CN103771450A - Preparation method of micropore hollow ball molecular sieve - Google Patents
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Abstract
The invention discloses a preparation method of a hollow ball ZSM-5 molecular sieve. The preparation method comprises the following steps: mixing TPAOH, NaAlO2, and water according to a specific ratio so as to prepare a solution, controlling the pH value of the solution in a range of 8 to 10, in a condition of reduced pressure suction filtration, dropwise adding the solution into mesoporous silicon dioxide solid ball molecular sieve dry glue, carrying out a suction filtration treatment and a wetting treatment, carrying out crystallization reactions for 1 to 2 days at a temperature of 160 to 180 DEG C, filtering and washing the crystallized slurry, and finally drying and burning so as to obtain the hollow ball ZSM-5 molecular sieve. The preparation method has the advantages of simple synthesis steps, easily-controllable operation process, cheap raw material, and little preparation time. The prepared molecular sieve can be applied to an FCC gasoline selective hydro-desulfurization process, has a very good olefin protection characteristic, and can maximally reduce the loss of gasoline octane value.
Description
Technical field
The present invention relates to a kind of preparation method of microporous hollow sphere molecule sieve, particularly a kind of preparation method of the microporous hollow sphere molecule sieve with ZSM-5 structure.This molecular sieve is specially adapted to FCC catalyst for selective hydrodesulfurizationof of gasoline.
Background technology
Recent years, people are more and more interested for the preparation of hollow ball molecular sieve.Because there is a larger cavity inside of hollow ball molecular sieve, although shell inner cavity and outside atmosphere have been isolated, the micropore that shell surface exists or mesoporously still can provide passage for molecule passes in and out cavity.Owing to having the structure of this uniqueness, hollow ball molecular sieve is expressed special hope in fields such as catalysis, absorption, acoustics, optics, electromagnetism, calorifics by people.
Conventionally, hollow ball molecular sieve, by realizing with organic formwork or dissolving kernel, need to be realized by the means such as roasting or chemical agent dissolves in order to produce cavity.For example, use organism ball (polymer particle) as hard template [B. Tan, S. E. Rankin, Langmuir 2005,21,8180-8187], the deficiency of the method is, prepares the method more complicated of spherical organic molecule, not easy to operate.Use emulsion drop as soft template [J. Wang, Y. Xia, W. Wang, M. Poliakoff, R. Mokaya, J. Mater. Chem. 2006,16,1751-1756] prepare hollow ball molecular sieve, the deficiency of the method is that the generation of emulsion drop is not easy to control.
The technology of synthetic hollow ball also has a lot of reports, as use spray-drying process [P. J. Bruinsma, A. Y. Kim, J. Liu, S. Baskaran, Chem. Mater. 1997, 9, 2507-2512], gas phase transfer method [A. Dong, Y. Wang, Y. Tang, N. Ren, Y. Zhang, Z. Gao, Chem. Mater. 2002, 14, 3217-3219], and use the layer laminate of being undertaken by electrostatic attraction with the polyelectrolyte of opposite charges to assemble method [F. Caruso, R. A. Caruso, H. M hwald, Science 1998, 282, 1111-1114].The shortcoming of these class methods is need to use accurate instrument, and operation to be very complicated, very difficult control.
Wu Peng etc. (J. Mater. Chem., 2010,20,10193 – 10199) disclose a kind of method of synthetic hollow ZSM-5 molecular sieve ball.The method is that employing Isopropylamine is structure directing agent, and take mesoporous silicon dioxide micro-sphere, (200 μ m ~ 300 μ, m) as silicon source, by controlling time and the temperature of hydrothermal crystallizing, have obtained hollow ZSM-5 molecular sieve ball.The method is the method that adopts hydrothermal crystallizing, adopting the weak Isopropylamine of alkalescence is that structure directing agent just can be made hollow ZSM-5 molecular sieve ball, and in this article, also point out to adopt the stronger TPAOH(TPAOH of alkalescence) because crystallization is too fast, globosity is caved in, connection between silicon oxide is easily ruptured, and cannot make hollow molecular sieve spheres.
Summary of the invention
In order to overcome the deficiencies in the prior art part, the preparation method of the microporous hollow sphere molecule sieve that the invention provides that a kind of synthesis step is simple, operating process is easily controlled, raw materials cost cheapness, preparation used time is few.This preparation method can make hollow ball molecular sieve keep having the microvoid structure of ZSM-5, the catalyzer of being made by hollow ball molecular sieve of the present invention, the feature in selective hydrodesulfurization process for FCC gasoline component with good guarantor's alkene, can reduce the loss of gasoline octane rating to greatest extent.
The preparation method of hollow ball ZSM-5 molecular sieve of the present invention, comprising:
(1) by (0.5～2.0) SiO
2: (0.1～0.5) Al
2o
3: (0.1～0.5) Na
2o:(1～5) H
2o:(0.1～0.5) TPAOH(TPAOH) mole proportioning, by TPAOH, NaAlO
2with water mixing wiring solution-forming, the pH value of solution is 8 ~ 10, then under the condition of decompress filter, above-mentioned solution is added drop-wise in the dry glue of mesoporous silicon oxide solid sphere molecular sieve, through suction filtration, wetting after, go in crystallizing kettle and carry out crystallization, crystallization condition is as follows: crystallization 1 ~ 2 day at 160～180 ℃;
(2) slurries after crystallization after filtration, washing, then drying, roasting obtain hollow ball ZSM-5 molecular sieve.
Described mesoporous silicon oxide solid sphere molecular sieve, its character is as follows: particle diameter is 300～400nm, and average pore diameter is 2.5～3.5nm, and specific surface area is 800～1100m
2/ g, pore volume is for being greater than 0.5cm
3/ g.
The described washing of step (2) is preferably under the condition of decompress filter to be carried out, until washings pH value approaches neutrality, general pH value reaches 7.0 ± 0.5; Described dry be under the condition of 60～80 ℃ dry 6～12 hours; Described roasting is to adopt ordinary method to carry out, and generally adopts aerobic pyroprocessing, 400～600 ℃ of roastings 5～20 hours.
The character of the ZSM-5 hollow ball molecular sieve that the inventive method makes is as follows: particle diameter 300～800nm, specific surface area 150m
2/ g～350m
2/ g, total pore volume 0.1mL/g～0.3mL/g, average pore diameter 0.45～0.60 nm, SiO
2/ Al
2o
3mol ratio 10～100, relative crystallinity is 75%～95%.
The inventive method adopts dry glue process to carry out crystallization, be that raw material in crystallizing kettle is just wetting with the solution that contains template, can guarantee that like this raw material (mesoporous silicon oxide solid sphere molecular sieve) only contacts with a small amount of water in crystallization process, template (TPAOH) just can enter into by mesopore orbit the inside of silicon-dioxide solid sphere molecular sieve like this, gradually unbodied inside silicon species is dissolved, form inner cavity.And stay under the template of silicon-dioxide solid sphere molecular sieve outer surface and the acting in conjunction of silicon-dioxide solid sphere molecular sieve, easily generate the microporous crystal with ZSM-5 structure.At the crystallization time through 1～2 day, will generate the microporous hollow sphere molecule sieve with hollow structure.The present invention adopts dry glue process to carry out crystallization, and the number of the water yield is very crucial.Because the water yield is excessive, in crystallization process, can cause the skeleton of raw material (mesoporous silicon oxide solid sphere molecular sieve) to subside, finally cause generating the ZSM-5 micro porous molecular sieve of random pattern.
The hollow ball molecular sieve that adopts the inventive method to prepare, make catalyzer by supporting hydrogenation active metals component, can be used in FCC gasoline selective hydrodesulfurizationmodification process, in this process, catalyzer has the feature of good guarantor's alkene, can reduce to greatest extent the loss of gasoline octane rating.
Accompanying drawing explanation
Fig. 1 is the X-ray diffractogram (XRD) of the synthetic hollow ball sieve sample of embodiment 1;
Fig. 2 is the fourier-infrared spectrogram (FT-IR) of the synthetic hollow ball sieve sample of embodiment 2;
Fig. 3 is the transmission electron microscope picture (TEM) of the synthetic hollow ball sieve sample of embodiment 1;
Fig. 4 is that HDS and the HDO of different catalysts leads comparison.
Embodiment
The following examples are used for illustrating in greater detail the present invention, but scope of the present invention is not only limited to the scope of these embodiment.
Embodiment 1
10.5 g NaAlO
2be dissolved in the deionized water of 100 mL with 56 mL TPAOH, obtain solution, the pH value of solution is about 9, then take raw material mesoporous silicon oxide solid sphere molecular sieve (character: particle diameter is 400nm, average pore diameter is 2.9nm, specific surface area is 1080m
2/ g, pore volume is for being greater than 0.35cm
3/ g) 100 grams, be transferred in the Büchner funnel with filter paper, under the state of decompress filter, the solution preparing above is dropwise added drop-wise in the raw material on filter paper.Through suction filtration, wetting after, then transfer in crystallizing kettle crystallization 48 hours at 170 ℃.By crystallization rear slurry cool to room temperature, the powder obtaining carries out under the condition of decompress filter, until washings pH value approaches neutrality; Dry is to be dried 10 hours under the condition of 70 ℃; Then roasting 6 hours at 540 ℃, gained molecular sieve label is HS-1, character is in table 1.
Embodiment 2
2.1 g NaAlO
2be dissolved in the deionized water of 50 mL with 28mL TPAOH, obtain solution, the pH value of solution is about 9, then take raw material (mesoporous silicon oxide solid sphere molecular sieve, particle diameter is 400nm, pore size is 2.9nm, specific surface area is 1080m
2/ g, pore volume is for being greater than 0.35cm
3/ g) 50 grams, be transferred in the Büchner funnel with filter paper, under the state of decompress filter, the solution preparing above is dropwise added drop-wise in the raw material on filter paper.Through suction filtration, wetting after, then transfer in crystallizing kettle crystallization 48 hours at 170 ℃.By crystallization rear slurry cool to room temperature, the powder obtaining carries out under the condition of decompress filter, until washings pH value approaches neutrality; Dry is to be dried 10 hours under the condition of 70 ℃; Then roasting 6 hours at 540 ℃, gained molecular sieve label is HS-2, character is in table 1.
Embodiment 3
2.1 g NaAlO
2be dissolved in the deionized water of 150 mL with 84 mL TPAOH, obtain solution, the pH value of solution is about 9, then take raw material (mesoporous silicon oxide solid sphere molecular sieve, particle diameter is 400nm, pore size is 2.9nm, specific surface area is 1080m
2/ g, pore volume is for being greater than 0.35cm
3/ g) 150 grams, be transferred in the Büchner funnel with filter paper, under the state of decompress filter, the solution preparing above is dropwise added drop-wise in the raw material on filter paper.Through suction filtration, wetting after, then transfer in crystallizing kettle crystallization 48 hours at 170 ℃.By crystallization rear slurry cool to room temperature, the powder obtaining carries out under the condition of decompress filter, until washings pH value approaches neutrality; Dry is to be dried 10 hours under the condition of 70 ℃; Then roasting 6 hours at 540 ℃, gained molecular sieve label is HS-3, character is in table 1.
Embodiment 4
Take HS-2, ZSM-5 and ZSM-5 (H type) as carrier, support Ni, Mo and make respectively catalyzer.The preparation of Hydrogen carrier, is that the carrier of sodium type is put into concentration is 0.4 mol/L aqueous ammonium nitrate solution, and by solid-to-liquid ratio (g/mL) 1:10,85 ℃ of dippings 2 times, each 2h, with deionized water wash, filters, dry, roasting, makes Hydrogen carrier.Respectively nickelous nitrate, ammonium molybdate are dissolved in a certain amount of deionized water by step impregnation method, load on successively on above-mentioned molecular sieve by equi-volume impregnating, after every step load, under room temperature, flood 24h, then put into dry 24h at 100 ℃, baking oven, again in retort furnace at 500 ℃ roasting 3h, cool to room temperature makes corresponding catalyzer.Wherein, NiO and MoO
3content be respectively 2.0 wt.% and 10.0wt.%.On micro-reactor, take catalytically cracked gasoline (FCC) as raw material, evaluate respectively HS-2, ZSM-5 and ZSM-5 (H type) catalyzer, the results are shown in Table 2, table 3, table 4.As seen from Figure 4, can find out from evaluation result the catalyst for selectively hydrodesulfurizing that the hollow ball molecular sieve prepared take the present invention is made as carrier, the catalyzer comparison made from traditional ZSM-5, in FCC gasoline selective hydrodesulfurizationmodification process, there is the feature of good guarantor's alkene, can reduce to greatest extent the loss of gasoline octane rating.
the character of table 1 embodiment gained hollow ball molecular sieve
| Sample | Specific surface area (m 2/g) | Total pore volume (cm 3/g) | SiO 2/Al 2O 3Mol ratio | Relative crystallinity, % | Average pore diameter (nm) |
| Embodiment 1 | 241 | 0.10 | 20 | 90 | 0.47 |
| Embodiment 2 | 297 | 0.13 | 50 | 88 | 0.48 |
| Embodiment 3 | 326 | 0.19 | 150 | 92 | 0.50 |
table 2 FCC gasoline carries out the products distribution that selective hydrodesulfurization different time obtains on NiMo/HS-2
| ? | n-p,% | i-p% | O,v% | N,v% | A,v% | S,(ug/g) | HDS/% | HYDO/% |
| Raw material | 5.2 | 34.2 | 32.1 | 7.0 | 21.6 | 293.9 | ? | ? |
| 12h | 6.9 | 33.2 | 31.4 | 6.8 | 21.7 | 154.4 | 47.5 | 2.3 |
| 24h | 6.7 | 33.3 | 31.7 | 6.6 | 21.8 | 142.8 | 51.4 | 1.5 |
| 36h | 6.7 | 33.4 | 31.6 | 6.6 | 21.8 | 132.1 | 55.1 | 1.6 |
| 48h | 6.7 | 33.3 | 32.1 | 6.7 | 21.3 | 142.6 | 51.5 | 0.2 |
| 60h | 6.6 | 32.8 | 31.8 | 6.8 | 22.1 | 137.7 | 53.1 | 1.2 |
| 72h | 6.6 | 33.1 | 31.9 | 6.7 | 21.8 | 140.9 | 52.1 | 0.8 |
In table 2, n-p: normal paraffin, i-p: isoparaffin, O: alkene, N: naphthenic hydrocarbon, A: aromatic hydrocarbons, HDS/%: hydrogenating desulfurization percentage, HYDO/%: olefin saturated massfraction.
table 3 FCC gasoline carries out the products distribution that selective hydrodesulfurization different time obtains on NiMo/ZSM-5
| ? | n-p,% | i-p% | O,v% | N,v% | A,v% | S,(ug/g) | HDS/% | HYDO/% |
| Raw material | 5.2 | 34.2 | 32.1 | 7.0 | 21.6 | 284.4 | ? | ? |
| 12h | 7.1 | 33.3 | 29.9 | 7.2 | 22.7 | 147.5 | 47.8 | 7.0 |
| 24h | 6.9 | 32.9 | 31.3 | 7.0 | 22.0 | 157.1 | 44.4 | 2.6 |
| 36h | 6.7 | 33.0 | 30.7 | 7.1 | 22.5 | 152.0 | 46.2 | 4.5 |
| 48h | 6.7 | 33.2 | 31.0 | 7.0 | 22.1 | 154.0 | 45.5 | 3.7 |
| 60h | 6.8 | 32.5 | 31.2 | 7.1 | 22.5 | 156.4 | 44.6 | 3.0 |
| 72h | 6.7 | 32.9 | 30.9 | 7.0 | 22.6 | 160.8 | 43.0 | 3.9 |
In table 3, n-p: normal paraffin, i-p: isoparaffin, O: alkene, N: naphthenic hydrocarbon, A: aromatic hydrocarbons, HDS/%: hydrogenating desulfurization massfraction, HYDO/%: olefin saturated massfraction.
table 4 FCC gasoline carries out the products distribution that selective hydrodesulfurization different time obtains on NiMo/ZSM-5 (H type)
| ? | n-p,% | i-p% | O,v% | N,v% | A,v% | S,(ug/g) | HDS/% | HYDO/% |
| Raw material | 5.2 | 34.2 | 32.1 | 7.0 | 21.6 | 285.6 | ? | ? |
| 12h | 8.3 | 35.2 | 25.5 | 7.4 | 23.7 | 139.2 | 51.3 | 20.5 |
| 24h | 7.9 | 34.3 | 27.3 | 7.3 | 23.2 | 167.5 | 41.3 | 15.1 |
| 36h | 7.7 | 33.9 | 28.3 | 7.2 | 23.0 | 170.7 | 40.2 | 12.0 |
| 48h | 7.4 | 33.5 | 29.2 | 7.1 | 22.9 | 158.0 | 44.7 | 9.3 |
| 60h | 7.2 | 33.1 | 29.8 | 7.3 | 22.7 | 169.8 | 40.5 | 7.3 |
| 72h | 7.1 | 33.5 | 29.5 | 7.0 | 22.8 | 170.1 | 40.4 | 8.2 |
In table 4, n-p: normal paraffin, i-p: isoparaffin, O: alkene, N: naphthenic hydrocarbon, A: aromatic hydrocarbons, HDS/%: hydrogenating desulfurization massfraction, HYDO/%: olefin saturated massfraction.
Claims (5)
1. a preparation method for hollow ball ZSM-5 molecular sieve, comprising:
(1) by (0.5～2.0) SiO
2: (0.1～0.5) Al
2o
3: (0.1～0.5) Na
2o:(1～5) H
2o:(0.1～0.5) mole proportioning of TPAOH, by TPAOH, NaAlO
2with water mixing wiring solution-forming, the pH value of solution is 8 ~ 10, then under the condition of decompress filter, above-mentioned solution is added drop-wise in the dry glue of mesoporous silicon oxide solid sphere molecular sieve, through suction filtration, wetting after, go in crystallizing kettle and carry out crystallization, crystallization condition is as follows: crystallization 1 ~ 2 day at 160～180 ℃;
(2) slurries after crystallization after filtration, washing, then drying, roasting obtain hollow ball ZSM-5 molecular sieve.
2. in accordance with the method for claim 1, it is characterized in that described mesoporous silicon oxide solid sphere molecular sieve, its character is as follows: particle diameter is 300～400nm, and average pore diameter is 2.5～3.5nm, and specific surface area is 800～1100m
2/ g, pore volume is greater than 0.5cm
3/ g.
3. in accordance with the method for claim 1, it is characterized in that the described washing of step (2) carries out under the condition of decompress filter, until washings pH value approaches neutrality.
4. in accordance with the method for claim 1, it is characterized in that described dry of step (2) is under the condition of 60～80 ℃ dry 6～12 hours; Described roasting was to adopt aerobic pyroprocessing, 400～600 ℃ of roastings 5～20 hours.
5. in accordance with the method for claim 1, it is characterized in that the character of described hollow ball ZSM-5 molecular sieve is as follows: particle diameter 300～800nm, specific surface area 150m
2/ g～350m
2/ g, total pore volume 0.1mL/g～0.3mL/g, average pore diameter 0.45～0.60 nm, SiO
2/ Al
2o
3mol ratio 10～100, relative crystallinity is 75%～95%.
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| CN105271285A (en) * | 2015-09-21 | 2016-01-27 | 清华大学 | Multi-stage structure molecular sieve hollow microsphere, preparation methods and application |
| CN106185981A (en) * | 2016-07-16 | 2016-12-07 | 太原理工大学 | A kind of preparation method of hollow ZSM 5 microsphere of zeolite |
| CN111569827A (en) * | 2020-05-26 | 2020-08-25 | 北京泷涛环境科技有限公司 | Hollow sphere molecular sieve adsorbent and preparation method thereof |
| CN113145164A (en) * | 2021-01-29 | 2021-07-23 | 鞍山师范学院 | Preparation method and application of Cu @ HS hollow-structure molecular sieve |
| CN113149029A (en) * | 2021-01-29 | 2021-07-23 | 鞍山师范学院 | Preparation method of B @ HS hollow sphere molecular sieve |
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