasting temperature, and then adding NH3And N2The mixture of (3) was calcined in a nitrogen atmosphere and then cooled to room temperature. The method not only can well retain the morphology and the pore structure of the lamellar catalyst, but also can control the acidity of the lamellar MFI type molecular sieve by adjusting the nitrogen doping condition; is suitable for both small molecule catalysis and large molecule catalysis, and has simple operation. The method for controlling the moderate acidity of the molecular sieve is beneficial to inhibiting side reactions and improving the selectivity of main reactions, and has better application prospects in the aspects of catalytic cracking, heavy oil cracking and alkylation reactions.
Description
Technical Field
The invention belongs to the technical field of molecular sieve modification, and particularly relates to an acidity adjusting method for an MFI type molecular sieve.
Background
In acid-catalyzed reactions, two key factors that affect the performance of the catalytic reaction are: first, mass transfer resistance; the second is acidity. However, the traditional MFI type molecular sieve is mainly microporous, the size of the crystal grain is large, the diffusion resistance of macromolecules in the crystal is large, carbon deposition is easy to generate, and the catalytic life of the molecular sieve is shortened.
The lamellar molecular sieve is a lamellar crystal material with a pore opening system on a plane vertical to the lamellar layer, has smaller thickness of a molecular sieve crystal layer, can effectively shorten a molecular diffusion path, improves the molecular mass transfer rate and exposes more accessible active sites, thereby improving the catalytic performance. The MFI molecular sieve is formed from TO4The tetrahedrons are formed by three-dimensional four-connection frameworks formed by sharing vertex surfaces, T atoms on the frameworks are generally atoms of Si, Al or P and the like, each T atom is coordinated with four oxygen atoms, and each oxygen atom is bridged with two T atoms to form a microporous pore channel structure in regular arrangement. In most molecular sieves, trivalent Al atoms are linked to O atoms in the crystalline molecular sieve framework to form a four coordinate environment, causing a charge mismatch between the Al atoms and the framework, which mismatch charge needs to be balanced by other cations, such as H +, to form a bronsted acid that plays a key role in acid-catalyzed reactions.
In order to obtain a proper acidity, the acidity can be adjusted by adjusting the silica-alumina ratio, but the channel structure of the obtained MFI-type molecular sieve may also be changed due to the difference of the silica-alumina ratio. Patent CN 103950951B adopts cheap silicon source, gallium source, aluminum source, mineralizer and organic template agent to directly synthesize heteroatom ZSM-5 molecular sieve, but the MFI type molecular sieve synthesized by the method still mainly adopts the traditional micropore structure, is feasible for small molecule catalysis, and has too large mass transfer resistance for large molecule catalysis. Patent CN 106865564A discloses a multi-level pore heteroatom MFI type molecular sieve and a preparation method thereof, wherein Tween, span and the like are mainly used as mesoporous carbon sources, and then high-temperature carbonization treatment is carried out to obtain the multi-level pore MFI. However, the mesopores obtained by the hard template method are not uniformly distributed.
Disclosure of Invention
In order to solve the above technical problems, the present invention has a main object to provide a method for adjusting the acidity of an MFI-type molecular sieve.
The specific technical scheme of the invention is as follows:
a method for regulating the acidity of MFI-type molecular sieve includes such steps as heating the laminar MFI-type molecular sieve, which has undergone ammonium ion exchange, to calcining temp, and calcining in NH3And N2The mixture of (3) was calcined in a nitrogen atmosphere and then cooled to room temperature.
Preferably, the rate of temperature rise is 2 ℃/min to 5 ℃/min.
Preferably, the roasting temperature is 700-1000 ℃.
Preferably, the roasting time is 0.5 h-2.0 h.
Preferably, in the mixed atmosphere, the NH is3Accounting for 5 to 20 percent of the total volume.
Preferably, the total gas flow of the mixed atmosphere is 10mL/min to 30 mL/min.
Preferably, the preparation method of the ammonium ion exchanged laminar MFI type molecular sieve comprises the following steps: mixing laminated MFI type molecular sieve and NH4NO3Mixing the solutions, refluxing, and performing ammonium ion exchange; filtering, washing, drying and roasting to obtain the catalyst;
the NH4NO3The concentration of the solution is 1 mol/L-2 mol/L;
the laminated MFI type molecular sieve and NH4NO3The mixing mass ratio of the solution is 1 (10-30);
the reflux temperature is 70-90 ℃ and the reflux time is 8-12 h.
Further, the above-mentioned filtering, washing and drying are well known to those skilled in the art, and are not described herein again; the roasting specifically comprises the following steps: heating to 400-700 ℃ at the heating rate of 2-20 ℃/min, and roasting for 3-6 h.
Preferably, the lamellar MFI type molecular sieve is a product synthesized by a hydrothermal synthesis method by taking a tetraammonium head Bola type surfactant as a template agent and tetraethoxysilane as a silicon source;
the quaternary ammonium head Bola type surfactant is C6-6-12Br4The structural formula can be represented as: [ C ]6H13-N+(CH3)2-C6H12-N+(CH3)2-(CH2)10-O-(p-C6H4)2-O-(CH2)10-N+(CH3)2-C6H12-N+(CH3)2-C6H13]·4[Br-]。
The invention also provides the nitrogen-doped lamellar MFI-type molecular sieve obtained by the acidity adjusting method.
The foregoing acidity adjustment method and/or the foregoing nitrogen-doped lamellar MFI-type molecular sieve can also be applied to the preparation of a catalyst.
The invention puts the laminar MFI type molecular sieve which is exchanged by ammonium ion into NH3And N2The nitrogen atoms are doped into the molecular sieve framework to partially or completely replace the positions of the oxygen atoms in the molecular sieve framework, so that the acidity of the molecular sieve is adjusted, and the catalytic selectivity of the molecular sieve is further improved.
Compared with the prior art, the acidity adjusting method provided by the invention not only can perfectly keep the appearance and the pore structure of the lamellar catalyst, but also can control the acidity of the lamellar MFI type molecular sieve by adjusting the nitrogen doping condition; is suitable for both small molecule catalysis and large molecule catalysis, and has simple operation. The nitrogen-doped lamellar MFI type molecular sieve obtained by the method has the advantages of stable structure, uniform mesoporous distribution, small mass transfer resistance and more contactable active sites.
When the acidity adjusting method is applied to the preparation of the catalyst, the moderate acidity of the molecular sieve is beneficial to inhibiting side reactions and improving the selectivity of main reactions, and has better application prospects in the aspects of catalytic cracking, heavy oil cracking and alkylation reactions.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the provided drawings without creative efforts.
FIG. 1 is an X-ray diffraction pattern of the nitrogen-doped lamellar MFI-type molecular sieve of example 2;
FIG. 2 is a scanning electron micrograph of the nitrogen-doped lamellar MFI-type molecular sieve of example 2;
FIG. 3 is a pyridine infrared diagram of the nitrogen-doped lamellar MFI-type molecular sieve of example 2;
FIG. 4 shows the results of the characterization of the catalytic performance of the nitrogen-doped lamellar MFI-type molecular sieves of examples 2-3 and comparative example 1.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
The present embodiment provides a method for adjusting acidity of an MFI-type molecular sieve, including:
1. preparation of laminar MFI type molecular sieve
With 0.04mol SiO2Taking NaOH and NaAlO as reference2Template agent (tetraammonium head Bola type surfactant C)6-6-12Br4) And tetraethoxysilane are dissolved in water, and are magnetically stirred for 30min at the room temperature of 600rpm until the mixture is uniform, so that a precursor solution is obtained, and the molar ratio of the precursor solution is 16.28Na2O:125SiO2:2.0Al2O3:5C6-6-12Br4:5000H2O; and transferring the precursor solution A to a reaction kettle, crystallizing for 7 days at 150 ℃, filtering the reactant, collecting filter residues, and drying in a vacuum drying oven at 120 ℃ for 10 hours to obtain the sheet MFI type molecular sieve.
The above preparation process is specifically referred to the following documents:
B.Liu,Q.Duan,C.Li et al.Template synthesis of the hierarchically structured MFI zeolite with nanosheet frameworks and tailored structure。
2. preparation H+Lamellar MFI type molecular sieve
Mixing a lamella MFI type molecular sieve and 1.0mol/L NH4NO3Mixing the solutions, placing the mixed solution at 80 deg.C for refluxing for 3 times, each time for 10 hr, filtering, washing, drying, and roasting at 550 deg.C muffle furnace at 2 deg.C/min for 5 hr to obtain H+Type laminated MFI type molecular sieve. Wherein, the laminated MFI type molecular sieve and NH4NO3The mixing mass ratio of the solution is 1: 30.
3. Acidity regulation
1.0g of H is taken+Putting the laminated MFI type molecular sieve into a tube furnace, heating to 700 ℃ at the heating rate of 2 ℃/min, and introducing NH3And N2Mixed gas (NH) of (2)3Accounting for 5 percent of the total mixed gas, the total gas flow is 30mL/min), and roasting for 0.5h in the mixed atmosphere; NH shut off3Valve to make it continue at N2Cooling to room temperature under the atmosphere to obtain the nitrogen-doped lamellar MFI type molecular sieve A1。
Example 2
The present embodiment provides a method for adjusting acidity of an MFI-type molecular sieve, including:
1. preparation of laminar MFI type molecular sieve
This step is the same as embodiment 1 and is not described in detail.
2. Preparation H+Lamellar MFI type molecular sieve
Mixing a lamella MFI type molecular sieve and 1.2mol/L NH4NO3Solutions ofMixing, refluxing the mixture at 80 deg.C for 3 times (each time for 10 hr), filtering, washing, drying, and calcining to obtain H+Type laminated MFI type molecular sieve. Wherein, the laminated MFI type molecular sieve and NH4NO3The mixing mass ratio of the solution is 1: 20.
3. Acidity regulation
1.2g of H are taken+Putting the laminated MFI type molecular sieve into a tube furnace, heating to 800 ℃ at the heating rate of 5 ℃/min, and introducing NH3And N2Mixed gas (NH) of (2)3Accounting for 10 percent of the total mixed gas, the total gas flow is 20mL/min), and roasting for 1.0h in the mixed atmosphere; NH shut off3Valve to make it continue at N2Cooling to room temperature under the atmosphere to obtain the nitrogen-doped lamellar MFI type molecular sieve A2。
Example 3
The present embodiment provides a method for adjusting acidity of an MFI-type molecular sieve, including:
1. preparation of laminar MFI type molecular sieve
This step is the same as embodiment 1 and is not described in detail.
2. Preparation H+Lamellar MFI type molecular sieve
Mixing a lamella MFI type molecular sieve and 1.2mol/L NH4NO3Mixing the solutions, refluxing the mixture at 80 deg.C for 3 times (each time for 10 hr), filtering, washing, drying, and calcining to obtain H+Type laminated MFI type molecular sieve. Wherein, the laminated MFI type molecular sieve and NH4NO3The mixing mass ratio of the solution is 1: 20.
3. Acidity regulation
1.2g of H are taken+Putting the laminated MFI type molecular sieve into a tube furnace, heating to 800 ℃ at the heating rate of 5 ℃/min, and introducing NH3And N2Mixed gas (NH) of (2)3Accounting for 10 percent of the total mixed gas, the total gas flow is 20mL/min), and roasting for 2.0 hours in the mixed atmosphere; NH shut off3Valve to make it continue at N2Cooling to room temperature under the atmosphere to obtain the nitrogen-doped lamellar MFI type molecular sieve A3。
Example 4
The present embodiment provides a method for adjusting acidity of an MFI-type molecular sieve, including:
1. preparation of laminar MFI type molecular sieve
This step is the same as embodiment 1 and is not described in detail.
2. Preparation H+Lamellar MFI type molecular sieve
Mixing a lamella MFI type molecular sieve and 1.5mol/L NH4NO3Mixing the solutions, refluxing the mixture at 80 deg.C for 3 times (each time for 10 hr), filtering, washing, drying, and calcining to obtain H+Type laminated MFI type molecular sieve. Wherein, the laminated MFI type molecular sieve and NH4NO3The mixing mass ratio of the solution is 1: 15.
3. Acidity regulation
1.5g of H are taken+Putting the laminated MFI type molecular sieve into a tube furnace, heating to 900 ℃ at the heating rate of 10 ℃/min, and introducing NH3And N2Mixed gas (NH) of (2)315 percent of the total mixed gas and 15mL/min of total gas flow), and roasting for 1.5h in the mixed atmosphere; NH shut off3Valve to make it continue at N2Cooling to room temperature under the atmosphere to obtain the nitrogen-doped lamellar MFI type molecular sieve A4。
Example 5
The present embodiment provides a method for adjusting acidity of an MFI-type molecular sieve, including:
1. preparation of laminar MFI type molecular sieve
This step is the same as embodiment 1 and is not described in detail.
2. Preparation H+Lamellar MFI type molecular sieve
Mixing a lamella MFI type molecular sieve and 2.0mol/L NH4NO3Mixing the solutions, refluxing the mixture at 80 deg.C for 3 times (each time for 10 hr), filtering, washing, drying, and calcining to obtain H+Type laminated MFI type molecular sieve. Wherein, the laminated MFI type molecular sieve and NH4NO3The mixing mass ratio of the solution is 1: 10.
3. Acidity regulation
2.0g of H are taken+Putting the laminated MFI type molecular sieve into a tube furnace, heating to 1000 ℃ at the heating rate of 10 ℃/min, and introducing NH3And N2Mixed gas (NH) of (2)3Accounting for 20 percent of the total mixed gas, the total gas flow is 10mL/min), and roasting for 2.0 hours in the mixed atmosphere; NH shut off3Valve to make it continue at N2Cooling to room temperature under the atmosphere to obtain the nitrogen-doped lamellar MFI type molecular sieve A5。
Comparative example 1
The method for adjusting the acidity of the MFI type molecular sieve comprises the following steps:
1. preparation of laminar MFI type molecular sieve
This step is the same as embodiment 1 and is not described in detail.
2. Preparation H+Lamellar MFI type molecular sieve
Mixing a lamella MFI type molecular sieve and 1.5mol/L NH4NO3Mixing the solutions, refluxing the mixture at 80 deg.C for 3 times (each time for 10 hr), filtering, washing, drying, and calcining to obtain H+Type laminated MFI type molecular sieve. Wherein, the laminated MFI type molecular sieve and NH4NO3The mixing mass ratio of the solution is 1: 20.
3. Acidity regulation
1.2g of H are taken+Putting the laminated MFI type molecular sieve into a tube furnace, heating to 800 ℃ at the heating rate of 5 ℃/min, and introducing N2The total gas flow is 20mL/min, roasting is carried out for 1.0h under the nitrogen atmosphere, and then cooling is carried out to room temperature, thus obtaining the molecular sieve B1。
Example 6
Taking trimethylbenzene and benzyl alcohol as examples, the final products of examples 2-3 and comparative example 1 are respectively used as catalysts of the reaction to evaluate the catalytic performance of the prepared molecular sieve. Wherein the reaction temperature is 100 ℃, the dosage of the catalyst is 100mg respectively, and the molar ratio of the trimethylbenzene to the benzyl alcohol is 10: 1.
The evaluation result is shown in fig. 4, when the nitrogen-doped lamellar MFI-type molecular sieves of examples 2-3 are used as catalysts, the alkylation selectivity of trimethylbenzene and benzyl alcohol is higher, and the reaction selectivity can reach 74% after reacting for 20 hours, which is obviously higher than 66% of that of comparative example 1.
Claims (4)
1. A nitrogen-doped laminar MFI type molecular sieve for catalyzing trimethylbenzene and benzyl alcohol is characterized in that the acidity adjusting method of the nitrogen-doped laminar MFI type molecular sieve comprises the following steps: heating the laminar MFI type molecular sieve subjected to ammonium ion exchange to a roasting temperature, and then adding NH3And N2Roasting in the mixed atmosphere of (1), and cooling to room temperature in a nitrogen atmosphere;
the heating rate is 2-5 ℃/min;
the roasting temperature is 700-1000 ℃;
the roasting time is 0.5-2.0 h;
in the mixed atmosphere, the NH3Accounting for 5 to 20 percent of the total volume.
2. The nitrogen-doped laminar MFI-type molecular sieve of claim 1, wherein the total gas flow rate of said mixed atmosphere is from 10mL/min to 30 mL/min.
3. The nitrogen-doped laminar MFI-type molecular sieve of claim 1, wherein said ammonium ion exchanged laminar MFI-type molecular sieve is prepared by a process comprising: mixing laminated MFI type molecular sieve and NH4NO3Mixing the solutions, refluxing, and performing ammonium ion exchange; filtering, washing, drying and roasting to obtain the catalyst;
the NH4NO3The concentration of the solution is 1 mol/L-2 mol/L;
the laminated MFI type molecular sieve and NH4NO3The mixing mass ratio of the solution is 1 (10-30);
the reflux temperature is 70-90 ℃ and the reflux time is 8-12 h.
4. The nitrogen-doped lamellar MFI-type molecular sieve of claim 1, wherein said lamellar MFI-type molecular sieve is a product synthesized by a hydrothermal synthesis method using a tetra-ammonium head Bola-type surfactant as a template agent and tetraethoxysilane as a silicon source;
the quaternary ammonium head Bola type surfactant is C6-6-12Br4The structural formula can be represented as: [ C ]6H13-N+(CH3)2-C6H12-N+(CH3)2-(CH2)10-O-(p-C6H4)2-O-(CH2)10-N+(CH3)2-C6H12-N+(CH3)2-C6H13]·4[Br-]。
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