Patent Application
20210101801
The present invention relates to a process for preparing a porous oxidic material which comprises micropores and mesopores and which comprises a zeolitic material having a framework type AEI and having a framework structure comprising a tetravalent element Y, a trivalent element X and oxygen. Further, the present invention relates to a porous oxidic material which comprises micropores and mesopores and which comprises a zeolitic material having a framework type AEI and having a framework structure comprising a tetravalent element Y, a trivalent element X, and oxygen, and further relates to the use of said porous oxidic material as a catalytically active material, as a catalyst, or as a catalyst component.
Zeolitic materials having a framework type AEI are known to be potentially effective as catalysts or catalyst components in industrial applications, for example for converting nitrogen oxides (NOx) in an exhaust gas stream and for converting methanol-to-olefin (MTO). Synthetic AEI zeolitic materials may generally be produced by using organic templates. CN107285334 discloses a process for preparing a zeolitic material having a framework structure AEI using an alkyl piperidinium template and CN107285333 discloses a process for preparing a nano-sized zeolitic material having a framework type AEI using an alkyl piperidinium template and microwave heating. However, these processes do not permit to obtain a mesoporous zeolitic material having AEI framework type.
Therefore, it was an object of the present invention to provide a process for preparing a porous oxidic material which comprises micropores and mesopores and which comprises a zeolitic material having a framework type AEI having a framework structure comprising a tetravalent element Y, a trivalent element X and oxygen.
Surprisingly, it was found that the process according to the present invention permits to provide a porous oxidic material comprising a zeolitic material having a framework type AEI and both micropores and mesopores while being cost effective.
Therefore, the present invention relates to a process for preparing a porous oxidic material which comprises micropores and mesopores and which comprises a zeolitic material having a framework type AEI and having a framework structure comprising a tetravalent element Y, a trivalent element X and oxygen, wherein said micropores have a pore diameter determined according to nitrogen adsorption-desorption at 77 K of less than 2 nm and wherein said mesopores have a pore diameter determined according to nitrogen adsorption-desorption at 77 K in the range of from 2 to 50 nm, said process comprising:
wherein Y is one or more of Si, Sn, Ti, Zr and Ge;
wherein X is one or more of Al, B, In and Ga.
Preferably, the AEI framework type structure directing agent comprises a quaternary phosphonium cation containing compound, a N,N-diethyl-2,6-dimethylpiperidinium cation containing compound, a N,N-diethyl-3,5-dimethylpiperidinium cation containing compound, a N,N-dimethyl-2,6-dimethylpiperidinium cation containing compound, a N,N-dimethyl-3,5-dimethylpiperidinium cation containing compound, a N,N,N-trimethyl-1-adamantamonium cation containing compound, cis-2,6-dimethylpiperidinium cation containing compound, cis-trans-3,5-dimethylpiperidinium cation containing compound, a 2,2,7,7-tetramethyl-2-azabicyclo[4.1.1]octan-2-ium cation containing compound, a 1,3,3,6,6-pentamethyl-6-azabicyclo[3.2.1]octan-6-ium cation containing compound, or mixture thereof. More preferably, the AEI framework type structure directing agent comprises a quaternary phosphonium cation containing compound, a N,N-diethyl-2,6-dimethylpiperidinium cation containing compound. a N.N-diethyl-3,5-dimethylpiperidinium cation containing compound, a N,N,N-trimethyl-1-adamantamonium cation containing compound or mixture thereof. More preferably, the AEI framework type structure directing agent comprises a quaternary phosphonium cation containing compound, a N,N-diethyl-2,6-dimethylpiperidinium cation containing compound, a N,N-diethyl-3,5-dimethylpiperidinium cation containing compound or mixture thereof. More preferably, the AEI framework type structure directing agent comprises a quaternary phosphonium cation containing compound, a N,N-diethyl-2,6-dimethylpiperidinium cation containing compound or mixture thereof.
The quaternary phosphonium cation containing compound is preferably a R1R2R3R4P+-containing compound, wherein R1, R2, R3, and R4 independently from one another stand for optionally substituted and/or optionally branched (C1-C6)alkyl, more preferably (C1-C5)alkyl, more preferably (01-C4)alkyl, more preferably (C7-C3)alkyl, and preferably for optionally substituted methyl or ethyl, more preferably R1, R2, R3, and R4 stand for optionally substituted ethyl, more preferably unsubstituted ethyl.
Preferably, the quaternary phosphonium cation containing compound is a salt, more preferably one or more of a hydroxide and a halide, more preferably one or more of an iodide, a chloride, a fluoride and a bromide, wherein more preferably the quaternary phosphonium cation containing compound comprises, more preferably is, a hydroxide.
The N,N-diethyl-2,6-dimethylpiperidinium cation containing compound is preferably one or more of a N,N-diethyl-trans-2,6-dimethylpiperidinium cation containing compound and a N.N-diethyl-cis-2.6-dimethylpiperidinium cation containing compound, more preferably a N,N-diethyl-cis-2,6-dimethylpiperidinium cation containing compound.
Preferably, the N,N-diethyl-2,6-dimethylpiperidinium cation containing compound is a salt, more preferably one or more of a hydroxide and a halide, more preferably one or more of an iodide, a chloride, a fluoride and a bromide, wherein more preferably the N,N-diethyl-2,6-dimethylpiperidinium cation containing compound comprises, more preferably is, a hydroxide.
The N,N-diethyl-3,5-dimethylpiperidinium cation containing compound is preferably one or more of a N,N-diethyl-trans-3,5-dimethylpiperidinium cation containing compound and a N,N-diethyl-cis-3,5-dimethylpiperidinium cation containing compound.
Preferably, the N,N-diethyl-3,5-dimethylpiperidinium cation containing compound is a salt, more preferably one or more of a hydroxide and a halide, more preferably one or more of an iodide, a chloride, a fluoride and a bromide, wherein more preferably the N,N-diethyl-3,5-dimethylpiperidinium cation containing compound comprises, more preferably is, a hydroxide.
The N.N-dimethyl-2,6-dimethylpiperidinium cation containing compound is preferably one or more of a N,N-dimethyl-trans-2,6-dimethylpiperidinium cation containing compound and a N,N-dimethyl-cis-2,6-dimethylpiperidinium cation containing compound.
Preferably, the N,N-dimethyl-2,6-dimethylpiperidinium cation containing compound is a salt, more preferably one or more of a hydroxide and a halide, more preferably one or more of an iodide, a chloride, a fluoride and a bromide, wherein more preferably the N,N-dimethyl-2,6-dimethylpiperidinium cation containing compound comprises, more preferably is, a hydroxide.
The N,N-dimethyl-3,5-dimethylpiperidinium cation containing compound is preferably one or more of a N,N-dimethyl-trans-3,5-dimethylpiperidinium cation containing compound and a N,N-dimethyl-cis-3,5-dimethylpiperidinium cation containing compound.
It is more preferred that the N,N-dimethyl-3,5-dimethylpiperidinium cation containing compound is a N,N-dimethyl-trans-3,5-dimethylpiperidinium cation containing compound or a N,N-dimethyl-cis-3,5-dimethylpiperidinium cation containing compound. Alternatively, it is more preferred that the N,N-dimethyl-3,5-dimethylpiperidinium cation containing compound is a mixture of a N,N-dimethyl-trans-3,5-dimethylpiperidinium cation containing compound and a N,N-dimethyl-cis-3,5-dimethylpiperidinium cation containing compound. It is more preferred that in the mixture of a N,N-dimethyl-trans-3,5-dimethylpiperidinium cation containing compound and a N,N-dimethyl-cis-3,5-dimethylpiperidinium cation containing compound, the ratio of the trans-isomer to the cis-isomer is of at least 15:85, more preferably of at least 20:80, more preferably of at least 30:70, more preferably of at least 60:40, more preferably in the range of from 60:40 to 85:15, more preferably in the range of from 50:50 to 80:20.
Preferably, the N,N-dimethyl-3,5-dimethylpiperidinium cation containing compound is a salt, more preferably one or more of a hydroxide and a halide, more preferably one or more of an iodide, a chloride, a fluoride and a bromide, wherein more preferably the N,N-dimethyl-3,5-dimethylpiperidinium cation containing compound comprises, more preferably is, a hydroxide.
The cis-2,6-dimethylpiperidinium cation containing compound is preferably a salt, more preferably one or more of a hydroxide and a halide, more preferably one or more of an iodide, a chloride, a fluoride and a bromide, wherein more preferably the cis-2,6-dimethylpiperidinium cation containing compound comprises, more preferably is, a hydroxide.
The cis-trans-3,5-dimethylpiperidinium cation containing compound is preferably a salt, more preferably one or more of a hydroxide and a halide, more preferably one or more of an iodide, a chloride, a fluoride and a bromide, wherein more preferably the cis-trans-3,5-dimethylpiperidinium cation containing compound comprises, more preferably is, a hydroxide.
The 2,2,7,7-tetramethyl-2-azabicyclo[4.1.1]octan-2-ium cation containing compound is preferably a salt, more preferably one or more of a hydroxide and a halide, more preferably one or more of an iodide, a chloride, a fluoride and a bromide.
The 1,3,3,6,6-pentamethyl-6-azabicyclo[3.2.1]octan-6-ium cation containing compound is preferably a salt, more preferably one or more of a hydroxide and a halide, more preferably one or more of an iodide, a chloride, a fluoride and a bromide.
More preferably, the AEI framework type structure directing agent comprises a N,N-diethyl-2,6-dimethylpiperidinium cation containing compound, wherein the N,N-diethyl-2,6-dimethylpiperidinium cation containing compound is one or more of a N,N-diethyl-trans-2,6-dimethylpiperidinium cation containing compound and a N,N-diethyl-cis-2,6-dimethylpiperidinium cation containing compound, more preferably a N,N-diethy-cis-2,6-dimethylpiperidinium cation containing compound.
It is preferred that the dimethyloctadecyl[3-(tri-methoxysilyl)propyl]ammonium cation containing compound is a salt, more preferably one or more of a hydroxide and a halide, more preferably a halide, more preferably one or more of an iodide, a chloride, a fluoride and a bromide, wherein more preferably the dimethyloctadecyl[3-(trimethoxysilyl)propyl]ammonium cation containing compound comprises, more preferably is, a chloride.
Preferably, from 92 to 100 weight-%, more preferably from 95 to 100 weight-%, more preferably from 98 to 100 weight-%, more preferably from 99 to 100 weight-%, more preferably from 99.5 to 100 weight-%, more preferably from 99.9 to 100 weight-%, of the porous oxidic material consist of the zeolitic material having a framework type AEI.
In the context of the present invention, impurities may be present in the porous oxidic material. Such impurities may be one or more zeolitic materials having a framework structure different than AEI. For example, such impurities may be one or more of a zeolitic material having a framework type MOR and a zeolitic material having a framework type FAU.
Preferably, the porous oxidic material consists of micropores, mesopores and the zeolitic material having a framework type AEI.
It is preferred that Y is Si.
Preferably, X is one or more of Al and B, more preferably Al. More preferably, Y is Si and X is Al.
It is preferred that the zeolitic material provided in (i) and having a framework type FAU is a zeolitic material selected from the group consisting of a faujasite zeolite, a zeolite Y, a zeolite X, an LSZ-210 zeolite, a zeolite US Y, and a mixture of two or more thereof, more preferably selected from the group consisting of zeolite Y, US Y and a mixture thereof. It is more preferred that the zeolitic material provided in (i) and having a framework type FAU is a zeolite US Y. Alternatively, it is more preferred that the zeolitic material provided in (i) and having a framework type FAU is a zeolite Y.
In the framework structure of the zeolitic material having a framework type FAU provided in (i), the molar ratio of Y:X, calculated as YO2:X2O3, is preferably in the range of from 5:1 to 100:1, more preferably in the range of from 10:1 to 60:1, more preferably in the range of from 18:1 to 45:1, more preferably in the range of from 20:1 to 37:1, more preferably in the range of from 20:1 to 30:1.
It is more preferred that the zeolitic material provided in (1) and having a framework type FAU is a zeolite US Y, wherein in the framework structure of the zeolitic material having a framework type FAU provided in (i), the molar ratio of Y:X, calculated as YO2:X2O3, is in the range of from 20:1 to 30:1. It is more preferred that the zeolitic material provided in (i) and having a framework type FAU is a zeolite Y, wherein in the framework structure of the zeolitic material having a framework type FAU provided in (i), the molar ratio of Y:X, calculated as YO2:X2O3, is in the range of from 20:1 to 37:1.
In the synthesis mixture in (i), it is preferred that the molar ratio of the first organic structure directing agent, FOSDA, relative to Y, calculated as FOSDA:YO2, is in the range of from 0.05:1 to 0.30:1, more preferably in the range of from 0.10:1 to 0.20:1.
In the synthesis mixture in (i), it is preferred that the molar ratio of the second organic structure directing agent, SOSDA, relative to Y, calculated as SOSDA:YO2, is in the range of from 0.001:1 to 0.070:1, more preferably in the range of from 0.002:1 to 0.060:1. More preferably, in the synthesis mixture in (i), the molar ratio of the second organic structure directing agent, SOSDA, relative to Y, calculated as SOSDA:YO2, is in the range of from 0.002:1 to 0.012:1, more preferably in the range of from 0.004:1 to 0.011:1, more preferably in the range of from 0.006:1 to 0.010:1, more preferably in the range of from 0.007:1 to 0.009:1. Alternatively, in the synthesis mixture in (i), the molar ratio of the second organic structure directing agent, SOSDA, relative to Y, calculated as SOSDA:YO2, is more preferably in the range of from 0.006:1 to 0.022:1, more preferably in the range of from 0.010:1 to 0.020:1, more preferably in the range of from 0.013:1 to 0.017:1, more preferably in the range of from 0.015:1 to 0.018:1. As a further alternative, in the synthesis mixture in (i), the molar ratio of the second organic structure directing agent, SOSDA, relative to Y, calculated as SOSDA:YO2, is more preferably in the range of from 0.018:1 to 0.040:1, more preferably in the range of from 0.021:1 to 0.028:1, more preferably in the range of from 0.023:1 to 0.026:1.
In the synthesis mixture in (i), the molar ratio of the second organic structure directing agent, SOSDA, relative to Y, calculated as SOSDA:YO2, is more preferably in the range of from 0.007:1 to 0.026:1 or is in the range of from 0.007:1 to 0.017:1.
Therefore, the present invention preferably relates to a process for preparing a porous oxidic material which comprises micropores and mesopores and which comprises a zeolitic material having a framework type AEI and having a framework structure comprising a tetravalent element Y, a trivalent element X and oxygen, wherein said micropores have a pore diameter determined according to nitrogen adsorption-desorption at 77 K of less than 2 nm and wherein said mesopores have a pore diameter determined according to nitrogen adsorption-desorption at 77 K in the range of from 2 to 50 nm, said process comprising:
wherein Y is one or more of Si, Sn, Ti, Zr and Ge;
wherein X is one or more of Al, B, In and Ga,
wherein the AEI framework type structure directing agent comprises a N,N-diethyl-2,6-dimethylpiperidinium cation containing compound, wherein the N,N-diethyl-2,6-dimethylpiperidinium cation containing compound is one or more of a N,N-diethyl-trans-2,6-dimethylpiperidinium cation containing compound and a N,N-diethyl-cis-2,6-dimethylpiperidinium cation containing compound, more preferably a N,N-diethyl-cis-2,6-dimethylpiperidinium cation containing compound,
wherein, in the synthesis mixture in (i), the molar ratio of the first organic structure directing agent, FOSDA, relative to Y, calculated as FOSDA:YO2, is in the range of from 0.05:1 to 0.30:1, more preferably in the range of from 0.10:1 to 0.20:1,
wherein, in the synthesis mixture in (i), the molar ratio of the second organic structure directing agent, SOSDA, relative to Y, calculated as SOSDA:YO2, is in the range of from 0.001:1 to 0.070:1, more preferably in the range of from 0.002:1 to 0.060:1.
In the context of the present invention, in the synthesis mixture in (i), it is preferred that the molar ratio of the source of a base relative to Y, calculated as a source of a base:YO2, is in the range of from 0.10:1 to 0.70:1, more preferably in the range of from 0.20:1 to 0.60:1, more preferably in the range of from 0.30:1 to 0.55:1. It is more preferred that in the synthesis mixture in (i), the molar ratio of the source of a base relative to Y, calculated as a source of a base:YO2, is in the range of from 0.40:1 to 0.50:1, more preferably in the range of from 0.43:1 to 0.48:1, more preferably in the range of from 0.44:1 to 0.47:1. Alternatively, it is more preferred that in the synthesis mixture in (i), the molar ratio of the source of a base relative to Y, calculated as a source of a base:YO2, is in the range of from 0.30:1 to 0.38:1, more preferably in the range of from 0.32:1 to 0.36:1.
It is more preferred that in the synthesis mixture in (i) which comprises a zeolite US Y, the molar ratio of the source of a base relative to Y, calculated as a source of a base:YO2, is in the range of from 0.39:1 to 0.50:1, more preferably in the range of from 0.40:1 to 0.48:1, more preferably in the range of from 0.44:1 to 0.47:1. Alternatively, it is more preferred that in the synthesis mixture in (i) which comprises a zeolite Y, the molar ratio of the source of a base relative to Y, calculated as a source of a base:YO2, is in the range of from 0.30:1 to 0.38:1, more preferably in the range of from 0.32:1 to 0.36:1.
It is more preferred that in the synthesis mixture in (i), the molar ratio of the source of a base relative to Y, calculated as a source of a base:YO2, is in the range of from 0.32:1 to 0.47:1.
Preferably, in the synthesis mixture in (i), the molar ratio of H2O relative to Y, calculated as H2O:YO2, is in the range of from 2:1 to 80:1, more preferably in the range of from 10:1 to 60:1, more preferably in the range of from 25:1 to 50:1, more preferably in the range of from 28:1 to 47:1, more preferably in the range of from 30:1 to 45:1.
There is no particular restriction as to the source of a base provided (i) provided that it permits to obtain a porous oxidic material which comprises micropores and mesopores and which comprises a zeolitic material having a framework type AEI and having a framework structure comprising a tetravalent element Y, a trivalent element X and oxygen. It is preferred that the source of a base provided in (i) comprises, more preferably is, a hydroxide.
It is preferred that the source of a base provided in (i) comprises, more preferably is, one or more of an alkali metal hydroxide and an alkaline earth metal hydroxide, more preferably an alkali metal hydroxide, more preferably sodium hydroxide.
In the context of the present invention, there is no particular restriction as to the type of seed crystals provided in (i). Preferably, the seed crystals provided in (i) comprise, more preferably consist of, a zeolitic material having a framework type selected from the group consisting of AEI, CHA and RTH, more preferably a zeolitic material having a framework type selected from the group consisting of AEI and CHA, wherein more preferably the seed crystals provided in (i) comprise, more preferably consist of, a zeolitic material having a framework type AEI.
Preferably, in the synthesis mixture (i), the weight ratio of the seed crystals to the zeolitic material having a framework type FAU is in the range of from 0.001:1 to 0.1:1, more preferably in the range of from 0.005:1 to 0.05:1, more preferably in the range of from 0.01:1 to 0.04:1.
Therefore, the present invention preferably relates to a process for preparing a porous oxidic material which comprises micropores and mesopores and which comprises a zeolitic material having a framework type AEI and having a framework structure comprising a tetravalent element Y, a trivalent element X and oxygen, wherein said micropores have a pore diameter determined according to nitrogen adsorption-desorption at 77 K of less than 2 nm and wherein said mesopores have a pore diameter determined according to nitrogen adsorption-desorption at 77 K in the range of from 2 to 50 nm, said process comprising:
wherein Y is one or more of Si, Sn, Ti, Zr and Ge;
wherein X is one or more of Al, B, In and Ga;
wherein the AEI framework type structure directing agent comprises a N,N-diethyl-2,6-dimethylpiperidinium cation containing compound, wherein the N,N-diethyl-2,6-dimethylpiperidinium cation containing compound is one or more of a N,N-diethyl-trans-2,6-dimethylpiperidinium cation containing compound and a N,N-diethyl-cis-2,6-dimethylpiperidinium cation containing compound, more preferably a N,N-diethyl-cis-2,6-dimethylpiperidinium cation containing compound,
wherein, in the synthesis mixture in (i), the molar ratio of the first organic structure directing agent, FOSDA, relative to Y, calculated as FOSDA:YO2, is in the range of from 0.05:1 to 0.30:1, more preferably in the range of from 0.10:1 to 0.20:1,
wherein, in the synthesis mixture in (i), the molar ratio of the second organic structure directing agent, SOSDA, relative to Y, calculated as SOSDA:YO2, is in the range of from 0.001:1 to 0.070:1, more preferably in the range of from 0.002:1 to 0.060:1,
wherein, in the synthesis mixture in (i), the molar ratio of the source of a base relative to Y, calculated as a source of a base:YO2, is in the range of from 0.10:1 to 0.70:1, more preferably in the range of from 0.20:1 to 0.60:1, more preferably in the range of from 0.30:1 to 0.55:1, more preferably in the range of from 0.32:1 to 0.47:1,
wherein, in the synthesis mixture (i), the weight ratio of the seed crystals to the zeolitic material having a framework type FAU is in the range of from 0.001:1 to 0.1:1, more preferably in the range of from 0.005:1 to 0.05:1, more preferably in the range of from 0.01:1 to 0.04:1.
In the context of the present invention, it is preferred that from 95 to 100 weight-%, more preferably from 98 to 100 weight-%, more preferably from 99 to 100 weight-%, more preferably from 99.5 to 100 weight-% of the synthesis mixture consist of the zeolitic material having a framework type FAU and having a framework structure comprising the tetravalent element Y, the trivalent element X and oxygen, water, the source of base, the first organic structure directing agent comprising an AEI framework type structure directing agent, the second organic structure directing agent comprising a dimethyloctadecyl[3-(trimethoxysilyl)propyl]ammonium cation containing compound and the seed crystals.
According to the present invention, there is no specific restriction on how the synthesis mixture is prepared in (i). Preferably, preparing the synthesis mixture in (i) comprises
Preferably, preparing the first mixture in (i.1) comprises adding the first organic structure directing agent dropwise to the zeolitic material.
Preferably, preparing the first mixture in (i.1) comprises agitating, more preferably mechanically agitating, more preferably stirring, the mixture. As to (i.1), agitating is preferably performed at a temperature of the mixture in the range of from 12 to 35° C., more preferably in the range of from 15 to 30 00. As to (i.1), agitating is preferably performed for a duration in the range of from 0.10 to 3 hours, more preferably in the range of from 0.25 to 2 hours, more preferably in the range of from 0.4 to 1.75 hours, more preferably in the range of from 0.5 to 1.5 hours.
Preferably, preparing the second mixture according to (i.2) comprises agitating, more preferably mechanically agitating, more preferably stirring, the mixture. As to (i.2), agitating is preferably performed at a temperature of the mixture in the range of from 12 to 35° C., more preferably in the range of from 15 to 30° C. As to (i.2), agitating is preferably performed for a duration in the range of from 0.10 to 3 hours, more preferably in the range of from 0.25 to 2 hours, more preferably in the range of from 0.4 to 1.75 hours, more preferably in the range of from 0.5 to 1.5 hours.
Preferably, preparing the third mixture according to (i.3) preferably comprises agitating, more preferably mechanically agitating, more preferably stirring, the mixture. As to (i.3), agitating is preferably performed at a temperature of the mixture in the range of from 12 to 35° C., more preferably in the range of from 15 to 30° C. As to (i.3), agitating is preferably performed for a duration in the range of from 0.25 to 10 hours. It is more preferred that agitating according to (i.3) is performed for a duration in the range of from 0.25 to 4 hours, more preferably in the range of from 0.5 to 3 hours, more preferably in the range of from 1 to 2 hours. Alternatively, it is more preferred that agitating according to (i.3) is performed for a duration in the range of from 1 to 8 hours, more preferably in the range of from 2 to 6 hours, more preferably in the range of from 3 to 5 hours.
Preferably, preparing the synthesis mixture according to (i.4) preferably comprises agitating, more preferably mechanically agitating, more preferably stirring, the mixture. As to (i.4), agitating is preferably performed at a temperature of the mixture in the range of from 12 to 35° C., more preferably in the range of from 15 to 30° C. As to (i.4), agitating is preferably performed for a duration in the range of from 5 to 50 minutes. It is more preferred that agitating according to (i.4) is performed for a duration in the range of from 10 to 30 minutes, more preferably in the range of from 15 to 25 minutes. Alternatively, it is more preferred that agitating according to (i.4) is performed for a duration in the range of from 5 to 13 minutes.
According to (ii), the hydrothermal crystallization conditions preferably comprise a crystallization duration in the range of from 0.75 to 20 days, more preferably in the range of from 0.9 to 15 days, more preferably in the range of from 1 to 12 days, more preferably in the range of from 2 to 10 days, more preferably in the range of from 2 to 8 days. It is more preferred that according to (ii) the hydrothermal crystallization conditions comprise a crystallization duration in the range of from 4 to 8 days. Alternatively, it is more preferred that according to (ii) the hydrothermal crystallization conditions comprise a crystallization duration in the range of from 2 to 3.5 days.
It is more preferred that, when the synthesis mixture prepared in (i) comprises a zeolite US Y, according to (ii) the hydrothermal crystallization conditions comprise a crystallization duration in the range of from 4 to 8 days. It is more preferred that, when the synthesis mixture prepared in (i) comprises a zeolite Y, according to (ii) the hydrothermal crystallization conditions comprise a crystallization duration in the range of from 2 to 3.5 days.
According to (ii), the hydrothermal crystallization conditions preferably comprise a crystallization temperature in the range of from 100 to 180° C., more preferably in the range of from 120 to 160 00, more preferably in the range of from 130 to 150° C.
It is preferred that, during the hydrothermal crystallization according to (ii), the mixture obtained in (i) and subjected to (ii) is agitated, more preferably mechanically agitated, more preferably stirred.
According to (ii), it is preferred that subjecting the synthesis mixture obtained in (i) to hydro-thermal crystallization conditions is carried out under autogenous pressure, more preferably in an autoclave.
According to the present invention, it is preferred that the process further comprises
It is preferred that the process according to the present invention further comprises
Preferably, (iv) comprises
As to (iv.2), the porous oxidic material is preferably washed with water, more preferably with deionized water.
As to (iv.3), the porous oxidic material is preferably dried in a gas atmosphere having a temperature in the range of from 60 to 200° C., more preferably in the range of from 80 to 140° C., more preferably in the range of from 90 to 110° C.
As to (iv.3), the porous oxidic material is preferably dried in a gas atmosphere for a duration in the range of from 0.5 to 5 hours, more preferably in the range of from 1 to 4 hours, more preferably in the range of from 1 to 3 hours,
More preferably, the gas atmosphere in (iv.3) comprises, more preferably is, one or more of air, lean air, and oxygen, more preferably air.
Therefore, the present invention preferably relates to a process for preparing a porous oxidic material which comprises micropores and mesopores and which comprises a zeolitic material having a framework type AEI and having a framework structure comprising a tetravalent element Y, a trivalent element X and oxygen, wherein said micropores have a pore diameter determined according to nitrogen adsorption-desorption at 77 K of less than 2 nm and wherein said mesopores have a pore diameter determined according to nitrogen adsorption-desorption at 77 K in the range of from 2 to 50 nm, said process comprising:
wherein Y is one or more of Si, Sn, Ti, Zr and Ge;
wherein X is one or more of Al, B, In and Ga,
wherein the AEI framework type structure directing agent comprises a N,N-diethyl-2,6-dimethylpiperidinium cation containing compound, wherein the N,N-diethyl-2,6-dimethylpiperidinium cation containing compound is one or more of a N,N-diethyl-trans-2,6-dimethylpiperidinium cation containing compound and a N,N-diethyl-cis-2,6-dimethylpiperidinium cation containing compound, more preferably a N,N-diethyl-cis-2.6-dimethylpiperidinium cation containing compound,
wherein, in the synthesis mixture in (i), the molar ratio of the first organic structure directing agent, FOSDA, relative to Y, calculated as FOSDA:YO2, is in the range of from 0.05:1 to 0.30:1, more preferably in the range of from 0.10:1 to 0.20:1,
wherein, in the synthesis mixture in (i), the molar ratio of the second organic structure directing agent, SOSDA, relative to Y, calculated as SOSDA:YO2, is in the range of from 0.001:1 to 0.070:1, more preferably in the range of from 0.002:1 to 0.060:1,
wherein, in the synthesis mixture in (i), the molar ratio of the source of a base relative to Y, calculated as a source of a base:YO2, is in the range of from 0.10:1 to 0.70:1, more preferably in the range of from 0.20:1 to 0.60:1, more preferably in the range of from 0.30:1 to 0.55:1, more preferably in the range of from 0.32:1 to 0.47:1,
wherein, in the synthesis mixture (i), the weight ratio of the seed crystals to the zeolitic material having a framework type FAU is in the range of from 0.001:1 to 0.1:1, more preferably in the range of from 0.005:1 to 0.05:1, more preferably in the range of from 0.01:1 to 0.04:1.
In the context of the present invention, it is preferred that the process further comprises
As to (v), the porous oxidic material is preferably calcined in a gas atmosphere having a temperature in the range of from 300 to 550° C.
As to (v), it is preferred that the porous oxidic material obtained from calcination has a total organic carbon content of at most 0.1 weight-%.
According to the present invention, it is preferred that said micropores have a micropore volume and said mesopores have a mesopore volume and wherein the ratio of mesopore volume to micropore volume of the porous oxidic material is of at least 0.5:1 and the ratio of rnesopore volume to the total pore volume of the porous oxidic material is of at least 0.3:1.
Preferably, said micropores have a micropore volume and said mesopores have a rnesopore volume, wherein the ratio of mesopore volume to micropore volume of the porous oxidic material is in the range of from 0.5:1 to 3:1, more preferably in the range of from 0.6:1 to 2:1.
It is preferred that said micropores have a micropore volume and said mesopores have a mesopore volume, wherein the ratio of mesopore volume to micropore volume of the porous oxidic material is in the range of from 0.75:1 to 2.5:1, more preferably in the range of from 1:1 to 2.1:1, more preferably in the range of from 1.35:1 to 2:1. Alternatively, it is preferred that said micropores have a micropore volume and said mesopores have a mesopore volume, wherein the ratio of mesopore volume to micropore volume of the porous oxidic material is in the range of from 0.55:1 to 2:1, more preferably in the range of from 0.6:1 to 1.25:1.
It is preferred that said micropores have a micropore volume and said mesopores have a mesopore volume, wherein the ratio of mesopore volume to the total pore volume of the porous oxidic material is in the range of from 0.3:1 to 1:1, more preferably in the range of from 0.35:1 to 0.95:1, more preferably in the range of from 0.38:1 to 0.7:1.
It is preferred that said micropores have a micropore volume and said mesopores have a mesopore volume, wherein the ratio of mesopore volume to the total pore volume of the porous oxidic material is in the range of from 0.4:1 to 0.9:1, more preferably in the range of from 0.50:1 to 0.75:1, more preferably in the range of 0.55:1 to 0.7:1. Alternatively, it is preferred that said micropores have a micropore volume and said mesopores have a mesopore volume, wherein the ratio of mesopore volume to the total pore volume of the porous oxidic material is in the range of from 0.35:1 to 0.6:1, more preferably in the range of from 0.38:1 to 0.55:1.
In the context of the present invention, the terms “total pore volume of the porous oxidic material” and “total pore volume” refer to the sum of the mesopore volume of the porous oxidic material and the micropore volume of a porous oxidic material.
Preferably, said mesopores of the porous oxidic material have a mesopore volume, determined as described in Reference Example 1 b), in the range of from 0.15 to 0.80 cm3/g.
It is more preferred that the mesopores of the porous oxidic material have a mesopore volume, determined as described in Reference Example 1 b), in the range of from 0.20 to 0.65 cm3/g, more preferably in the range of from 0.25 to 0.55 cm3/g, more preferably in the range of from 0.30 to 0.50 cm3/g. More preferably, the mesopore volume, determined as described in Reference Example 1 b), is in the range of from 0.30 to 0.40 cm3/g, more preferably in the range of from 0.32 to 0.38 cm3/g. As an alternative, more preferably the mesopore volume, determined as described in Reference Example 1 b), is in the range of from 0.40 to 0.50 cm3/g, more preferably in the range of from 0.42 to 0.48 cm3/g.
Alternatively, it is more preferred that the mesopores of the porous oxidic material have a mesopore volume, determined as described in Reference Example 1 b), in the range of from 0.15 to 0.50 cm3/g, preferably in the range of from 0.15 to 0.40 cm3/g, more preferably in the range of from 0.16 to 0.30 cm3/g.
It is preferred that said micropores of the porous oxidic material have a micropore volume, determined as described in Reference Example 1 b), in the range of from 0.05 to 0.50 cm3/g, more preferably in the range of from 0.10 to 0.40 cm3/g, more preferably in the range of from 0.20 to 0.30 cm3/g.
According to the present invention, the process preferably further comprises
In particular, (vi) preferably comprises
More preferably, the solution comprising ammonium ions according to (vi.1) is an aqueous solution comprising a dissolved ammonium salt, preferably a dissolved inorganic ammonium salt, more preferably a dissolved ammonium nitrate.
According to (vi.1), it is preferred that the solution comprising ammonium ions according to (vi.1) has an ammonium concentration in the range of from 0.10 to 3 mol/l, more preferably in the range of from 0.20 to 2 mol/l, more preferably in the range of from 0.5 to 1.5 mol/l.
According to (vi.1), it is preferred that the solution comprising ammonium ions is brought in contact with the zeolitic material obtained from (iv) or (v) at a temperature of the solution in the range of from 60 to 100° C., more preferably in the range of from 70 to 90° C.
According to (vi.1), it is preferred that the solution comprising ammonium ions is brought in contact with the zeolitic material obtained from (iv) or (v) for a period of time in the range of from 1 to 6 hours, more preferably in the range of from 1.5 to 4 hours.
According to (vi.1), bringing the solution in contact with the porous oxidic material preferably comprises one or more of impregnating the porous oxidic material with the solution and spraying the solution onto the porous oxidic material, more preferably impregnating the porous oxidic material with the solution.
Preferably, (vi) further comprises
According to (iv.2), calcining preferably is performed in gas atmosphere for a duration in the range of from 2 to 6 hours, more preferably in the range of from 3 to 5 hours.
Preferably, (vi.1) and (vi.2) are carried out at least once, more preferably twice.
Preferably, as to (vi.2), the gas atmosphere comprises, more preferably is, one or more of air, lean air, and oxygen, more preferably air.
Preferably, (vi) further comprises
According to (vi.3), it is preferred that the solution comprising ions of one or more transition metals is an aqueous solution comprising a dissolved salt of one or more transition metals, more preferably a dissolved organic copper salt, more preferably a dissolved copper acetate.
According to (vi.3), it is preferred that the solution comprising ions of one or more transition metals has a transition metal concentration, more preferably a copper concentration, in the range of from 0.10 to 3 mol/l, more preferably in the range of from 0.20 to 2 moll!, more preferably in the range of from 0.5 to 1.5 mol/l.
According to (vi.3), the solution comprising ions of one or more transition metals is preferably brought in contact with the porous oxidic material obtained from (vi.2) at a temperature of the solution in the range of from 60 to 100° C., more preferably in the range of from 70 to 90° C.
According to (vi.3), the solution comprising ions of one or more transition metals is preferably brought in contact with the zeolitic material obtained from (vi.2) for a period of time in the range of from 0.5 to 3 hours, more preferably in the range of from 0.5 to 2 hours.
It is preferred that (vi) further comprises
As to (vi.4), calcining is preferably performed in gas atmosphere for a duration in the range of from 1 to 6 hours, more preferably in the range of from 3 to 5 hours.
As to (vi.4), the gas atmosphere preferably comprises, more preferably is, one or more of air, lean air, and oxygen, more preferably air.
Therefore, the present invention preferably relates to a process for preparing a porous oxidic material which comprises micropores and mesopores and which comprises a zeolitic material having a framework type AEI and having a framework structure comprising a tetravalent element Y, a trivalent element X and oxygen, wherein said micropores have a pore diameter determined according to nitrogen adsorption-desorption at 77 K of less than 2 nm and wherein said mesopores have a pore diameter determined according to nitrogen adsorption-desorption at 77 K in the range of from 2 to 50 nm, said process comprising:
wherein Y is one or more of Si, Sn, Ti, Zr and Ge;
wherein X is one or more of Al, B, In and Ga,
wherein the AEI framework type structure directing agent comprises a N,N-diethyl-2.6-dimethylpiperidinium cation containing compound, wherein the N,N-diethyl-2,6-dimethylpiperidinium cation containing compound is one or more of a N,N-diethyl-trans-2,6-dimethylpiperidinium cation containing compound and a N,N-diethyl-cis-2,6-dimethylpiperidinium cation containing compound, more preferably a N,N-diethyl-cis-2,6-dimethylpiperidinium cation containing compound,
wherein, in the synthesis mixture in (i), the molar ratio of the first organic structure directing agent, FOSDA, relative to Y, calculated as FOSDA:YO2, is in the range of from 0.05:1 to 0.30:1, more preferably in the range of from 0.10:1 to 0.20:1,
wherein, in the synthesis mixture in (i), the molar ratio of the second organic structure directing agent, SOSDA, relative to Y, calculated as SOSDA:YO2, is in the range of from 0.001:1 to 0.070:1, more preferably in the range of from 0.002:1 to 0.060:1,
wherein, in the synthesis mixture in (i), the molar ratio of the source of a base relative to Y, calculated as a source of a base:YO2, is in the range of from 0.10:1 to 0.70:1, more preferably in the range of from 0.20:1 to 0.60:1, more preferably in the range of from 0.30:1 to 0.55:1,
wherein, in the synthesis mixture (i), the weight ratio of the seed crystals to the zeolitic material having a framework type FAU is in the range of from 0.001:1 to 0.1:1, more preferably in the range of from 0.005:1 to 0.05:1, more preferably in the range of from 0.01:1 to 0.04:1.
In the context of the present invention, it is preferred that the process further comprises
Ageing in (vii) is preferably performed in gas atmosphere, more preferably in air, having a temperature in the range of from 400 to 1000° C., more preferably in the range of from 600 to 800° C. As to (vii), ageing is preferably performed for a duration in the range of from 5 to 100 hours, more preferably in the range of from 10 to 60 hours.
As to (vii), it is preferred that the gas atmosphere comprises, more preferably is, one or more of air, lean air, and oxygen, more preferably air.
It is preferred that the process of the present invention consists of (i) and (ii), more preferably of (i), (ii) and (iv), and more preferably (i), (ii), (iv) and (v). It is more preferred that the process of the present invention consists of (i), (ii), (iii), (iv) and (v), more preferably of (i), (ii), (iii), (iv), (v), and (vi). It may be more preferred that the process of the present invention consists of (i), (ii), (iii), (iv), (v), (vi) and (vii).
The present invention further relates to a porous oxidic material which comprises micropores and mesopores and which comprises a zeolitic material having a framework type AEI and having a framework structure comprising a tetravalent element Y, a trivalent element X, and oxygen, wherein said micropores have a pore diameter determined according to nitrogen adsorption-desorption at 77 K of less than 2 nm and wherein said mesopores have a pore diameter determined according to nitrogen adsorption-desorption at 77 K in the range of from 2 to 50 nm, wherein Y is one or more of Si, Sn, Ti, Zr, and Ge and wherein X is one or more of Al, B, In, and Ga. wherein said micropores have a micropore volume and said mesopores have a mesopore volume, the ratio of mesopore volume to micropore volume being of at least 0.5:1 and the ratio of mesopore volume to the total pore volume of the porous oxidic material being of at least 0.3:1, wherein the porous oxidic material is obtainable or obtained by a process according to the present invention.
The present invention further relates to a porous oxidic material which comprises micropores and mesopores and which comprises a zeolitic material having a framework type AEI and having a framework structure comprising a tetravalent element Y, a trivalent element X, and oxygen, wherein said micropores have a pore diameter determined according to nitrogen adsorption-desorption at 77 K of less than 2 rim arid wherein said mesopores have a pore diameter determined according to nitrogen adsorption-desorption at 77 K in the range of from 2 to 50 rim, wherein Y is one or more of Si, Sn, Ti, Zr, and Ge and wherein X is one or more of Al, B, In, and Ga, wherein said micropores have a micropore volume and said mesopores have a mesopore volume, the ratio of mesopore volume to micropore volume being of at least 0.5:1 and the ratio of mesopore volume to the total pore volume of the porous oxidic material being of at least 0.3:1, wherein the porous oxidic material is preferably obtainable or obtained by a process according to the present invention.
Preferably, Y is Si and X is one or more of Al and B. More preferably, Y is Si and X is Al.
It is preferred that the zeolitic material having a framework type AEI is a zeolite SSZ-39.
Preferably, from 92 to 100 weight-%, more preferably from 95 to 100 weight-%, more preferably from 98 to 100 weight-%, more preferably from 99 to 100 weight-%, more preferably from 99.5 to 100 weight-%, more preferably from 99.9 to 100 weight-%, of the porous oxidic material consist of a zeolitic material having a framework type AEI.
In the context of the present invention, impurities may be present in the porous oxidic material. Such impurities may be one or more zeolitic materials having a framework structure different than AEI. For example, such impurities may be one or more of a zeolitic material having a framework type MOR and a zeolitic material having a framework type FAU.
Preferably, in the framework structure of the zeolitic material having framework type AEI, the molar ratio of Y:X, calculated as a YO2:X2O3, is in the range of from 2:1 to 40:1, more preferably in the range of from 10:1 to 30:1, more preferably in the range of from 14:1 to 26:1, more preferably in the range of from 16:1 to 24:1.
It is preferred that the porous oxidic material has a BET specific surface area, determined as described in Reference Example 1 b), in the range of from 500 to 900 m2/g, more preferably in the range of from 540 to 820 m2/g.
It is preferred that the porous oxidic material has a BET specific surface area, determined as described in Reference Example 1 b), in the range of from 600 to 900 m2/g, more preferably in the range of from 650 to 850 m2/g, more preferably in the range of from 750 to 830 m2/g, more preferably in the range of from 785 to 820 m2/g. Alternatively, it is preferred that the porous oxidic material preferably has a BET specific surface area, determined as described in Reference Example 1 b), in the range of from 520 to 600 m2/g, more preferably in the range of from 540 to 575 m2/g.
Preferably, the mesopore volume, determined as described in Reference Example 1 b), is in the range of from 0.15 to 0.80 cm3/g, more preferably in the range of from 0.15 to 0.50 cm3/g, more preferably in the range of from 0.16 to 0.48 cm3/g.
It is preferred that the mesopore volume, determined as described in Reference Example 1 b), is in the range of from 0.20 to 0.65 cm3/g, more preferably in the range of from 0.25 to 0.55 cm3/g, more preferably in the range of from 0.30 to 0.50 cm3/g. More preferably, the mesopore volume, determined as described in Reference Example 1 b), is in the range of from 0.30 to 0.40 cm3/g, more preferably in the range of from 0.32 to 0.38 cm3/g. Alternatively, more preferably the mesopore volume, determined as described in Reference Example 1 b), is in the range of from 0.40 to 0.50 cm3/g, more preferably in the range of from 0.42 to 0.48 cm3/g.
Alternatively, it is preferred that the mesopore volume, determined as described in Reference Example 1 b), is in the range of from 0.15 to 0.50 cm3/g, more preferably in the range of from 0.15 to 0.40 cm3/g, more preferably in the range of from 0.16 to 0.30 cm3/g.
It is preferred that the micropore volume, determined as described in Reference Example 1 b), is in the range of from 0.05 to 0.50 cm3/g, more preferably in the range of from 0.10 to 0.40 cm3/g, more preferably in the range of from 0.20 to 0.30 cm3/g.
Preferably, the ratio of mesopore volume to micropore volume is in the range of from 0.5:1 to 3:1. More preferably, the ratio of mesopore volume to micropore volume is in the range of from 0.75:1 to 2.5:1, more preferably in the range of from 1:1 to 2.1:1, more preferably in the range of from 1.35:1 to 2:1. Alternatively, it is more preferred that the ratio of mesopore volume to micropore volume is in the range of from 0.55:1 to 2:1, more preferably in the range of from 0.6:1 to 1.25:1.
Preferably, the ratio of mesopore volume to the total pore volume of the porous oxidic material is in the range of from 0.3:1 to 1:1, more preferably in the range of from 0.35:1 to 0.95:1, more preferably in the range of from 0.38:1 to 0.7:1.
It is preferred that the ratio of mesopore volume to the total pore volume is in the range of from 0.4:1 to 0.9:1, more preferably in the range of from 0.50:1 to 0.75:1, more preferably in the range of 0.55:1 to 0.7:1. Alternatively, it is preferred that the ratio of mesopore volume to the total pore volume is in the range of from 0.35:1 to 0.6:1, more preferably in the range of from 0.38:1 to 0.55:1.
It is preferred that the porous oxidic material has a crystallinity, determined as described in Reference Example 1 e), in the range of from 80 to 100%, preferably in the range of from 90 to 100%, more preferably in the range of from 99 to 100%.
It is preferred that the zeolitic material having a framework type AEI has an X-ray diffraction pattern comprises at least the following reflections:
wherein 100% relates to the intensity of the maximum peak in the X-ray powder diffraction pattern. More preferably, the zeolitic material having a framework type AEI has an X-ray diffraction pattern comprises at least the following reflections:
wherein 100% relates to the intensity of the maximum peak in the X-ray powder diffraction pattern.
Preferably. the porous oxidic material additionally comprises one or more transition metals.
more preferably one or more of Cu and Fe, more preferably Cu. More preferably, the porous oxidic material contains the one or more transition metals in a total amount of from 1.5 to 5.0 weight-%, more preferably of from 2.5 to 4.5 weight-%, more preferably of from 3.0 to 4.0 weight-%, based on the total weight of the porous oxidic material, calculated as elemental transition metal.
The present invention further relates to a use of a porous oxidic material according to the present invention as a catalytically active material, as a catalyst, or as a catalyst component. Preferably, the use is for the selective catalytic reduction of nitrogen oxides in an exhaust gas stream of a diesel engine. Alternatively, the use is preferably for converting methanol to one or more olefins.
The present invention further relates to a method for selectively catalytically reducing nitrogen oxides in an exhaust gas stream of a diesel engine, said method comprising preparing a porous oxidic material according to a process according to the present invention, preparing a catalyst comprising said porous oxidic material, and bringing said exhaust gas stream in contact with said catalyst.
The present invention further relates to a method for selectively catalytically reducing nitrogen oxides in an exhaust gas stream of a diesel engine, said method comprising preparing a catalyst comprising a porous oxidic material according to the present invention, and bringing said exhaust gas stream in contact with said catalyst.
The present invention further relates to a catalyst, preferably for selectively catalytically reducing nitrogen oxides in an exhaust gas stream of a diesel engine, said catalyst comprising a porous oxidic material according to the present invention.
The present invention further relates to a catalyst, preferably for catalytically converting methanol to one or more olefins, said catalyst comprising a porous oxidic material according to the present invention.
The present invention further relates to a method for catalytically converting methanol to one or more olefins, the method comprising
It is preferred that (i) further comprises pretreating the catalyst in a reactor in a gas stream comprising nitrogen.
It is preferred that the catalyst provided in (i) is prepared by tableting the porous oxidic material according to the present invention, or the porous oxidic material prepared according to a process according to the present invention.
It is preferred that pretreating is performed in the gas stream comprising nitrogen at a temperature in the range of from 300 to 700° C., more preferably in the range of from 400 to 600° C.
It is preferred that contacting according to (iii) is effected at a temperature in the range of from 200 to 750° C. more preferably in the range of from 250 to 600° C., more preferably in the range of from 300 to 400° C.
It is preferred that contacting according to (iii) is effected at a pressure of the gas stream in the range of from 0.75 to 5 bar, more preferably in the range of from 0.9 to 1.5 bar.
It is preferred that contacting according to (iii) is carried out at a weight hourly space velocity in the range of from 0.2 to 100 h−1, more preferably in the range of from 0.3 to 20 h−1, more preferably in the range of from 0.4 to 10 h−1, more preferably in the range of from 0.5 to 2 h−1.
It is preferred that the reactor is a fixed-bed reactor.
The present invention is illustrated by the following set of embodiments and combinations of embodiments resulting from the dependencies and back-references as indicated. In particular, it is noted that in each instance where a range of embodiments is mentioned, for example in the context of a term such as “The process of any one of embodiments 1 to 4”, every embodiment in this range is meant to be explicitly disclosed for the skilled person, i.e. the wording of this term is to be understood by the skilled person as being synonymous to “The process of any one of embodiments 1, 2, 3 and 4”.
21. The process of any one of embodiments 1 to 20, wherein the source of a base provided in (i) comprises, preferably is, one or more of an alkali metal hydroxide and an alkaline earth metal hydroxide, preferably an alkali metal hydroxide, more preferably sodium hydroxide.
61. The process of any one of embodiments 1 to 60, wherein said micropores of the porous oxidic material have a micropore volume, determined as described in Reference Example 1 b), in the range of from 0.05 to 0.50 cm3/g, preferably in the range of from 0.10 to 0.40 cm3/g, more preferably in the range of from 0.20 to 0.30 cm3/g.
wherein 100% relates to the intensity of the maximum peak in the X-ray powder diffraction pattern, preferably having a framework type AEI has an X-ray diffraction pattern comprising at least the following reflections:
wherein 100% relates to the intensity of the maximum peak in the X-ray powder diffraction pattern.
The present invention is further illustrated by the following examples, reference examples, and comparative examples.
Finally, 29.7 g of the solid product was mixed with 75 g of H2O and 110 g of Amberlite IRN-78 ion-exchange resin, OH−form, and stirred for 1 day. The mixture was filtered and the solution obtained is the hydroxide form of N,N-diethyl-cis-2,6-dimethylpiperidinium.
a) Preparing a mesoporous zeolitic material having a framework type AEI
Materials:
11.04 g of N,N-diethyl-cis-2,6-dimethylpiperidinium hydroxide solution (0.21 M) (the first structure directing agent, FOSDA) was added dropwise to 1 g of zeolite Y in a beaker and the mixture was stirred magnetically for 1 hour at room temperature. 0.29 g of NaOH was added and the mixture was stirred magnetically for 1 hour.
0.20 g of dimethyloctadecyl[3-(trimethoxysilyl)propyl]ammonium chloride (the second structure directing agent, SOSDA) was added to the mixture and the resulting mixture was stirred magnetically for 1.5 hours at room temperature. Finally, 0.02 g of AEI seed crystals was added and the mixture was stirred for 20 minutes at room temperature. The synthesis mixture composition was 0.23 Na2O: 0.15 FOSDA: 0.016 SOSDA: 1.0 SiO2: 0.042 Al2O3: 37.5 H2O. The term SiO2 refers to the silicon comprised in the zeolite Y calculated as silica. The obtained mixture was transferred in a Teflon-lined autoclave with a volume of 25 ml. The autoclave was sealed and the mixture crystallized at 140° C. for 7 days (168 hours) under rotation (at a constant speed of 50 rpm). After pressure release and cooling to room temperature, the obtained suspension was subjected to filtration. The filter cake was washed with deionized water and was then dried for 2 hours at a temperature of 100° C. 0.80 g of a zeolitic material was obtained. The SiO2: Al2O3 molar ratio of the zeolitic material was 20.
The XRD patterns of the respectively obtained zeolitic material show the characteristic peaks of AEI framework structure, namely a peak at around 9.5 2Theta (highest intensity, 100%), a peak at around 16.1° 2Theta (intensity: 85.9%), a peak at around 16.9° 2Theta (intensity: 92.0%), a peak at around 17.2° 2Theta (intensity: 97.2%), a peak at around 20.7° 2Theta (intensity: 90.1%), a peak at around 21.4° 2Theta (intensity: 62.0%), a peak at 24.0° 2Theta (intensity: 90.8%), a peak at 26.3° 2Theta (intensity: 43.9%) and a peak at 31.2° 2Theta (intensity: 53.3%), as shown in
The BET specific surface area of the respectively obtained zeolitic material, after calcination in air at 550° C. for 4 hours, was 796.3 m2/g determined as described in Reference Example 1 b).
The mesopore volume was of 0.36 cm3/g as determined as described in Reference Example 1 b) and the micropore volume was of 0.26 cm3/g as determined as described in Reference Example 1 b). The ratio of mesopore volume to micropore volume was 1.38:1 and the ratio of mesopore volume to the total pore volume was 0.581:1.
The SEM images of the respectively obtained fresh AEI zeolitic material (low magnification: scale bar 1 micrometer) are shown in
b) Preparing the H-form of a mesoporous zeolitic material having a framework type AEI
The dried zeolitic material obtained from a) is ion-exchanged with a 1M NH4NO3 solution at 80 ° C. for 2 hours and calcined in air at 550° C. for 4 hours. The procedure was repeated once.
c) Preparing the Cu-form of a mesoporous zeolitic material having a framework type AEI The H-form zeolitic material obtained from b) was ion-exchanged with 1 M Cu(CH3COO)2 aqueous solution at 80° C. for 1 hour and calcined in air at 550° C. for 4 hours.
Copper content (Cu) of the Cu-exchanged AEI zeolitic material: 3.32 weight-%, calculated as elemental Cu, based on the total weight of the zeolitic material.
a) Preparing a mesoporous zeolitic material having a framework type AEI Materials:
11.04 g of N,N-diethyl-cis-2,6-dimethylpiperidinium hydroxide solution (0.21 M) (the first structure directing agent, FOSDA) was added dropwise to 1 g of zeolite Y in a beaker and the mixture was stirred magnetically for 1 hour at room temperature. 0.29 g of NaOH was added and the mixture was stirred magnetically for 1 hour.
0.10 g of dimethyloctadecyl[3-(trimethoxysilyl)propyl]ammonium chloride (the second structure directing agent, SOSDA) was added to the mixture and the resulting mixture was stirred magnetically for 1.5 hours at room temperature. Finally, 0.02 g of AEI seed crystals was added and the mixture was stirred for 20 minutes at room temperature. The synthesis mixture composition was 0.23 Na2O: 0.15 FOSDA: 0.008 SOSDA: 1.0 SiO2: 0.042 Al2O3: 37.5 H2O. The term SiO2 refers to the silicon comprised in the zeolite Y calculated as silica. The obtained mixture was transferred in a Teflon-lined autoclave with a volume of 25 ml. The autoclave was sealed and the mixture crystallized at 140° C. for 7 days (168 hours) under rotation (at a constant speed of 50 rpm). After pressure release and cooling to room temperature, the obtained suspension was subjected to filtration. The filter cake was washed with deionized water and was then dried for 2 hours at a temperature of 100° C. 0.80 g of a zeolitic material was obtained. The SiO2: Al2O3 molar ratio of the zeolitic material was 20.
The XRD patterns of the respectively obtained zeolitic material show the characteristic peaks of AEI framework structure, namely a peak at around 9.5° 2Theta (highest intensity), a peak at around 16.1° 2Theta, a peak at around 16.9 2Theta, a peak at around 17.2 2Theta, a peak at around 20.7° 2Theta, a peak at around 21.4 2Theta, a peak at 24.0° 2Theta, a peak at 26.3 2Theta and a peak at 31.2° 2Theta, as shown in
The BET specific surface area of the respectively obtained zeolitic material, after calcination in air at 550° C. for 4 hours, was 798.4 m2/g determined as described in Reference Example 1 b).
The mesopore volume was of 0.44 cm3/g as determined as described in Reference Example 1 b) and the micropore volume was of 0.23 cm3/g as determined as described in Reference Example 1 b). The ratio of the mesopore volume to the micropore volume was 1.91:1 and the ratio of the mesopore volume to the total pore volume was 0.657:1.
The SEM images of the respectively obtained fresh AEI zeolitic material (low magnification: scale bar 1 micrometer) are shown in
b) Preparing the H-form of a mesoporous zeolitic material having a framework type AEI The dried zeolitic material obtained from a) is ion-exchanged with a 1M NH4NO3 solution at 80° C. for 2 hours and calcined in air at 550° C. for 4 hours. The procedure was repeated once.
c) Preparing the Cu-form of a mesoporous zeolitic material having a framework type AEI The H-form zeolitic material obtained from b) was ion-exchanged with 1 M Cu(CH3COO)2 aqueous solution at 80° C. for 1 hour and calcined in air at 550° C. for 4 hours. Copper content (Cu) of the Cu-exchanged AEI zeolitic material: 3.46 weight-%, calculated as elemental Cu, based on the total weight of the zeolitic material.
a) Trying to prepare a mesoporous zeolitic material having a framework type AEI Materials:
11.04 g of N,N-diethyl-cis-2,6-dimethylpiperidinium hydroxide solution (0.21 M) (FOSDA) was added dropwise to 1 g of zeolite Y in a beaker and the mixture was stirred magnetically for 1 hour at room temperature. 0.29 g of NaOH was added and the mixture was stirred magnetically for 1 hour.
Finally, 0.02 g of AEI seed crystals was added and the mixture was stirred for 20 minutes at room temperature. The synthesis mixture composition was 0.23 Na2O: 0.15 FOSDA: 1.0 SiO2: 0.042 Al2O3: 37.5 H2O. The term SiO2 refers to the silicon comprised in the zeolite Y calculated as silica. The obtained mixture was transferred in a Teflon-lined autoclave with a volume of 25 ml. The autoclave was sealed and the mixture crystallized at 140° C. for 3 days (72 hours) under homogeneous rotation (50 rpm). After pressure release and cooling to room temperature, the obtained suspension was subjected to filtration. The filter cake was washed with deionized water and was then dried for 2 hours at a temperature of 100° C. 0.80 g of a zeolitic material was obtained. The SiO2: Al2O3 molar ratio of the zeolitic material was 20.
The XRD patterns of the respectively obtained zeolitic material show the characteristic peaks of AEI framework structure, namely a peak at around 9.5° 2Theta (highest intensity), a peak at around 16.1° 2Theta, a peak at around 16.9° 2Theta, a peak at around 17.2° 2Theta, a peak at around 20.7° 2Theta, a peak at around 21.4° 2Theta, a peak at 24.0° 2Theta, a peak at 26.3° 2Theta and a peak at 31.2° 2Theta, as shown in
After calcination in air at 550° C. for 4 hours, the BET specific surface area was 782.9 m2/g determined as described in Reference Example 1 b).
The mesopore volume was of 0.07 cm3/g determined as described in Reference Example 1 b) and the micropore volume was of 0.29 cm3/g determined as described in Reference Example 1 b). The ratio of the mesopore volume to the micropore volume was 0.241:1 and the ratio of the mesopore volume to the total pore volume was 0.194:1.
The SEM images of the respectively obtained fresh AEI zeolitic material (low magnification: scale bar 1 micrometer) are shown in
b) Preparing the H-form of a zeolitic material having a framework type AEI
The dried zeolitic material obtained from a) is ion-exchanged with a 1M NH4NO3 solution at 80° C. for 2 hours and calcined in air at 550° C. for 4 hours. The procedure was repeated once.
c) Preparing the Cu-form of a zeolitic material having a framework type AEI The H-form zeolitic material obtained from c) was ion-exchanged with 1 M Cu(CH3COO)2 aqueous solution at 80° C. for 1 hour and calcined in air at 550° C. for 4 hours. Copper content (Cu) of the Cu-exchanged AEI zeolitic material: 3.65 weight-%, calculated as elemental Cu, based on the total weight of the zeolitic material.
The zeolitic material obtained according to the synthesis of Comparative Example 1 a) and having a framework structure of the type AEI is not rnesoporous. In particular, this is illustrated by the measurements of the micropore volume and the mesopore volume. It results from said data that the mesopore volume is not significant compared to the total pore volume (mesopore volume+micropore volume) as it represents less than 20% of the total pores. Thus, Comparative Example 1 demonstrates that a dimethyloctadecyl[3-(trimethoxysilyl)propyl]ammonium containing compound is an essential compound for preparing a mesoporous zeolitic material having a framework type AEI.
Catalysts comprising the zeolitic materials respectively obtained from Examples 1 and 2 and from Comparative Example 1 were prepared by tableting and squashing to 40-60 mesh and subjected to a selective catalytic reduction test. The amount of catalysts used in the fixed bed is 0.5 g each. For this purpose, the catalytic activities of the respectively obtained fresh catalysts were measured with a fixed-bed quartz reactor in a gaseous mixture containing 500 ppm of NO, 500 ppm of NH3, 10% of O2, and N2 as a balance gas. The gas hourly space velocity (GHS/) was 80 000 h−1 at temperature of the feed stream of 100 to 550° C. The results are illustrated in
As can be seen from
Example 2 according to the present invention permits to provide an improved NOx conversion at high temperatures compared to a catalyst comprising the zeolitic material having a framework structure type AEI of Comparative Example 1 not according to the present invention.
a) Preparing a zeolitic material having a framework type AEI
Materials:
9.4 g of N,N-diethyl-cis-2,6-dimethylpiperidinium hydroxide solution (0.24 M) (the first structure directing agent, FOSDA) was added dropwise to 1 g of zeolite Y in a beaker and the mixture was stirred magnetically for 30 minutes at room temperature. 0.24 g of NaOH was added and the mixture was stirred magnetically for 30 minutes. The synthesis mixture composition was 0.17 Na2O: 0.14 FOSDA: 1.0 SiO2: 0.05 Al2O3: 30 H2O. The term SiO2 refers to the silicon comprised in the zeolite Y calculated as silica. The obtained mixture was transferred in a Teflon-lined autoclave. The autoclave was sealed and the mixture crystallized at 140° C. for 3 days (72 hours) under rotation (at a constant speed of 50 rpm). After pressure release and cooling to room temperature, the obtained suspension was subjected to filtration. The filter cake was washed with deionized water and was then dried for 2 hours at a temperature of 100° C. 0.8 g of a zeolitic material was obtained. The SiO2: Al2O3 molar ratio of the zeolitic material was 16.4.
The XRD patterns of the respectively obtained zeolitic material show the characteristic peaks of AEI framework structure, as shown in
The SEM images of the respectively obtained AEI zeolitic material (magnification: scale bar 1 micrometer) are shown in
Elemental analysis of the respectively obtained zeolitic material determined as described in Reference Example 1 f):
C %—11.8
N %—1.2
C/N—9.8
The BET specific surface area of the respectively obtained zeolitic material, after calcination in air at 550° C. for 4 hours, was 534 m2/g determined as described in Reference Example 1 b).
The mesopore volume was of 0.02 cm3/g as determined as described in Reference Example 1 b) and the micropore volume was of 0.24 cm3/g as determined as described in Reference Example 1 b). The ratio of mesopore volume to micropore volume was 0.08:1 and the ratio of mesopore volume to the total pore volume was 0.08:1.
b) Preparing the H-form of a zeolitic material having a framework type AEI
The dried zeolitic material obtained from a) is ion-exchanged with a 1M NH4NO3 solution at 80° C. for 2 hours and calcined in air at 550° C. for 4 hours. The procedure was repeated once.
a) Preparing a mesoporous zeolitic material having a framework type AEI
Materials:
9.4 g of N,N-diethyl-cis-2,6-dimethylpiperidinium hydroxide solution (0.24 M) (the first structure directing agent, FOSDA) was added dropwise to 1 g of zeolite Y in a beaker and the mixture was stirred magnetically for 30 minutes at room temperature. 0.24 g of NaOH was added and the mixture was stirred magnetically for 30 minutes.
0.10 g of dimethyloctadecyl[3-(trimethoxysilyl)propyl]ammonium chloride (the second structure directing agent, SOSDA) was added to the mixture and the resulting mixture was stirred magnetically for 4 hours at room temperature. Finally, 0.02 g of SSZ-39 seed crystals was added and the mixture was stirred for 10 minutes at room temperature. The synthesis mixture composition was 0.17 Na2O: 0.14 FOSDA: 0.008 SOSDA: 1.0 SiO2: 0.05 Al2O3: 30 H2O. The term SiO2 refers to the silicon comprised in the zeolite Y calculated as silica. The obtained mixture was transferred in a Teflon-lined autoclave. The autoclave was sealed and the mixture crystallized at 140° C. for 3 days (72 hours) under rotation (at a constant speed of 50 rpm). After pressure release and cooling to room temperature, the obtained suspension was subjected to filtration. The filter cake was washed with deionized water and was then dried for 2 hours at a temperature of 100° C. 0.8 g of a zeolitic material was obtained. The SiO2: Al2O3 molar ratio of the zeolitic material was 16.2.
The XRD patterns of the respectively obtained zeolitic material show the characteristic peaks of AEI framework structure, as shown in
The SEM images of the respectively obtained AEI zeolitic material (magnification: scale bar 1 micrometer) are shown in
Elemental analysis of the respectively obtained zeolitic material determined as described in Reference Example 1 f):
C %—14.3
N %—1.3
C/N—11.0
The C/N ratio of this zeolitic material is higher than those of the zeolitic material of Comparative Example 2 (conventional SSZ-39).
The BET specific surface area of the respectively obtained zeolitic material, after calcination in air at 550° C. for 4 hours, was 559 m2/g determined as described in Reference Example 1 b).
The mesopore volume was of 0.17 cm3/g as determined as described in Reference Example 1 b) and the micropore volume was of 0.25 cm3/g as determined as described in Reference Example 1 b). The ratio of mesopore volume to micropore volume was 0.68:1 and the ratio of mesopore volume to the total pore volume was 0.4:1.
b) Preparing the H-form of a mesoporous zeolitic material having a framework type AEI
The dried zeolitic material obtained from a) is ion-exchanged with a 1M NH4NO3 solution at 80° C. for 2 hours and calcined in air at 550° C. for 4 hours. The procedure was repeated once.
a) Preparing a mesoporous zeolitic material having a framework type AEI
Materials:
9.4 g of N,N-diethyl-cis-2,6-dimethylpiperidinium hydroxide solution (0.24 M) (the first structure directing agent, FOSDA) was added dropwise to 1 g of zeolite Y in a beaker and the mixture was stirred magnetically for 30 minutes at room temperature. 0.24 g of NaOH was added and the mixture was stirred magnetically for 30 minutes.
0.20 g of dimethyloctadecyl[3-(trimethoxysilyl)propyl]ammonium chloride (the second structure directing agent, SOSDA) was added to the mixture and the resulting mixture was stirred magnetically for 4 hours at room temperature. Finally, 0.02 g of SSZ-39 seed crystals was added and the mixture was stirred for 10 minutes at room temperature. The synthesis mixture composition was 0.17 Na2O: 0.14 FOSDA: 0.016 SOSDA: 1.0 SiO2: 0.05 Al2O3: 30 H2O. The term SiO2 refers to the silicon comprised in the zeolite Y calculated as silica. The obtained mixture was transferred in a Teflon-lined autoclave. The autoclave was sealed and the mixture crystallized at 140° C. for 3 days (72 hours) under rotation (at a constant speed of 50 rpm). After pressure release and cooling to room temperature, the obtained suspension was subjected to filtration. The filter cake was washed with deionized water and was then dried for 2 hours at a temperature of 100° C. 0.8 g of a zeolitic material (SSZ-39) was obtained. The SiO2: Al2O3 molar ratio of the zeolitic material was 17.4.
The XRD patterns of the respectively obtained zeolitic material show the characteristic peaks of AEI framework structure, as shown in
The SEM images of the respectively obtained fresh AEI zeolitic material (magnification: scale bar 1 micrometer) are shown in
Elemental analysis of the respectively obtained zeolitic material determined as described in Reference Example 1 f):
C %—16.8
N %—1.5
C/N—11.2
The C/N ratio of this zeolitic material is higher than those of the zeolitic material of Comparative Example (conventional SSZ-39) and those of the mesoporous zeolitic material AEI of Example 5. Thus, this shows that the C/N ratio increases with the amount of SOSDA. Thus, without wanting to be bound to any theory, it is believed that the SOSDA is encapsulated in the zeolitic materials.
The BET specific surface area of the respectively obtained zeolitic material, after calcination in air at 550° C. for 4 hours, was 566 m2/g determined as described in Reference Example 1 b).
The mesopore volume was of 0.28 cm3/g as determined as described in Reference Example 1 b) and the micropore volume was of 0.24 cm3/g as determined as described in Reference Example 1 b). The ratio of mesopore volume to micropore volume was 1.17:1 and the ratio of mesopore volume to the total pore volume was 0.54:1.
b) Preparing the H-form of a mesoporous zeolitic material having a framework type AEI
The dried zeolitic material obtained from a) is ion-exchanged with a 1M NH4NO3 solution at 80° C. for 2 hours and calcined in air at 550° C. for 4 hours. The procedure was repeated once.
The zeolitic materials of Comparative Examples 3a-3g were prepared as the zeolitic materials of Example 5 except that the conditions outlined in Table 1 below were applied.
11:1
The zeolitic materials of Examples 7a-7c were prepared as the zeolitic materials of Example 5 except that the conditions outlined in Table 2 below were applied.
35:1
As may be taken from Tables 1 and 2, the ratios of SOSDA/SiO2 and Na2O/SiO2, the SiO2/Al2O3 ratio of the zeolite Y as starting materials, and the addition of SSZ-39 zeolite seeds are critical for the successful synthesis of mesoporous zeolitic material having a framework type AEI.
When the SOSDA/SiO2 ratio was of 0.024, a mesoporous SSZ-39 zeolitic material was obtained with a zeolitic material MOR as impurity phase (7a). When the Na2O/SiO2 ratio was lower than 0.13, the product was the starting material zeolite Y (3a). Increasing the Na2O/SiO2 ratio to 0.20 permitted to obtain a mesoporous zeolitic material SSZ-39 with a zeolitic material MOR as impurity phase (7b). A Na2O/SiO2 ratio in the starting gel of about 0.17 permitted to obtain only a mesoporous zeolitic material SSZ-39 as may be taken from Examples 5 and 6. Moreover, when the starting gel is crystallized without addition of SSZ-39 seeds, the product was always a zeolitic material FAU (3b). On the contrary, when the SSZ-39 seeds were added, mesoporous SSZ-39 zeolitic materials with high crystallinity were obtained as illustrated by Examples 5 and 6. In addition, it is further believed that the SiO2/Al2O3 molar ratio of the starting zeolite Y is of great importance in the synthesis of mesoporous AEI zeolitic materials. As may be taken from Tables 1 and 2, when the SiO2/Al2O3 molar ratio of Y zeolite was 11.0, there was no interzeolite transformation and the product was the starting material (3c). Further, increasing the SiO2/Al2O3 ratio of zeolite Y to 35.0, resulted in a mesoporous zeolitic, material SSZ-39 and the formation of impurities, a zeolitic material MOR mixed with zeolite Y, the starting material (7c). Finally, when the SiO2/Al2O3 ratio of zeolite Y was further increased to 256, there was no transformation (3d). However, with a SiO2/Al2O3 ratio of zeolite Y of 21.6, mesoporous SSZ-39 zeolitic materials with high crystallinity were obtained as illustrated by Examples 5 and 6.
Methanol-to-olefin (MTO) reactions were carried out in a fixed-bed reactor at atmospheric pressure. A total of 0.5 g of a catalyst comprising the zeolitic material according to b) of Example 6 (20-40 mesh—Catalyst b below) was loaded into the reactor. Said catalyst was prepared by tableting the H-form of the zeolitic material according to b) of Example 6 to 20-40 mesh. The sample was pretreated in flowing nitrogen at 500° C. for 2 hours, and then the temperature of the reactor was decreased to 350° C. CH3OH was pumped into the reactor under nitrogen. The weight hourly space velocity (WHSV) was 0.8 h−1. Same was performed for a catalyst comprising the zeolitic material according to b) of Comparative Example 2 (Catalyst a below). The products were analyzed online using an Agilent 6890 gas chromatograph equipped with a FID detector and an HP-PONA methyl siloxane capillary column.
The catalytic data in MTO reactions at a reaction e of 60 min at 350° C. are displayed in Table 3 below.
The dependence of the methanol conversion on time in MTO is illustrated in
CN 107285333 A
CN 107285334 A
| Number | Date | Country | Kind |
|---|---|---|---|
| PCT/CN2018/083928 | Apr 2018 | CN | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/CN2019/072638 | 1/22/2019 | WO | 00 |
