Patent Application
20220306481
The present invention relates to a high-silica Y molecular sieve having FAU topology and a method for synthesizing high-silica Y molecular sieve by introducing organic templating agent into synthetic gel system and adding silica-alumina molecular sieve having FAU or EMT topology as seed crystal, and further relates to a method for synthesizing high-silica Y molecular sieve by introducing organic templating agent into synthetic gel system and adding directing agent solution. The present invention belong to the field of catalyst preparation.
Y zeolite is a silica zeolite having FAU topology. It is mainly used in fluid catalytic cracking (FCC) and is currently the most used zeolite material. The framework silica-alumina ratio of Y molecular sieve plays a decisive role in its catalytic performance. The higher the silica-alumina ratio, the better the catalytic activity and stability. The high-silica Y zeolite currently used in industry is mainly obtained by chemical/physical deabomination etc. This post-treatment process cumbersome, energy-consuming, and polluting. The direct hydrothermal synthesis electively avoids the above shortcomings while maintaining the completeness and uniformity of aluminum distribution of the crystal structure. Therefore, exploring the direct synthesis of Y molecular sieve having high silica-alumina ratio is of great significance to the catalytic cracking process.
For the direct synthesis of high-silica Y molecular sieve, people initially synthesize in non-templating agent system. That is, people do not add any organic templating agent to reaction gel, and only adjust the proportioning of the gel, adjust the crystallization time, seed crystal or inorganic directing agent so as to expect to achieve the purpose of increasing the silica-alumina ratio of the Y molecular sieve. However, limited success is achieved, and the silica-alumina ratio is difficult to reach 6.
The use of organic templating agent has brought the synthesis of Y molecular sieve into a new field. In 1987, U.S. Pat. No. 4,174,601 disclosed a FAU homogenous polymorph named ECR-4 with a silica-alumina ratio of greater than 6, which was prepared by hydrothermal crystallization at a temperature ranging bran 70° C. to 120° C. using alkyl or hydroxyalkyl quaternary ammonium salt as templating agent in the presence of seed crystal.
In 1990, U.S. Pat. No. 4,931,267 disclosed a FAU homogeneous polymorph named ECR-32 with a silica-alumina ratio of greater than 6 and high thermal stability, which was prepared by hydrothermal crystallization at a temperature ranging from 90° C. to 120° C. using tetrapropyl and/or tetrabutylammonium hydroxide as templating agent.
In 1990, French Delprato et. al. (Zeolites, 1990, 10(6):546˜552) used crown ether as templating agent to synthesize FAU zeolite with cubic structure for the first time. The framework silica-to-aluminum ratio is close to 9.0, which is the highest value currently reported in the literatures. However, the expensive and highly toxic crown ether limits in industrial application. Later, the U.S. Pat. No. 5,335,717 used polyethylene oxide as templating agent to synthesize Y zeolite with a silica-alumina ratio of greater than 6.
According to one aspect of the present application there is provided a high-silica Y molecular sieve having FAU topology.
The high-silica Y molecular sieve having FAU topology is characterized in that the anhydrous chemical constitution of the molecular sieve is as shown in formula I:
kM.mR1.nR2.(SixAly)Oz Formula I
Optionally, m=0.01˜0.20.
Optionally, k=0.01˜0.15; m=0.01˜0.1; n=0.02˜0.15.
Optionally, k=0.02˜0.13; m=0.01˜0.04; n=0.03˜0.08.
Optionally, the “C1˜C12 alkyl” includes “C7˜C12 phenyl alkyl”.
Optionally, the “aryl” includes “C7˜C12 aryl”.
Optionally, the “C7˜C12 aryl” includes “C7˜C12 alkyl aryl”.
Optionally, M is at least one of Na, K, and Cs, and 2x/y=7˜30.
Optionally, M is at least one of Na, K, and Cs, and 2x/y=8˜30.
Optionally, the upper limit of 2x/y is 8, 9, 10, 11. 12, 13, 14, 15, 16, 17. 18.19. 33, 22, 23, 24, 25, 26, 27, 28, 29 or 30, and the lower limit thereof is 7, 8, 9, 10, 11, 12, 13. 14, 15, 16, 17, 18, 19, 20. 22, 23. 24, 25, 26, 27, 28 or 29.
Optionally, R1 and R2 are independent one of quaternary ammonium compounds.
Optionally, R1 and R2 are independently at least one of tetramethylammonium hydroxide, tetramethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, tetrapentylammonium hydroxide, tetrahexylammonium hydroxide, tetrapropylammonium bromide, tetrabutylammonium chloride, tetrapentylammonium bromide, tripropyl-isoburylammonium bromide, triburyl-cyclohexylammonium hydroxide, diburyl-dihexyl ammonium hydroxide, choline, triethyl-hydroxyethyl ammonium hydroxide tripropyl-hydroxyethyl ammonium hydroxide, triethyl-hydroxyethyl ammonium hydroxide, tributyl-benzyl ammonium hydroxide, triethyl-benzyl ammonium hydroxide, tropropyl-benzyl ammonium hydroxide, N,N,N-triethyl-adamantyl ammonium chloride, and N,N,N-tripropyl ammonium chloride.
Optionally, R1 is at least one of tetraethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide and choline;
R1 is at least one of tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, tetrapentylammonium hydroxide, tetrahexylammonium hydroxide, tetrapropylammonium bromide, tetrabutylammonium chloride, tetrapentylammonium bromide, tripropyl-isobutyl ammonium bromide, tributyl-cyclohexylammonium hydroxide, dibutyl-dihexyl at ammonium hydroxide, triethyl-hydroxyethyl ammonium hydroxide, tripropyl-hydroxyethyl ammonium hydroxide, triburyl-hydroxyethyl ammonium hydroxide, tributyl-benzyl ammonium hydroxide, triethyl-benzyl ammonium hydroxide, tripropyl-benzyl ammonium hydroxide N,N,N-triethyl-adamantyl ammonium chloride, and N,N,N-tripropyl-adamantyl ammonium chloride
Optionally, R1 is at least one of quaternary ammonium compounds; and R2 is at least one of nitrogen-containing heterocyclic compounds and derivatives thereof.
Optionally, R1 is at least one of tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide and choline;
R2 is at least one of nitrogen heterocyclic compounds and derivatives thereof.
Optionally, R2 at least ore of pyridine, N-methylpyridine N-ethylpyridine N-propylpyridine, N-butylpyridine, N-ethyl-3-butylpyridine, 1-ethyl-propylpyridine hydroxide, piperidine, N,N-dimethylpiperidine, N,N-dimethyl-3,5-diethylpiperidine hydroxide, N,N-dimethyl-3,5-dipropylpiperidine hydroxide, N,N-diethyl-3,5-dipropylpiperidine hydroxide, N,N-diethyl-2,6-dimethylpiperidine hydroxide, N,N-dimethyl-2,6-diethylpiperidine hydroxide, imidazole, 1-ethyl-3-butylimidazole hydroxide, 1-ethyl-3-butyl-1-propylimidazole hydroxide, 1-benzyl-3-methylimidazole hydroxide, 1-benzyl-3-ethylimidazole hydroxide, 1-benzyl-3-butylimidazole hydroxide, piperazine, N-methylpiperazine, 1,4-dipropylpiperazine, 1-methyl-1-ethylpiperazine, and 1-ethyl-1-butyl-5-methylpiperazine.
Optionally, the high-silica Y molecular sieve having FAU topology is an octahedral structure.
Optionally, the particle size of the high-silica Y molecular sieve having FAU topology ranges from 50 min to 2500 nm.
According to another aspect of the meal application, there is provided a method for synthesizing high-silica Y molecular sieve having FAU topology by using silica-alumina molecular sieve having FAU or EMT topology as seed crystal and introducing organic templating agent under alkaline hydrochemical conditions. A high-silica (silica-alumina molar ratio in a range from 7 to 40) Y molecular sieve is synthesized.
The method for synthesizing high-silica Y molecular sieve having FAU topology is characterized in that it comprises the following steps:
SiO2/Al2O3=10˜200,
M2O/Al2O3=0˜30, wherein M is at least one of alkali metal elements;
R/Al2O3=1˜45;
H2O/Al2O3=50˜8000;
b) adding silica-alumina molecular sieve seed crystal having FAU or EMT topology to the initial gel mixture I obtained in step a) to obtain a mixture II;
c) placing the mixture II obtained in step b) in a sealed reactor to perform crystallization to obtain the high-silica Y molecular sieve having FAU topology;
wherein, the number of moles of silicon source is calculated by SiO2; the number of moles of aluminium source is calculated by Al2O1; the number of mole of templating agent R is calculated by the number of moles of R itself; and the number of moles of alkali metal source is calculated by the number of moles of corresponding metal oxide M2O.
Optionally, in step a), H2O/Al2O3=50˜6000.
Optionally, in step a), H2O/Al2O3=100˜8000.
Optionally, in step a), R/Al2O3=0.1˜40.
Optionally, the organic templating agent R in step a) is at least one of nitrogen-containing heterocyclic compounds and derivatives thereof and quaternary ammonium compounds; the structural formula of it quaternary ammonium compound is as shown in formula II:
In formula II R21, R22, R23 and R24 are independently at least one of C1˜C12 alkyl, C1˜C12 alkoxy, C1˜C12 hydroxyalkyl, aryl and adamantyl;
Xn− is one of OH−, Cl−, Br−, I−, NO3−, HSO4−, H2PO3−, SO42−, HPO32−, and PO33−.
Optionally, the organic templating agent R in step a) is at least one of tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, tetrapentylammonium hydroxide, tetrahexylammonium hydroxide, tetrapropylammonium bromide, tetrabutylammonium chloride, tetrapentylammonium bromide, tripropyl-isobutyl ammonium bromide, tributyl-cyclohexylammonium hydroxide, dibutyl-dihexyl ammonium hydroxide, choline triethyl-hydroxyethyl ammonium hydroxide, tripropyl-hydroxyethyl ammonium hydroxide, tributyl-hydroxyethyl ammonium hydroxide, tributyl-benzyl ammonium hydroxide, triethyl-benzyl ammonium hydroxide tripropyl-benzyl ammonium hydroxide, N,N,N-triethyl-adamantyl ammonium chloride, and N,N,N-tripropyl-adamantyl ammonium chloride.
Optionally, the nitrogen-containing heterocyclic templating agent R in step a) is at least one of nitrogen-containing heterocyclic compounds and derivatives thereof.
Optionally, in step a), the nitrogen-containing heterocyclic templating agent R is at least one of pyridine, N-methylpyridine, N-ethylpyridine, N-propylpyridine, N-butylpyridine, N-ethyl-3-butylpyridine, 1-ethyl-2-propylpyridine hydroxide, piperidine N,N-dimethylpiperidine, N,N-dimethyl-3,5-diethylpiperidine hydroxide, N,N-dimethyl-3,5-dipropylpiperidine hydroxide, N,N-diethyl-3,5-dipropylpiperidine hydroxide, N,N-diethyl-2,6-dimethylpiperidine hydroxide, N,N-dimethyl-2,6-diethylpiperidine hydroxide, imidazole, 1-ethyl-3-butylimidazole hydroxide, 1-ethyl-3-butyl-4-propylimidazole-4-propylimidazole hydroxide, 1-benzyl-3-methylimidazole hydroxide, 1-benzyl-3-ethylimidazole hydroxide, 1-butyl-3-butylimidazole hydroxide, piperazine, N-methylpiperazine, 1,4-dipropylpiperazine, 1-methyl-4-ethylpiperazine, and 1-ethyl-4-butyl-5-methylpiperazine.
Optionally the silicon source in step a) is at least one of methyl orthosilicate, ethyl orthosilicate, silica sol, solid silica gel, fumed silica, and sodium silicate;
Optionally step a) comprises mixing the aluminum source, the alkali metal source, the organic templating agent R, and water, and then adding the silicon source to mix to obtain an initial gel mixture I.
Optionally, the aluminum source, silicon source, alkali metal source, organic templating agent R and water in the raw materials in step a) have the following molar ratios:
SiO2/Al2O3=10˜200;
M2O/Al2O3=0˜30. wherein M is at least one of alkali metal elements:
R/Al2O3=1˜45.
H2O/Al2O3=100˜6000.
Optionally, the upper limit of SiO2/Al2O3 is 15, 20, 30, 40, 45, 50, 60, 70, 93, 90, 100, 110, 120, 130, 140, 150, 160, 170, 180, 190 or 200, and the lower limit thereof 10, 15, 20, 30, 40, 45, 50, 60. 70, 80, 90, 100, 110, 120, 130, 140, 150, 160, 170, 180 or 190.
Optionally, the upper limit of M2O/Al2O3 is 1.8, 2.0, 3.0, 4.0, 4.5, 4.8, 5.0, 6.0, 7.0, 8.0, 9.0, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 22, 25, 28, 29 or 30; the lower limit thereof is 0.1, 1.8, 2.0, 3.0, 4.0, 4.5, 4.5, 4.8, 5.0, 6.0, 7.0, 8.0, 9.0, 10, 11. 12, 13, 14, 15, 16, 17, 18, 19, 20, 22, 25, or 28.
Optionally, the upper limit of the malar ratio of R/Al2O3 is 2, 3, 3.6, 4, 4.5, 4.8, 5, 5.2, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 22, 25, 28, 29, 30, 32, 35, 38, 40, 42 or 45: the lower limit thereof is 1, 2, 3, 3.6, 4, 4.5, 4.8, 5, 5.2, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 22, 25, 28, 29, 30, 32, 35, 38, 40, or 42.
Optionally the upper limit of the molar ratio of R/Al2O3 is 200, 300, 400, 500, 603, 700, 800, 900, 1000, 1100, 1200, 1300, 1400, 1500, 1600, 1700, 1800, 1900, 2000, 2100, 2200, 2300, 2400, 2500, 2600, 2700, 2800, 2900, 3400, 3200, 3500, 3800, 4000, 5000 or 6000; the lower limit thereof is 100, 200, 300, 400, 500, 600, 700, 800, 900, 1000, 1100, 1200, 1300, 1400, 1500, 1600, 1700, 1800, 1900, 2000, 2100, 2200, 2300, 2400, 2500, 2600, 2700, 2800, 2900, 3000, 3200, 3500, 3800, 4000 or 5000.
Optionally, in step b), the silica-alumina molecular sieve seed crystal having FAU or EMT topology is added to the initial gel mixture I obtained in step a), and after stirring and mixing, the mixture II is obtained.
Optionally, in step b), the stirring is performed for 1 to 48 hours.
Optionally, the upper limit of the stirring time in step b) is 48 hours, 44 hours, 40 hours, 36 hours, 32 hours, 28 hours, 24 hours, 20 hours, 16 hours, 12 hours, 8 hours, 4 hours, or 2 hours; the lower limit thereof is 1 hour, 2 hours, 4 hours, 8 hours, 12 hours, 16 hours, 20 hours, 24 hours, 28 hours, 32 hours, 36 hours 40 hours or 44 hours.
Optionally, the weight ratio of silica alumina molecular sieve seed crystal having FAU or EMT topology added in the mixture II in step b), to the silicon source in the initial gel mixture I ranges from 0.01:1 to 0.3:1;
wherein, the weight of the silicon source in the initial gel mixture I is calculated by the weight of SiO2.
Optionally, the silica-alumina molar ratio SiO2/Al2O3 of the silica-alumina molecular sieve seed crystal having FAU or EMT topology in step b) is 2˜∞.
Optionally, the silica-alumina molar ratio SiO2/Al2O3 of the silica-alumina molecular sieve seed crystal having FAU or EMT topology in step b) ranges from 2.5 to 200.
Optionally, a crystallization temperature in step c) from 90 to 180° C. and a crystallization time in step c) ranges from 0.1 to 15 days.
Optionally, the upper limit of the crystallization temperature in step c) is 100° C., 120° C., 140° C., 160° C., or 180° C., and the lower limit thereof is 80° C., 90° C., 100° C., 110° C., 120° C., 140° C. or 160° C.
Optionally, the upper limit of crystallization time in step c) is 0.1 day, 0.5 day, 1 day, 1.5 days, 2.5 days, 4 days, 5 days or 6 days, and the lower limit thereof is 2 days, 4 days, 5 days, 6 days, 7 days, 8 days, 9 days or 10 days.
Optionally, the upper limit of the silica-alumina molar ratio SiO2/Al2O3 of the silica-alumina molecular sieve seed crystal having FAU or EMT topology in step b) is 2.5, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30; the lower limit thereof is 2.2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28 or 29.
Optionally, the silica-alumina moles ratio SiO2/Al2O3 of the silica-alumina molecular sieve seed crystal having FAU or EMT topology is step b) ranges from 3 to 10.
Optionally, the crystallization in step c) is performed dynamically or statically.
Optionally, the crystallization in step c) is rotational crystallization.
Optionally, in step c), after the crystallization is completed the obtained solid product is filtered, washed and dried to obtain the high-silica Y molecular sieve.
In the method, washing, filtering, separating and drying the obtained Y molecular sieve are all conventional operations, wherein the drying can be performed by placing the separated Y molecular sieve at a temperature ranging from 100 to 110° C. for 12 hours.
In a specific embodiment, the synthesis process of the high-silica Y molecular sieve is as follows:
As a specific embodiment, the method comprises following steps:
As an embodiment, the synthesis process of the high-silica Y molecular sieve having FAU topology is as follows:
According to further aspect of the present application, a directing agent method for synthesizing high silica Y molecular sieve having FAU topology Y provided.
The method for synthesizing high-silica Y molecular sieve having FAU topology is characterized in that it comprises the following steps:
Optionally the aluminum source A1, silicon source Si1, alkali metal source M1, organic templating agent R1 and water in the raw materials I in step a) have the following molar ratios:
Optionally, the upper limit of the molar ratio of SiO2/Al2O3 is till 6.0, 7.0, 8.0, 9.0, 10, 11, 12, 13, 14, 15, 20 or 30 and the lower limit thereof is 5.0, 6.0, 7.0, 8.0, 9.0, 10, 11, 12, 13, 14, 15 or 20.
Optionally, the upper limit of the molar ratio of M2O/Al2O3 in step a) is 0.5. 1.8, 2.0, 3.0, 4.0, 4.5, 4.8 or 5.0, and the lower limit thereof is 0.1, 0.5, 1.8, 2.0, 3.0, 4.0, 4.5 or 4.8.
Optionally, the upper limit of the molar ratio of R/Al2O3 in step a) is 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 22, 25, 28, 29, 30, 32, 35, 34, 38 or 40, and the lower limit thereof is 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 22, 25, 28, 29, 30, 32, 35, 34, or 38.
Optionally, the upper limit of the molar ratio of H2O/Al2O3 in step a) is 150, 180, 200, 250, 300, 350, 400, 450, 500, 550 or 600. and the lower limit thereof is 100, 150, 180, 200, 250, 300, 350, 400, 450, 500, or 550.
Optionally, the silicon sources Si1 and Si2 in step a) and step b) are independently at least one of methyl orthosilicate, ethyl orthosilicate, silica soL solid silica gel, fumed silica, and sodium silicate,
Optionally, the organic templating agents R1 and R2 in step a) and step b) are independently one of nitrogen-containing heterocyclic compounds and derivative thereof and quaternary ammonium compounds;
Optionally, R1 and R2 are independently at least one of tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrahexylammonium hydroxide, tetrapentylammonium hydroxide, tetrahexylammonium hydroxide tetrapropylammonium bromide, tetrabutylammonium chloride, tetrapentylammonium bromide, tripropyl-isoburylammonium bromide, triburyl-cyclohexylammonium hydroxide, dibutyl-dihexyl ammonium hydroxide, choline, triethyl-hydroxyethyl ammonium hydroxide, tripropyl-hydroxyethyl ammonium hydroxide, tributyl-hydroxyethyl ammonium hydroxide, tributyl-benzyl ammonium hydroxide, triethyl-benzyl ammonium hydroxide, tripropyl-benzyl ammonium hydroxide, N,N,N-triethyl-adamantyl ammonium chloride, and N,N,N-tripropyl-adamantyl ammonium chloride.
Optionally, R1 is at least one of tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide and choline:
Optionally, R1 one of quaternary ammonium compounds;
Optionally, R1 at least one of tetramethylammonium hydroxide tetraethylammonium hydroxide, tetrapropylammonium hydroxide and choline.
Optionally, R2 is at least one of pyridine, N-methylpyridine, N-ethylpyridine, N-propylpyridine, N-butylpyridine, N-ethyl-3-butylpyridine, 1-ethyl-2-propylpyridine hydroxide, piperidine N,N-dimethylpiperidine, N,N-dimethyl-3,5-diethylpiperidine hydroxide, N,N-dimethyl-3,5-dipropylpiperidine hydroxide, N,N-diethyl-3,5-dipropylpiperidine hydroxide, N,N-diethyl-2,6-dimethylpiperidine hydroxide, N,N-dimethyl-2,6-diethylpiperidine hydroxide, imidazole, 1-ethyl-3-butylimidazole hydroxide, 1-ethyl-3-butyl-4-propylimidazole hydroxide, 1-benzyl-3-methylimidazole hydroxide, 1-benzyl-3-ethylimidazole hydroxide, 1-benzyl-3-butylimidazole hydroxide piperazine, N-methylpiperazine, 1,4-dipropylpiperazine, 1-methyl-4-ethylpiperazine, and 1-ethyl-4-butyl-5-methylpiperazine.
Optionally, an aging temperature in step a) rangs from 25 to 140° C. for an aging time in a range from 0.5 to 30 days.
Optionally, the upper limit of the aging temperature is 30° C., 35° C., 40° C., 45° C., 50° C., 55° C., 60° C., 65° C., 70° C., 75° C., 80° C., 85° C., 90° C., 95° C., 100° C., 110° C., 120° C., 130° C. or 140° C., and the low kit limit is 20° C., 30° C., 35° C., 40° C., 45° C., 50° C., 55° C., 60° C., 65° C., 70° C., 75° C., 80° C., 85° C., 90° C., 95° C., 100° C., 110° C. 120° C., or 130° C.
Optionally, the upper limit of aging time is 1 day, 2 days, 3 days, 4 days, 5 days, 6 days, days, 8 days, 9 days, 10 days, 11 days, 12 days, 13 days, 14 days, 15 days, 18 days, 20 days, 25 days or 30 days, and the lower limit thereof is 0.5 day, 1 day, 2 days, 3 days, 4 days, 5 days, 6 days, 7 days, 8 days, 9 days, 10 days, 11 days, 12 days, 13 days, 14 days, 15 days, 18 days, 20 days or 25 days.
Optionally, as aging temperature in step a) range from 25 to 140° C. far as aging time in a range from 1 to 30 days.
Optionally, an aging temperature in step a) ranges from 30 to 120° C. for an aging time in a range from 1 to 25 days.
Optionally, the aging in step a) is a two-stage aging, the temperature for the first stage aging ranges firm 30 to 40° C., the time for the first stage aging ranges from 0.5 to 5 days while the temperature for the second stage aging ranges from 50 to 100° C., and the time for second stage aging ranges from 2 to 8 days.
Optionally, step a) comprises: mixing the aluminum source A1, the alkali metal source M1, the organic templating agent R1 and water uniformly, adding the silicon source S1 therein. stirring, mixing and it aging, wherein an aging temperature ranges from 25 to 140° C., and an aging time ranges from 1 to 30 days to obtain the directing agent.
Optionally, the aluminum source A2, the silicon source Si2, the alkali metal source M2, the organic templating agent R2, and water in step b) have the following molar ratios:
Optionally, the aluminum source A2, silicon source Si2, alkali metal source M2, organic templating agent R2, and water in the raw material II in step b) have the following molar ratios:
Optionally, the upper limit of the molar ratio of SiO2/Al2O3 in step b) is 15, 20, 30, 40, 45, 50, 60, 70, 80, 90, 100, 110, 120, 130, 140, 150, 160, 170, 180, 190 or 200: and the lower limit thereof is 10, 15, 20, 30, 40, 45, 50, 60, 70, 80, 90, 100, 110, 120, 130, 140, 150, 160, 170, 180, or 190.
Optionally the upper limit of the molar ratio of M2O/Al2O3 in step b) 1.8, 2.0, 3.0, 4.0, 4.5, 4.8, 5.0. 6.0, 7.0, 8.0. 9.0, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 22, 25, 28, 29 or 30, and the lower limit hereof is 0.1, 1.8, 2.0, 3.0, 4.0, 4.5, 4.5, 5.0, 6.0, 7.0, 8.0, 9.0, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 22, 25, or 28.
Optionally, the upper limit of the molar ratio of R/Al2O3 in step b) is 2, 3, 3.6, 4, 4.5, 4.8, 5, 5.2, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 22, 25, 28, 29, 30, 32, 35, 38, 40, 42 or 45, and the bitter limit thereof is 1, 2, 3, 3.6, 4, 4.5, 4.8, 5, 5.2, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 22, 25, 28, 29, 30, 32, 35, 38, 40, or 42.
Optionally the upper limit of the molar ratio of H2O/Al2O3 in step b) is 200, 300, 400, 500, 600, 700, 800, 900, 1000, 1100, 1200, 1300, 1400, 1500, 1600, 1700, 1800, 1900, 2000, 2100, 2200, 2300, 2400, 2500, 2600, 2700, 2800, 2900, 3000, 3200, 3500, 3800, 4000, 5000 or 6000, and the lower limit thereof is 100, 200, 300, 400, 500, 600, 700, 800, 900, 1000, 1100, 1200, 1300, 1400, 1500, 1600, 1700, 1800, 1900, 2000, 2100, 2200, 2300, 2400, 2500, 2600, 2700, 2800, 2900, 3000, 3200, 3500, 3800, 4000 or 5000.
Optionally the weight ratio of the silica in the directing agent to the silica in the initial gel in step c) ranges from 0.01:1 to 0.3:1.
Optionally the weight ratio of the silica in the directing agent to the silica in the initial gel in step c) is airy one of the following mike or a range ratio defined by any two ratios; 0.01:1, 0.02:1, 0.03:1, 0.04:1, 0.05:1, 0.06:1, 0.07:1, 0.08:1, 0.091, 0.1:1, 0.11:1, 0.12:1, 0.13:1, 0.14:1, 0.15:1, 0.16:1, 0.23:1, 0.25:1, 0.30:1.
Optionally, the weight ratio of the silica in the directing agent to the silica in the initial gel in step c) ranges from 0.01:1 to 0.3:1.
Optionally, the weight ratio of the silica in the directing agent to the silica in the initial gel in step c) ranges from 0.01:1 to 0.2:1.
Optionally, a crystallization temperature in step c) ranges from 90 to 180° C. for the crystallization time in a rage from 1 to 15 days.
Optionally, the upper limit of the crystallization temperature is 100° C., 120° C., 140° C., 160° C., or 180° C. while the lower limit of the crystallization temperature 90° C., 100° C., 110° C., 140° C., or 150° C.
Optionally the upper limit of the crystallization time in step c) is 2 days, 3 days, 4 days, 5 days, 6 days, 7 days, 8 days, 9 days, 10 days, 11 days, 12 days, 13 days, 14 days or 15 days, and the lower limit thereof is 2 days, 3 days, 4 days, 5 days, 6 days, 7 days, 8 days, 9 days, 10 days, 11 days, 12 days, 13 days or 14 days.
Optionally, a crystallization temperature in step c) ranges from 90 to 140° C. for the crystallization time in a range from 3 to 15 days.
Optionally, the crystallization in step c) is performed dynamically or statically.
Optionally, the crystallization in step c) is performed in a combination of dynamical and statical manners.
Optionally, the crystallization in step c) is rotational crystallization.
Optionally, step c) includes: adding the directing agent in step a) to the initial gel in step b), stirring and mixing, and then placing the obtained mixture in a sealed reactor to perform crystallization to obtain the high-silica Y molecular sieve having FAU topology.
Optionally, in step c), the stirring is performed for 1 to 48 hours.
Optionally, the upper limit of the stirring time is 48 hours, 44 hours, 40 hours, 36 hours, 32 hours, 28 hours, 24 hours, 20 hours, 16 hours, 12 hours, 8 hours, 4 hours or 2 hours, and the lower limit thereof is 1 hour, 2 hours, 4 hours, 8 hours, 12 hours, 16 hours, 20 hours, 24 hours, 28 hours, 32 hours, 36 hours, 40 hours or 44 hours.
Optionally, step c) includes: adding the directing agent in step a) to the initial gel in step b), mixing uniformly and placing the obtained mixture in a sealed reactor to perform crystallization, wherein a crystallization temperature ranges from 90 to 140° C., and a crystallization time ranges from 3 to 15 days; after the crystallization is completed, separating, washing, and drying the obtained solid to obtain the high-silica Y molecular sieve having FAU topology.
Optionally, the method comprises the following steps:
As an embodiment, the synthesis process of the high-silica molecular sieve is as follows:
According to another aspect of the present application, there is provided use of the high-silica Y molecular sieve prepared by the above method in fluid catalytic cracking (FCC), wherein the prepared molecular sieve has a high silica alumina oxide ratio ranging from 7 to 30, good hydrothermal/thermal stability, and has good catalytic reaction ativity.
The anhydrous chemical constitution of the molecular sieve is shown in formula I:
kM.mR1.mR2.(SixAly)Oz Formula I
the structural formula of the quaternary ammonium compound is as shown in formula II;
wherein, in formula II, R21, R22, R23 and R24 are independently at least one of C1˜C12 alkyl, C1˜C12 alkoxy, C1˜C12 hydroxyalkyl, aryl and adamantyl;
Xn− is one of OH−, Cl−, Br−, I−, NO3−, HSO4−, H2PO3−, SO42−, HPO32−, and PO33−.
Optionally, m=0.01˜0.20.
Optionally, k=0.01˜0.15; m=0.01˜0.1; n=0.02˜0.15.
Optionally k=0.02˜0.13; m=0.01˜0.04; n=0.03˜0.08.
Optionally the “C1˜C12 alkyl” includes “C1˜C12 phenyl alkyl”.
Optionally, the “aryl” includes “C7˜C12 aryl”.
Optionally, the “C7˜C12 aryl” includes “C7˜C12 alkyl aryl”.
Optionally, M is at least one of Na, K, and Cs, and 2x/y=7˜30.
Optionally, M is at least one of Na, K, and Cs, and 2x/y=8˜30.
Optionally, the upper limit of 2x/y is 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29 or 30, and the lower limit thereof is 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 22, 23, 24, 25, 26, 27, 28 or 29.
Optionally, R1 and R2 are independently one of quaternary ammonium compounds,
Optionally, R1 and R2 are independently at least one of tetramethylammonium hydroxide tetraethylammonium hydroxide, tetrapropylammonium hydroxide tetrabutylammonium hydroxide, tetrapentylammonium hydroxide, tetrahexylammonium hydroxide, tetrapropylammonium bromide, tetrabutylammonium chloride, tetrapentylammonium bromide, tripropyl-isobutylammonium bromide, tributyl-cyclohexylammonium hydroxide, dibutyl-dihexyl ammonium hydroxide, choline, triethyl-hydroxyethyl hydroxide, tripropyl-hydroxyethyl ammonium hydroxide, tributyl-hydroxyethyl ammonium hydroxide tributyl-benzyl ammonium hydroxide, triethyl-benzyl ammonium hydroxide, tripropyl-benzyl ammonium hydroxide, N,N,N-triethyl-adamantyl ammonium chloride, and N,N,N-tripropyl-adamantyl ammonium chloride.
Optionally R1 is at least one of tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, and choline;
Optionally, R1 is at least one of quaternary ammonium compound and R2 is at least one of nitrogen-containing heterocyclic compounds and derivatives thereof.
Optionally, R1 is at least one of tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide and choline;
Optionally, R2 is at least one of pyridine, N-methylpyridine, N-ethylpyridine, N-propylpyridine, N-butylpyridine, N-ethyl-3-butylpyridine, 1-ethyl-2-propylpyridine hydroxide, piperidine, N,N-dimethylpiperidine, N,N-dimethyl-3,5-diethylpiperidine hydroxide, N,N-dimethyl-3,5-dipropylpiperidine hydroxide, N,N-diethyl-3,5-dipropylpiperidine hydroxide, N,N-diethyl-2,6-dimethylpiperidine hydroxide, N,N-dimethyl-2,6-diethylpiperidine hydroxide, imidazole, 1-ethyl-3-butylimidazole hydroxide, 1-ethyl-3-butyl-4-propylimidazole hydroxide, 1-benzyl-3-methylimidazole hydroxide, 1-benzyl-3-ethylimidazole hydroxide, 1-benzyl-3-butylimidazole hydroxide, piperidine, N-methylpiperazine, 1,4-dipropylpiperazine, 1-methyl-4-ethylpiperazine, and 1-ethyl-4-butyl-5-methylpiperazine.
Optionally, the high-silica Y molecular sieve having FAU topology is an octahedral structure.
Optionally the particle size of the high-silica Y molecular sieve having FAU topology ranges from 50 mn to 2500 nm.
According to another aspect of the present application, there is provided a catalyst. The high-silica Y molecular sieve having FAU topology prepared according to the method described in the preset application can be used as a fluidized catalytic cracking catalyst and, support and catalyst for dual-function catalysis reaction such as hydrocracking, hydrogenation desulfurization and so on.
In the present application, dynamic crystallization means that the slurry in the crystallization reactor is in a non-stationary state, and static crystallization means that the slurry in the crystallization reactor is in a stationary state.
In the context of the present application, the term “silica-alumina ratio” refers to the molar ratio of silicon to aluminium in terms of SiO2 and Al2O3 in the molecular sieve, which has the same meaning as “2x/y” and “silicon-aluminum oxide ratio”.
In the present application, C1˜C12, C7˜C12 and the like all refer to the number of carbon atoms contained in the group. For example, “C1˜C12 alkyl” refers to an alkyl having 1˜12 carbon atoms.
In the present application, “alkyl” is a group formed by the loss of any hydrogen atom on —OH group of the molecule of an alkane compound. The alkane compound includes straight chain alkanes, branched chain alkanes, cycloalkanes, and branched cycloalkanes.
In the present application, “alkoxy” is a group formed by the loss of hydrogen atoms on —OH group of the molecule of an alkyl alcohol compound. For example, the methoxy —OCH7 is formed by the loss of the hydrogen atom on the —OH group of the CH7OH molecule.
In the present application, “hydroxyalkyl” is a group formed by the loss of any one hydrogen atom on non —OH group of the molecule of an alkyl alcohol compound. For example, the hydroxymethyl HOCH7 is formed by the loss of the hydrogen atom on the methyl of the CH7OH molecule.
In the present application, “aryl” is a group formed by the loss of one hydrogen atom in the aromatic ring of an aromatic compound. For example, p-methylphenyl is formed by the loss of the hydrogen atom on para position of methyl on the benzene ring.
In the present application, “alkylphenyl” refers to a group formed by the loss of a hydrogen atom on a bezene ring containing substituent. For example, p-methylphenyl is formed by the loss of the hydrogen atom on para position of methyl on the benzene ring.
In the present application, “phenylalkyl” refers to a group formed by the loss of one hydrogen atom of the alkyl substituent on the benzene ring. For example, the benzyl group (benzyl) is formed by the loss of one hydrogen atom of the methyl on toluene.
The present application will be described in detail below with reference to the examples, but the present application is not limited to these examples.
The analysis methods in the examples of the present application are as follows.
The X-ray powder diffraction phase analysis (XRD) of the product adopts to XPert PRO X-ray diffraction from PANalytical, the Netherlands. Cu target, Kα radiation source (λ=0.15418 nm), voltage 40 KV, current mA.
The instrument used in the scanning electron microscope (SEM) test is Hirachi SU8020 emission scanning electron microscope, and the accelerating voltage is 2 kV.
The elemental constitution was measured by Philips Magix 2424 X-ray fluorescence analyzer (XRF).
The silicon nuclear magnet (29Si-NMR) experiment was carried out on a Braker Avance III 600 (14.1 Tesla) spectrometer using a 7 mm double resonance probe with a rotation speed of 6 kHz. Using high-power proton decoupling program, sampling times are 1024, ×4 pulse width is 2.5 μs, sampling delay is 10 s, and 4,4-dimethyl-4-propanesulfonate (DSS) is used as chemical shift reference which is calibrated to be 0 ppm.
The carbon nuclear magnetic (13C MAS NMR) experiment was carried out on a Braker Avance III 600 (14.1 Tesla) spectrometer using a 4 mm triple resonance probe with a rotation speed of 12 kHz, wherein amantadine was used as the chemical shift reference which was calibrated to be 0 ppm.
Preparation of synthetic gel: 0.7 g sodium aluminate (Al2O3:48.3 wt %, Na2O: 35.3 wt %, China National Pharmaceutical (Group) Shanghai chemical Reagent Company), 0.20 g sodium hydroxide, 13.0 g tetrapropylammonium (25 wt %) were dissolved in 2.40 g deionized water and stirred until to be clear. 13.3 g silica gel (SiO2: 30 wt %, Shenyang Chemical Co., Ltd) was added therein dropwise and stirred for 0.5 hour. Then 0.4 g Y zeolite as seed crystal with silica-alumina ratio of 3 was added, and stirring was continued for 2 hours.
Synthesis of high-silica Y zeolite: The synthetic gel was transferred into a stainless-steel reactor, and was subject to rotational crystallization at 130° C. for 5 days. After the crystallization was completed, the obtained solid was separated from liquid, washed to be neutrality, then dried at 100° C. for 12 hours. The obtained sample was denoted as sample X #1.
X-ray diffraction (XRD) spectrum of sample X #1 is shown in
The preparation process of any one of samples X #2-X #30 is the same as that of Example 1. The raw materials for preparing samples X #2-X #30, molar ratio thereof, addition amount of seed crystal (weight ratio of seed crystal to SiO2 in gel), crystallization conditions, crystal structure, silica-alumina ration (the silica-alumina ratio of the obtained product is measured by X-ray fluorescence analyzer (XRF)) and the product constitutent are shown in Table 1.
Samples X #1-X #20 were prepared using silica-alumina molecular sieves having FAU topology as seed crystals, of which silica-alumina ratios were 3, 2.8. 3. 3.5, 45. 6. 6, 6, 6, 7, 70, 10. 4. 5, 6, 8, 3.5, 35, 12. 20 respectively, and which were purchased from Zibo Rumxin Chemical Technology Co., Ltd. Samples X #21-X #30 were prepared using silica-alumina molecular sieves having EMT topology as seed crystals, of which silica-alumina ratios were 10, 8, 8.5, 7, 7, 8, 21, 7, 8, 22 respectively, and which were purchased from Henan Huanyu Molecular Sieve Co., Ltd.
The specific types of raw materials for preparing synthetic gel, molar ratio thereof, preparation process and crystallization conditions are the same as those of sample X #1 in Example 1, except than the seed crystal addition step is omitted. The specific types of raw materials, molar ratio thereof, crystallization conditions, and crystal structure of the product are shown in Table 2. The obtained samples are denoted as comparative samples V #1-V #30.
The phases of samples X #1-X #30 and comparative samples V #1-V #30 were analyzed by X-ray diffraction method.
The results show that each of the samples X #1-X #30 prepared in Examples 1 and 2 is Y molecular sieve with both high purity and high crystallinity. The XRD spectrum of sample X #1 as typical representative is shorn in
Each of V #1-V #30 as products in Table 2 is amorphous, and the XRD spectrum of the comparative sample V #1 as typical represenative is shown in
:2.0Na2O:4.8R21:360H2O
Al
)O2
:1.8Na2O:3.6R21:200H2O
Al
)O2
:1.8Na2O:5.2R21:400H2O
Al
)O2
:8.0Na2O:13R22:800H2O
Al
)O2
:3.0Na2O:5R22:400H2O
Al
)O2
:3Na2O:4.5R23:400H2O
(Si
Al
)O2
:25Na2O:45R2
:3000H2O
(Si
Al
)O2
:7Na2O:11R2
:800H2O
(Si
Al
)O2
:8.0Na2O:15R2
:900H2O
(Si
Al
)O2
:20Cs2O:10R24:800H2O
Al
)O2
:4.0Na2O:7R24:500H2O
Al
)O2
:15K2O:20R24:1500H2O
Al
)O2
:4.0Na2O:7R2
:500H2O
(Si
Al
)O2
:12Na2O:25R2
:2000H2O
(Si
Al
)O2
:15Na2O:35R2
:2800H2O
(Si
Al
)O2
:10Na2O:18R2
:1500H2O
(Si
Al
)O2
:12Na2O:23R2
:1800H2O
(Si
Al
)O2
:7Na2O:15R2
:1100H2O
(Si
Al
)O2
:1Al2O3
:4Na2O:9R2
:800H2O
(Si
Al
)O2
:1Al2O3
:0.1Na2O:5R2
:150H2O
(Si
Al
)O2
:1Al2O3
:1.8Na2O:5R2
:200H2O
Al
)O2
:1Al2O3
:1.8Na2O:4.8R2
:400H2O
Al
)O2
:1Al2O3
:5Na2O:12R2
:800H2O
Al
)O2
:1Al2O3
:4.0Na2O:4R2
:400H2O
(Si
Al
)O2
:3.0Na2O:4R2
:280H2O
(Si
Al
)O2
:10Na2O:18R210:2000H2O
Al
)O2
:15Na2O:30R210:2800H2O
Al
)O2
:10Na2O:15R211:1500H2O
Al
)O2
:5Na2O:10R211:1500H2O
Al
)O2
:14Na2O:25R211:2500H2O
Al
)O2
indicates data missing or illegible when filed
:1Al2O3
:2.0Na2O:4.8R2
:360H2O
:1Al2O3
:1.8Na2O:3.6R2
:200H2O
:1Al2O3
:1.8Na2O:5.2R2
:400H2O
:1Al2O3
:8.0Na2O:13R22:800H2O
:400H2O
:3Na2O:4.5R2
:400H2O
:3000H2O
:800H2O
:900H2O
:4.0Na2O:7R24:500H2O
:15K2O:20R24:1500H2O
:4.0Na2O:7R25:500H2O
:12Na2O:25R25:2000H2O
:15Na2O:35R25:2800H2O
:10Na2O:18R25:1500H2O
:1Al2O3
:12Na2O:23R26:1800H2O
:1Al2O3
:7Na2O:15R26:1100H2O
:1Al2O3
:4Na2O:9R26:800H2O
:0.1Na2O:5R2
:150H2O
:1Al2O3
:1.8Na2O:5R27:200H2O
:1Al2O3
:1.8Na2O:4.8R28:400H2O
:1Al2O3
:5Na2O:12R2
:800H2O
:1Al2O3
:4.0Na2O:4R29:400H2O
:3.0Na2O:4R29:280H2O
:10Na2O:18R210:2000H2O
:15Na2O:30R210:2800H2O
:14Na2O:25R2
:2500H2O
indicates data missing or illegible when filed
Al
)O2
Al
)O2
Al
)O2
:8.0Na2O:13R2:800H2O
Al
)O2
Al
)O2
:3Na2O:4.5R1:400H2O
(Si
Al
)O2
:6000H2O
(Si
Al
)O2
(Si
Al
)O2
(Si
Al
)O2
Al
)O2
:4.0Na2O:7R4:500H2O
Al
)O2
:2.5Na2O:5R4:400H2O
Al
)O2
:4.0Na2O:7R2
:500H2O
(Si
Al
)O2
:12Na2O:25R2
:2000H2O
(Si
Al
)O2
:1Al2O32:15Na2O:35R2
:2800H2O
(Si
Al
)O2
:1Al2O3
:10Na2O:18R2
:1500H2O
(Si
Al
)O2
:1Al2O3
:12Cs2O:23R
:1800H2O
(Si
Al
)O2
:1Al2O3
:7Na2O:15R
:1100H2O
(Si
Al
)O2
:1Al2O3
:4Na2O:9R
:800H2O
(Si
Al
)O2
:1Al2O3
:0.1Na2O:5R
:150H2O
(Si
Al
)O2
:1Al2O3
:1.8Na2O:5R
:200H2O
(Si
Al
)O2
:1Al2O3
:1.8Na2O:4.8R8:400H2O
(Si
Al
)O2
:1Al2O3
:5Na2O:12R8:800H2O
(Si
Al
)O2
:4.0Na2O:4R9:400H2O
(Si
Al
)O2
(Si
Al
)O2
Al
)O2
Al
)O2
:10Na2O:15R11:1500H2O
Al
)O2
:5Na2O:10R11:1500H2O
Al
)O2
Al
)O2
indicates data missing or illegible when filed
:1Al2O3
:2.0Na2O:4.8R
:360H2O
:1Al2O31:1.8Na2O:3.6R
:200H2O
:1Al2O32:1.8K2O:5.2R
:400H2O
:1Al2O3
:8.0Na2O:13R
:800H2O
:400H2O
:1Al2O3
:3Na2O:4.5R
:400H2O
:1Al2O3
:25Na2O:45R
:6000H2O
:1Al2O3
:7Na2O:11R
:800H2O
:1Al2O3
:8.0Na2O:15R2
:900H2O
:1Al2O3
:4R4:200H2O
:1Al2O3
:4.0Na2O:7R
:500H2O
:1Al2O3
:2.5Na2O:5R
:400H2O
:1Al2O3
:4.0Na2O:7R
:500H2O
:1Al2O3
:12Na2O:25R
:2000H2O
:1Al2O3
:15Na2O:35R
:2800H2O
:1Al2O3
:10Na2O:18R
:1500H2O
:1Al2O3
:12Cs2O:23R
:1800H2O
:1Al2O3
:7Na2O:15R
:1100H2O
:1Al2O3
:4Na2O:9R
:800H2O
:1Al2O3
:0.1Na2O:1.5R
:150H2O
:1Al2O3
:1.8Na2O:5R
:200H2O
:1Al2O3
:1.8Na2O:4.8R
:400H2O
:1Al2O3
:5Na2O:12R
:800H2O
:1Al2O3
:4.0Na2O:4R
:400H2O
:1Al2O3
:3Na2O:4R
:280H2O
:1Al2O3
:10Na2O:18R
:2000H2O
:1Al2O3
:15Na2O:30R
:2800H2O
:1Al2O3
:10Na2O:15R11:1500H2O
:1Al2O3
:5Na2O:10R11:1500H2O
:1Al2O3
:14Na2O:25R
:2500H2O
indicates data missing or illegible when filed
Preparation of synthetic gel: 0.7 g sodium aluminate (Al2O3:48.3 wt %, Na2O: 36.3 wt %, China National Pharmaceutical (Group) Shanghai Chemical Reagent Company), 0.20 g sodium hydroxide, 13.74 g N,N-dimethyl-3,5-dipropylpiperidine hydroxide (25 wt %.) were dissolved in 1.82 g deionized water and stirred until to be clear. 13.3 g silica sol (SiO2:30 wt % Shenyang Chemical Co., Ltd.) was added therein dropwise and stirred for 2 hours. Then 0.4 g Y zeolite as seed crystal with silica-alumina ratio of 3 was added, and stirring was continued for 2 hours.
Synthesis at high-silica Y zeolite: The synthesis gel was transferred into a stainless-steel reactor, and was subject to rotational crystallization at 130° C. for 5 days. After the crystallization was completed, the obtained solid was separated from liquid, washed to be neutrality, then dried at 100° C. for 12 hours. The obtained sample was denoted as sample X1.
X-ray diffraction (XRD) spectrum of sample X1 is shown in
The preparation process of any one of sample X2-X30 is the same as that of Example 4. The raw materials for preparing samples X2-X30, molar ratio thereof, addition amount of seed crystal (weight ratio of seed crystal to SiO2 in gel), crystallization conditions, crystal structure, silica-alumina ratio (the silica-alumina radio of the obtained product is measured by X-ray fluorescence analyzer (XRF)) and the product constitution are shown in Table 3.
Samples X1-X20 were prepared using silica-alumina to molecular sieves having FAU topology as seed crystals, of which silica-alumina ratios were 3, 2.8, 3.5, 40, 5, 6.6, 6, 6, 7, 92, 10, 3.5, 4. 6, 8, 4. 35, 12, 20 respectively, and which were purchased from Zibo Runxin Chemical Technology Co., Ltd. Samples X21-X30 were prepared using silica-alumina molecular sieves having EMT topology as seed crystals, of which silica-alumina ratios were 7, 7, 8.5, 7, 8, 10, 21, 32.8 and 7 respectively, and which were purchased from Henan Purchased by Hnamyu Molecular Steve Co., Ltd.
The preparation process of any one of samples V1-V30 is the same as that of Example 4, except that there is no seed crystal addition step. Types of raw materials, molar ratio thereof, crystallization conditions, and crystal structure of samples V1-V30 are shown in Table 4. The samples obtained are denoted as comparative samples V1-V30.
The phases of sample X1-X30 and comparative samples V1-V30 were analyzed by X-ray diffraction method.
The results show that each of the samples X1-X30 prepared in Examples 4 and 5 is Y molecular sieve with both high purity and high crystallinity. The XRD spectrum of sample X1 as typical representative is shown in
In Table 4, each of the comparative samples V1-V30 is amorphous, and a XRD spectrum of the comparative sample V1 as typical representative is shown in
:2.0Na2O:4.8R1:360H2O
Al
)O2
:1.8Na2O:3.6R1:200H2O
Al
)O2
Al
)O2
:8.0Na2O:13R2:800H2O
Al
)O2
Al
)O2
:3Na2O:4.5R1:400H2O
(Si
Al
)O2
(Si
Al
)O2
(Si
Al
)O2
(Si
Al
)O2
:4R4:200H2O
Al
)O2
:4.0Na2O:7R4:500H2O
Al
)O2
:2.5Na2O:5R4:400H2O
Al
)O2
:4.0Na2O:7R1:500H2O
(Si
Al
)O2
:12Na2O:25R2
:2000H2O
(Si
Al
)O2
:1Al2O32:15Na2O:35R2
:2800H2O
(Si
Al
)O2
:1Al2O32:10Na2O:18R2
:1800H2O
(Si
Al
)O2
:1Al2O3
:12Cs2O:23R
:1800H2O
(Si
Al
)O2
:1Al2O3
:7Na2O:15R
:1100H2O
(Si
Al
)O2
:1Al2O3
:4Na2O:9R
:800H2O
(Si
Al
)O2
:1Al2O3
:0.1Na2O:5R
:150H2O
(Si
Al
)O2
:1Al2O3
:1.8Na2O:5R
:200H2O
Al
)O2
:1Al2O3
:1.8Na2O:4.8R8:400H2O
Al
)O2
:1Al2O3
:5Na2O:12R
:800H2O
Al
)O2
:1Al2O3
:4.0Na2O:4R
:400H2O
(Si
Al
)O2
:3.0Na2O:4R9:280H2O
Al
)O2
Al
)O2
Al
)O2
Al
)O2
Al
)O2
:2500H2O
Al
)O2
indicates data missing or illegible when filed
:2.0Na2O:4.8R1:360H2O
:1.8Na2O:3.6R1:200H2O
:8.0Na2O:13R2:800H2O
:3Na2O:4.5R1:400H2O
:4R4:200H2O
:4.0Na2O:7R4:500H2O
:2.5Na2O:5R4:400H2O
:4.0Na2O:7R1:500H2O
:12Na2O:25R2
:2000H2O
:1Al2O32:15Na2O:35R2
:2800H2O
:1Al2O32:10Na2O:18R2
:1800H2O
:1Al2O3
:12Cs2O:23R
:1800H2O
:1Al2O3
:7Na2O:15R
:1100H2O
:1Al2O3
:4Na2O:9R
:800H2O
:1Al2O3
:0.1Na2O:5R
:150H2O
:1Al2O3
:1.8Na2O:5R
:200H2O
:1Al2O3
:1.8Na2O:4.8R8:400H2O
:1Al2O3
:5Na2O:12R
:800H2O
:1Al2O3
:4.0Na2O:4R
:400H2O
:3.0Na2O:4R9:280H2O
:2500H2O
1: Alumina:
2: Aluminum isopropoxide:
3: Sodium aluminate:
4: Aluminum nitrate:
5: Aluminum tri-sec-butoxide:
6: Aluminum sulfate:
7: Aluminum powder:
indicates data missing or illegible when filed
Preparation of directing agent 1.3 g sodium hydroxide (analytical purity, Tianjin Koenion Chemical Reagent Co., Ltd.) and 1.7 g alumina (chemical purity, China National Pharmaceutical (Group) Shanghai Chemical Reagent Co., Ltd.) were dissolved in 84.1 g tetraethylammonium hydroxide (35 wt % aqueous solution, Aladdin reagent (Shanghai) Co., Ltd.) and stirred until to be clear. 34.7 g ethyl orthosilicate was added therein dropwise (chemical purity. China pharmaceutical (Group) Shanghai chemical reagent company) and stirred for 2 hours. The obtained solution was allowed to stand at 50° C. for 12 hours to perform aging, and then stand at 100° C. for 45 hours.
Preparation of synthetic gel: 0.7 g sodium aluminate (Al2O3: 48.3 wt %, Na2O: 34.3 wt %, China National Pharmaceutical (Grow) Shanghai Chemical Reagent Company), 0.20 g sodium hydroxide, and 9.8 g tetrapropylammonium hydroxide (25 wt %) were dissolved in 4.8 g deionized water and stirred until to be clear. 13.3 g silica sol (SiO2: 30 wt %, Shenyang Chemical Co., Ltd.) was added therein dropwise and stirred far 2 hours. Then 4.9 g the above-mentioned directing agent was added therein and stirred for 3 hours.
Synthesis of high-silica Y molecular sieve: The synthetic gel was transferred into a stainless-steel reactor, and was subject to rotational crystallization at 130° C. for 5 days. After the crystallization was completed, the obtained solid was separated from liquid, washed to be neutrality, then dried at 100° C. for 12 hours. The obtained sample was denoted as sample Y #1.
X-ray diffraction (XRD) spectrum of sample Y #1 is shown in
The preparation process of any one of samples Y #2-Y #30 is the same as that of Example 7. The raw materials for preparing samples Y #2-Y #30, molar ratio thereof, crystallization conditions, crystal structure, and silica-alumina ratio (the silica-alumina ratio of the obtained product is measured by X-ray fluorescence analyzer (XRF)) are shown in Table 5. Aging temperature and time for preparing directing agent, aging manner, addition amount of directing agent and sample constitution are shown in Table 6.
:400H2O
:800H2O
:900H2O
:1Al2O3
:1.8Na2O:12R11:180H2O
:1Al2O32:1Na2O:10R1
:180H2O
:5.0Na2O:6R24:500H2O
:1Al2O3
:1.8Na2O:12R11:180H2O
:3.0Na2O:5R24:400H2O
:1Al2O32:1Na2O:10R1
:180H2O
:5.0Na2O:6R2
:500H2O
:1Na2O:10R11:200H2O
:12Na2O:20R2
:2000H2O
:2Na2O:8R14:100H2O
:2800H2O
:1Al2O32:10Na2O:15R2
:1500H2O
:12Na2O:20R26:180H2O
:1Al2O3
:1Na2O:10R11:100H2O
:1Al2O3
:5Na2O:12R26:1100H2O
:1Al2O3
:4Na2O:8R26:800H2O
:200H2O
:280H2O
:5Na2O:8R28:800H2O
:0.5Na2O:18R1
:400H2O
:1Al2O3
:4.0Na2O:4R29:400H2O
:0.5Na2O:8R1
:400H2O
:3.0Na2O:4R2
:280H2O
:1Al2O3
:8R11:150H2O
:1Al2O3
:2Na2O:7R1
:180H2O
:0.5Na2O:8R1
:150H2O
:10Na2O:15R211:1500H2O
:1Na2O:8R12:480H2O
:5Na2O:10R2
:1500H2O
:3Na2O:40R1
:600H2O
indicates data missing or illegible when filed
Al
)O2
0.05R21(Si
Al
)O2
0.05R21(Si
Al
)O2
0.05R22(Si
Al
)O2
0.08R22(Si
Al
)O2
0.06R23(Si
Al
)O2
0.04R2
(Si
Al
)O2
0.04R23(Si
Al
)O2
0.04R23(Si
Al
)O2
0.05R24(Si
Al
)O2
0.04R24(Si
Al
)O2
0.06R24(Si
Al
)O2
0.05R2
(Si
Al
)O2
0.04R2
(Si
Al
)O2
(Si
Al
)O2
0.04R2
(Si
Al
)O2
0.04R26(Si
Al
)O2
0.04R26(Si
Al
)O2
Al
)O2
0.05R27(Si
Al
)O2
0.05R27(Si
Al
)O2
0.03R28(Si
Al
)O2
Al
)O2
0.05R29(Si
Al
)O2
0.04R29(Si
Al
)O2
0.03R210(Si
Al
)O2
0.03R210(Si
Al
)O2
0.03R211(Si
Al
)O2
0.05R211(Si
Al
)O2
0.04R211(Si
Al
)O2
indicates data missing or illegible when filed
The specific types of raw materials for preparing synthetic gel, molar ratio thereof, preparation process and crystallization conditions are the same as those in the preparation of sample Y #1 in Example 7. There is no directing agent preparation step, and there is not addition of directing agent in the subsequent gel synthesis step. The type of raw materials, molar ratio thereof, crystallization conditions, and crystal structures of product are shown in Table 7. The obtained samples are denoted as comparative samples S #1-S #30.
:1.8Na2O:3R21:200H2O
:8.0Na2O:9R22:800H2O
:4.0Na2O:4R2
:400H2O
:3000H2O
:800H2O
:900H2O
:200H2O
:5.0Na2O:6R2
:500H2O
:3.0Na2O:5R2
:400H2O
:5.0Na2O:6R2
:500H2O
:12Na2O:20R2
:2000H2O
:1Al2O3
:15Na2O:28R2
:2800H2O
:1Al2O3
:10Na2O:15R2
:1500H2O
:1Al2O3
:12Na2O:20R26:1800H2O
:1Al2O3
:5Na2O:12R26:1100H2O
:1Al2O3
:4Na2O:8R26:800H2O
:1.8Na2O:4R28:400H2O
:5Na2O:8R28:800H2O
:4.0Na2O:4R29:400H2O
indicates data missing or illegible when filed
The specific types of raw materials, molar ratio thereof, preparation process and crystallization conditions are the same as those of sample Y #1 in Example 7, except that after the batching step of the directing agent is completed, only stirring at room temperature for 2 hours without aging was performed. The types of raw materials, molar ratio thereof, crystallization conditions, addition amount of directing agent, and the crystal structure of the prepared product are shown in Table 8. The obtained samples were denoted a comparative samples T #1-T #30.
:180H2O
:1.5K2O:30R11:600H2O
:8R11:400H2O
:8.0Na2O:9R22:800H2O
:200H2O
:4.0Na2O:4R2
:40020H2O
:180H2O
:3000H2O
:800H2O
:900H2O
:1Al2O3
:1.8Na2O:12R1
:180H2O
:1Al2O32:1Na2O:10R1
:180H2O
:5.0Na2O:6R24:500H2O
:180H2O
:3.0Na2O:5R24:400H2O
:180H2O
:5.0Na2O:6R23:500H2O
:1Na2O:10R1
:200H2O
:2000H2O
:2Na2O:8R1
:100H2O
:2800H2O
:1500H2O
:20R11:600H2O
:1Al2O3
:12Na2O:20R26:1800H2O
:1Al2O3
:1Na2O:10R11:100H2O
:1100H2O
:1Al2O3
:0.1Na2O:4R27:150H2O
:1Al2O32:1.8Na2O:3R27:200H2O
:280H2O
:1Al2O3
:1.8Na2O:4R28:400H2O
:1Al2O3
:0.5Na2O:10R14:200H2O
:1Al2O3
:5Na2O:8R28:800H2O
:0.5Na2O:18R11:400H2O
:1Al2O3
:4.0Na2O:4R2
:400H2O
:1Al2O3
:0.5Na2O:8R11:400H2O
:3.0Na2O:4R29:280H2O
:1Al2O3
:8R11:150H2O
:1Al2O3
:2Na2O:7R11:180H2O
:150H2O
:10Na2O:15R211:1500H2O
:5Na2O:10R211:1500H2O
indicates data missing or illegible when filed
The phase of samples Y #1-Y #30 and comparative samples S #1-S #30 and T #1-T #30 were analyzed by X-ray diffraction method.
The result show that the each of samples Y #1-Y #30 prepared in Examples 7 and 8 is Y molecular sieve with both high purity and high crystallinity. The XRD spectrum of sample Y #1 as typical representative is shown in
The comparative samples S #1-S #30 and the comparative samples T #1-T #30 in Table 7 and Table 8 am amorphous. The XRD spectra of the comparative sample S #1 and the comparative sample T #1 are shown in
Preparation of directing agent: 1.3 g sodium hydroxide (analytical parity, Tianjin Kocniou Chemical Reagent Co., Ltd.) and 1.7 g alumina (chemical purity. China National Pharmaceutical (Group) Shanghai Chemical Reagent Co., Ltd.) were dissolved in 84.1 g tetraethylammonium hydroxide (35 wt % aqueous solution, Aladdin reagent (Shanghai) Co., Ltd.) and stirred until to be clear. 34.7 g ethyl orthosilicate was added therein dropwise (chemical purity. China pharmaceutical (Group) Shanghai chemical reagent company) and stirred for 2 hours. The obtained solution was allowed to stand at 50° C. for 12 hours to perform aging and then to stand at 70° C. for 2 days.
Preparation of synthetic gel: 0.7 g sodium aluminate (Al2O3: 48.3 wt %, Na2O: 36.3 wt %, China National Pharmaceutical (Group) Shanghai Chemical Reagan Company), 0.20 g sodium hydroxide, and 10.30 g N,N-dimethyl-3,5-dipropylpiperidine hydroxide (25 wt %) were dissolved in 4.4 g deionized water and stirred until to be clear. 13.3 g silica sol (SiO2: 30 wt %, Shenyang Chemical Co., Ltd.) was added thereof dropwise and stirred for 2 hours. Then 4.9 g the above-motored directing agent was added therein and stirred for 3 hours.
Synthesis of high-silica Y molecular sieve: The synthetic gel was transferred into a stainless-steel reactor, was placed at 120° C. for 5 days under autogenous pressure. Then the obtained solid was separated from liquid, washed to be neutrality, and dried at 100° C. for 12 hours. The obtained sample was denoted as sale Y1.
X-ray diffraction (XRD) spectrum of sample Y1 is shown in
The preparation process of any one of samples Y2-Y30 is the same as that of Example 10. The raw materials for preparing samples Y2-Y30, molar ratio thereof, crystallization conditions, crystal structure, and silica-alumina ratio (the silica-alumina ratio of the obtained product is measured by X-ray fluorescence analyzer (XRF) are shown in Table 3. Aging temperature and time for preparing directing agent, addition amount of directing agent and sample constitution are shown in Table 10.
The specific preparation process is the same as that in the preparation of sample Y1 in Example 10, except that there is no directing agent preparation step, and there is not addition of directing agent in the subsequent gel synthesis step. The types of raw materials, molar ratio thereof, crystallization conditions and product structure of the prepared products are shown in Table 11. The samples obtained are denoted as comparative samples S1-S30.
The specific preparation process is the same as that m to preparation of sample Y1 in Example 10, except that after the batching step of the directing agent is completed, only stirring at room temperature for 2 hours without aging was performed. Types of raw materials, molar ratio thereof, crystallization conditions, addition amount of directing agent and product structure of each synthesized product are shown in Table 12. The samples obtained are denoted as comparative samples T1-T30.
The phases of samples Y1-Y30 and comparative samples S1-S30 and T1-T30 were analyzed by X-my diffraction method.
The results show that each of samples Y1-Y30 prepared in Examples 10 and 11 is Y molecular sieve with both high purity and high crystallinity. The XRD spectrum of sample Y1 as typical representative is shown in
In tables 9 and 10, the comparative samples S1-S30 and the comparative samples T1-T30 are all amorphous. As a typical representative, the XRD spectra of the comparative sample S1 and the comparative sample T1 are shown in
:8.0Na2O:9R22:800H2O
:4.0Na2O:4R2
:400H2O
:180H2O
:3000H2O
:800H2O
:900H2O
:1Al2O3
:1.8Na2O:12R1
:180H2O
:1Al2O32:1Na2O:10R1
:180H2O
:5.0Na2O:6R24:500H2O
:1Al2O3
:1.8Na2O:12R1
:180H2O
:3.0Na2O:5R24:400H2O
:1Al2O32:1Na2O:10R1
:180H2O
:5.0Na2O:6R2
:500H2O
:1Al2O3
:1Na2O:10R1
:200H2O
:12Na2O:20R2
:2000H2O
:1Al2O3
:2Na2O:8R1
:100H2O
:1Al2O32:15Na2O:28R2
:2800H2O
:1Al2O32:15R1
:150H2O
:1Al2O32:10Na2O:15R2
:1500H2O
:1Al2O3
:20R1
:600H2O
:1Al2O3
:12Na2O:20R2
:1800H2O
:1Al2O3
:1Na2O:10R1
:100H2O
:1Al2O3
:5Na2O:12R2#Z,8996:1100H2O
:1Al2O3
:1.8Na2O:12R14:180H2O
:1Al2O3
:4Na2O:8R26:800H2O
:400H2O
:1Al2O32:0.1Na2O:4R27:150H2O
:200H2O
:1Al2O32:1.8Na2O:3R27:200H2O
:280H2O
:1Al2O3
:1.8Na2O:4R28:400H2O
:1Al2O37:0.5Na2O:10R14:200H2O
:1Al2O3
:5Na2O:8R28:800H2O
:0.5Na2O:18R1
:400H2O
:1Al2O3
:4.0Na2O:4R29:400H2O
:1Al2O3
:0.5Na2O:8R1
:400H2O
:3.0Na2O:4R29:280H2O
:1Al2O3
:8R1
:150H2O
:1Al2O3
:2Na2O:7R1
:180H2O
:1Al2O37:15Na2O:30R210:2800H2O
:150H2O
:10Na2O:15R211:1500H2O
:5Na2O:10R211:1500H2O
:600H2O
indicates data missing or illegible when filed
Al
)O2
0.05R21(Si
Al
)O2
0.05R21(Si
Al
)O2
0.05R22(Si
Al
)O2
0.08R22(Si
Al
)O2
Al
)O2
0.04R23(Si
Al
)O2
Al
)O2
Al
)O2
0.05R24(Si
Al
)O2
0.04R24(Si
Al
)O2
0.06R24(Si
Al
)O2
0.05R25(Si
Al
)O2
0.04R25(Si
Al
)O2
0.03R25(Si
Al
)O2
0.04R25(Si
Al
)O2
0.04R26(Si
Al
)O2
0.04R26(Si
Al
)O2
0.04R26(Si
Al
)O2
0.05R27(Si
Al
)O2
0.05R27(Si
Al
)O2
0.03R28(Si
Al
)O2
0.04R28(Si
Al
)O2
0.05R29(Si
Al
)O2
0.04R29(Si
Al
)O2
0.03R210(Si
Al
)O2
0.03R210(Si
Al
)O2
0.03R211(Si
Al
)O2
0.05R211(Si
Al
)O2
0.04R211(Si
Al
)O2
indicates data missing or illegible when filed
:2.0Na2O:3.6R2
:360H2O
:1.8Na2O:3R2
:200H2O
:400H2O
:8.0Na2O:9R22:800H2O
:4.0Na2O:4R2
:400H2O
:3000H2O
:800H2O
:900H2O
:1.8Na2O:4R24:200H2O
:5.0Na2O:6R24:500H2O
:3.0Na2O:5R24:400H2O
:5.0Na2O:6R25:500H2O
:12Na2O:20R25:2000H2O
:1Al2O3
:15Na2O:28R25:2800H2O
:1Al2O3
:10Na2O:15R25:1500H2O
:1Al2O3
:12Na2O:20R26:1800H2O
:1Al2O3
:5Na2O:12R26:1100H2O
:1Al2O3
:4Na2O:8R26:800H2O
:1Al2O3
:1.8Na2O:3R27:200H2O
:1Al2O3
:1.8Na2O:4R2
:400H2O
:1Al2O3
:5Na2O:8R28:800H2O
:1Al2O3
:4.0Na2O:4R2
:400H2O
:3.0Na2O:4R29:280H2O
:10Na2O:18R210:2000H2O
:15Na2O:30R210:2800H2O
:10Na2O:15R210:1500H2O
:5Na2O:10R211:1500H2O
:14Na2O:25R211:2500H2O
:1Al2O3
:1.8Na2O:3R2
:200H2O
indicates data missing or illegible when filed
:1Al2O31:1Na2O:12R12:180H2O
:1Al2O31:1Na2O:10R1
:180H2O
:200H2O
:1.8Na2O:4R22:400H2O
:1Al2O3
:10R1
:8R1
:400H2O
:1Al2O3
:8.0Na2O:9R2
:800H2O
:200H2O
:400H2O
:1Na2O:10R1
:180H2O
:3000H2O
:800H2O
:900H2O
:1Al2O3
:1.8Na2O:12R1
:180H2O
:1Al2O32:1Na2O:10R1
:180H2O
:5.0Na2O:6R24:500H2O
:1Al2O3
:1.8Na2O:12R1
:180H2O
:3.0Na2O:5R24:400H2O
:1Al2O32:1Na2O:10R1
:180H2O
:5.0Na2O:6R2
:500H2O
:1Al2O3
:1Na2O:10R1
:200H2O
:12Na2O:20R2
:2000H2O
:1Al2O3
:2Na2O:8R1
:100H2O
:1Al2O32:15Na2O:25R2
:2800H2O
:1Al2O32:15R1
:250H2O
:1Al2O32:10Na2O:15R2
:1500H2O
:1Al2O3
:R:600H2O
:1Al2O3
:12Na2O:20R26:1800H2O
:1Al2O3
:1Na2O:10R1
:100H2O
:1Al2O3
:5Na2O:12R2
:1100H2O
:1Al2O3
:1.8Na2O:12R14:180H2O
:1Al2O3
:4Na2O:8R26:800H2O
:400H2O
:1Al2O32:0.1Na2O:4R2
:150H2O
:0.5Na2O:8R1
:200H2O
:1Al2O32:1.8Na2O:3R2
:200H2O
:280H2O
:1Al2O3
:1.8Na2O:4R2
:400H2O
:1Al2O37:0.5Na2O:10R14:200H2O
:1Al2O3
:5Na2O:8R28:800H2O
:0.5Na2O:18R1
:400H2O
:4.0Na2O:4R2
:400H2O
:1Al2O3
:0.5Na2O:8R1
:400H2O
:3.0Na2O:4R2
:280H2O
:1Al2O3
:8R1
:150H2O
:1Al2O3
:2Na2O:7R1
:180H2O
:150H2O
:1Al2O3
:10Na2O:15R211:1500H2O
:1Na2O:8R1
:480H2O
:1Al2O3
:5Na2O:10R211:1500H2O
:3Na2O:40R1
:600H2O
:1Al2O37:14Na2O:25R211:2500H2O
indicates data missing or illegible when filed
The above example are only illustrative, and do not limit the present application in any form. Any change or modification made by the skilled in the art based on the technical content disclosed above, without departing from the spirit of the present application is equivalent example and falls within the scope of the present application.
| Number | Date | Country | Kind |
|---|---|---|---|
| 201910312157.0 | Apr 2019 | CN | national |
| 201910312310.X | Apr 2019 | CN | national |
| 201910312333.0 | Apr 2019 | CN | national |
| 201910312367.X | Apr 2019 | CN | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/CN2019/106165 | 9/17/2019 | WO |
