CN101428817A - Process for producing cavity type ZSM-5 modified zeolite molecular sieve - Google Patents
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Abstract
The invention relates to a method for preparing hollow cavity type ZSM-5 modified zeolite molecular sieve, and aims to solve the problems that the microcellular structure diffusion admittance is narrow, the modified zeolite molecular sieve has lower relative degree of crystallinity, and the adjustable range of apertures inside molecular sieve is small, thereby facilitating macromolecule reaction limited by diffusion. The invention adopts at least one 0.1-8.5 mol/L acid solution of hydrochloric acid, nitric acid, sulphuric acid or acetic acid to treat ZSM-5 molecular sieve raw powder with the silica alumina ratio SiO2/Al2O3 being 20-1000 and the particle size being 0.4-10 Mum for 1-8 h; then at least one 0.1-5.0 mol/L aqueous alkali of sodium hydroxide, magnesium hydrate, potassium hydroxide, sodium carbonate or sodium bicarbonate is used for treatment for 1-48 h at 20-90 DEG C; and at least one 0.1-8.5 mol/L acid solution of hydrochloric acid, nitric acid, sulphuric acid or acetic acid is used for treatment for 1-48 h at 20-90 DEG C to obtain the modified ZSM-5 molecular sieve. The problems are well solved, and the invention can be used in industrial production of macromolecule catalysis and transformation catalysts.
Description
Technical field
The present invention relates to a kind of preparation method of cavity type ZSM-5 modified zeolite molecular sieve.
Background technology
Zeolite molecular sieve material has special shape selective catalysis performance because of the duct size of its uniform composition, regular structure, adjustable surface acidity and molecular size.But because the restriction of its aperture size makes this class material no longer be suitable as macromole and participates in catalyst for reaction, as has macromolecular vacuum oil cracking.The researchist of U.S. Mobil company in 1992 successfully synthesizes M41S series mesopore molecular sieve, has big specific surface area, arrange in order in the duct, pore size distribution is adjustable in 2～10 nanometer range, can address this problem (Kresge C T, Leonowivz M E, Roth W J, et al.Nature, 1992,359:710～712).Yet because the skeleton structure of the noncrystalline attitude of M41S has determined its stability all can't compare with zeolite molecular sieve with acidity.Microporous-mesoporous composite molecular sieve has micropore and mesoporous dual model pore distribution, combines the duct advantage of mesoporous material and the strongly-acid and the high hydrothermal stability of micro porous molecular sieve, can make two kinds of material advantage complementations, synergy.Utilization six alkyl trimethyl ammonium bromides such as Karlsson and two kinds of template of Tetradecyl Trimethyl Ammonium Bromide, through two step crystallization, original position has been synthesized micropore one mesoporous composite molecular sieve with micropore (MFI) and mesoporous (MCM-41) structure.Scanning electron microscopic observation is found, MFI crystallization of molecular sieves thing is partially submerged in the MCM-41 molecular sieve aggregate, part surface is covered by MCM-41 molecular sieve thin layer, some MFI molecular sieve and MCM-41 molecular sieve have formed complicated aggregate (Karlsson A in addition, Stocker M, Microporous Mesoporous Mater, 1999,27:181～192).Le VanMao once attempted zeolite molecular sieve is carried out different acid-alkali treatment to obtain diplopore molecular sieve, but their result of study is unsatisfactory, distribution as the hole is too wide, the too low grade of degree of crystallinity (Le Van Mao R, Lavigne J, Sjiariel A B, et al.J.Mater.Chem., 1993,3:679～683).Can on established zeolite crystal, produce secondary pore by certain technology (as hydrothermal treatment consists), but the secondary pore pore size distribution that prior art forms is in a very wide scope, usually be that several nanometers arrive the hundreds of nanometer, the shape selective catalysis function of molecular sieve is had a greatly reduced quality.So it is very necessary that exploitation contains regular mesoporous zeolite molecular sieve.Zhang etc. with the ZSM-5 molecular sieve 950～1100 ℃ of following heat treated 2～10 hours, obtain having the micropore-mesopore matrix material of dual model pore distribution, this material has generated the narrow hole of some pore size distributions in the part microvoid structure that keeps the ZSM-5 molecular sieve, experiment shows, the constitutional features of matrix material depends on heat-treat condition (ZhangCunman strongly, Liu Qian, Xu Zheng, et al., Microporous Mesoporous Mater, 2003,62:157～163).Above method complex process, and the relative crystallinity of above-mentioned molecular sieve is lower, and molecular sieve internal cavity variable range is little, is unfavorable for being subjected to the macromolecular reaction of diffusional limitation, is restricted in suitability for industrialized production.
Summary of the invention
Technical problem to be solved by this invention is to exist the microvoid structure diffusion admittance narrow in the prior art, the modified zeolite molecular sieve relative crystallinity is lower, molecular sieve internal cavity variable range is little, be unfavorable for being subjected to the problem of the macromolecular reaction of diffusional limitation, a kind of preparation method of new cavity type ZSM-5 modified zeolite molecular sieve is provided.The modified zeolite molecular sieve catalyzer that makes with this method has higher relative crystallinity, the big cavity narrow, homogeneous that distributes, the characteristics that the cavity variable range is big.
In order to solve the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of preparation method of cavity type ZSM-5 modified zeolite molecular sieve may further comprise the steps:
A) with silica alumina ratio SiO
2/ Al
2O
3Be 20～1000, grain size is that 0.4～10 micron ZSM-5 molecular sieve concentration is that at least a acid solution that 0.01～8.5 mol is selected from hydrochloric acid, nitric acid, sulfuric acid or the acetate was handled 1～8 hour under 20～90 ℃ of conditions of temperature, gets modified zeolite molecular sieve presoma I;
B) be that at least a alkaline solution that 0.1～5.0 mol is selected from sodium hydroxide, magnesium hydroxide, potassium hydroxide, calcium hydroxide, yellow soda ash or the sodium bicarbonate was handled 1～48 hour under 20～90 ℃ of conditions of temperature with modified zeolite molecular sieve precursor I concentration, get modified zeolite molecular sieve precursor II;
C) be that at least a acid solution that 0.01～8.5 mol is selected from hydrochloric acid, nitric acid, sulfuric acid or the acetate was handled 1～8 hour under 20～90 ℃ of conditions of temperature with modified zeolite molecular sieve precursor II concentration, get modified zsm-5 zeolite.
In the technique scheme, ZSM-5 molecular sieve silica alumina ratio SiO
2/ Al
2O
3Preferable range is 50～200; ZSM-5 molecular sieve grain size preferable range is 0.4～2 micron; A) the concentration preferable range of acid solution is 0.1～2 mol in the step; B) the concentration preferable range of alkaline solution is 0.1～3 mol in the step, and alkaline solution treatment temp preferable range is 50～90 ℃, and alkaline solution treatment time preferable range is 10～36 hours; C) the concentration preferable range of acid solution is 1～5 mol in the step.
The sign of catalyzer crystallization degree adopts Japanese D/max-1400 type X-ray diffractometer of science to measure Cu target, K α line, tube voltage 40kV, tube current 100mA, 5～50 ° of sweep limits among the present invention.The degree of crystallinity of described molecular sieve is relative crystallinity, with the diffracted intensity of five main diffraction peaks in the described molecular sieve x-ray diffraction spectra (23.18 °, 23.32 °, 23.74 °, 23.99 °, 24.45 °) add and value is calculated.Be defined as 100% with sieve sample degree of crystallinity before being untreated.Carry out on the TriStar3000 type that the is determined at physical adsorption appearance of molecular sieve specific surface area and pore volume.With N
2Be adsorption medium, under liquid nitrogen boiling point (77K), record, by the specific surface area of BET method calculating material, and according to distribution of BJH formula calculated hole diameters and pore volume.
The present invention is by adopting the pore size distribution of alkali treatment method regulation and control ZSM-5 molecular sieve.Basic solution selectively dissolves framework silicon in the zeolite molecular sieve.Because the zeolite molecular sieve framework aluminum has electronegativity, the silicon around can protecting is not by etched with alkali solution, and the rich aluminium in molecular sieve surface; body phase inner skeleton aluminium content is less; therefore alkaline solution at first corrodes the inner mutually framework silicon of body, makes its dissolving, detaches framework of molecular sieve.Along with removing of molecular sieve inner skeleton silicon, body phase framework aluminum is to surface transport, causes molecular sieve outer surface to form one deck aluminum hull, the inner holes that produce different sizes of molecular sieve, even many molecular sieves inside hollowed out fully, forms big cavity.Acid treatment flush away molecular sieve surface hexa-coordinate aluminium after the alkaline purification reduces the acidic zeolite bit density.The modified zeolite molecular sieve that above modification is obtained carries out XRD and N
2Adsorption-desorption characterizes, and can obtain having 92% relative crystallinity, and the narrow and cavity volume of aperture in 160～190 nanometer range of pore size distribution accounts for the modified zeolite molecular sieve of all cavity volume 90% more than the 2nm; Molecular sieve bore diameter is distributed in 10～190 nanometer range adjustable, has obtained better technical effect.
The present invention is further elaborated below by embodiment.
Embodiment
[comparative example 1]
With concentration is that 5 mol salpeter solutions are handled silica alumina ratio SiO under 90 ℃ of conditions of temperature
2/ Al
2O
3Be 110 ZSM-5 molecular screen primary powder 5 hours, washing, dry back is that 550 ℃ of following roastings get molecular sieve in temperature.
[embodiment 1～6]
With concentration is that 0.1,1.0,5.0 mol hydrochloric acid or salpeter solution are handled silica alumina ratio SiO under 20,50,90 ℃ of conditions of temperature
2/ Al
2O
3Be 110 ZSM-5 molecular screen primary powder 2,5,8 hours, washing, dry back is 550 ℃ of following roastings in temperature; Temperature is under 80 ℃ then, is the sodium carbonate solution dipping 24 hours of 0.8 mol with concentration, washing, and dry back is 550 ℃ of following roastings in temperature; Be that 0.1,2.0,5.0 mol hydrochloric acid or salpeter solution were handled 2,5,8 hours under 40,70,90 ℃ of conditions of temperature with concentration at last, washing, dry back is that 550 ℃ of following roastings get required modified zeolite molecular sieve in temperature.
[embodiment 7～11]
With concentration is that 1 mol hydrochloric acid soln is handled silica alumina ratio SiO under 90 ℃ of conditions of temperature
2/ Al
2O
3Be 40,110,220, grain size is 0.4,2.0,8.0 micron a ZSM-5 molecular screen primary powder 5 hours, washing, and dry back is 550 ℃ of following roastings in temperature; Temperature is under 20,60,80 ℃ then, is sodium hydroxide, magnesium hydroxide, the sodium carbonate solution dipping 12,24,36 hours of 0.1,0.6,1.0,2.0 mol with concentration, washing, and dry back is 550 ℃ of following roastings in temperature; Be that 5 mol salpeter solutions were handled 5 hours under 70 ℃ of conditions of temperature with concentration at last, washing, dry back is that 550 ℃ of following roastings get required modified zeolite molecular sieve in temperature.
[embodiment 12]
The modified zeolite molecular sieve that embodiment 1～11 and comparative example make is measured XRD on Japan's D/max-1400 type of science X-ray diffractometer, on TriStar3000 type physical adsorption appearance, carry out the research of cryogenic nitrogen adsorption-desorption, by the specific surface area of BET method calculating material, and according to distribution of BJH formula calculated hole diameters and pore volume.The results are shown in table 1 and the table 2.
Table 1 nitrogen adsorption-desorption result
| Embodiment | 1 | 2 | 3 | 4 | 5 | 6 |
| Acid exchange kind | Hydrochloric acid | Hydrochloric acid | Hydrochloric acid | Nitric acid | Nitric acid | Nitric acid |
| Acid exchange concentration/mole rises -1 | 0.1 | 1.0 | 5.0 | 0.1 | 1.0 | 5.0 |
| Acid exchange temperature/℃ | 20 | 50 | 90 | 90 | 50 | 20 |
| Acid swap time/hour | 2 | 5 | 8 | 8 | 5 | 2 |
| Pickling kind after the alkaline purification | Hydrochloric acid | Hydrochloric acid | Hydrochloric acid | Nitric acid | Nitric acid | Nitric acid |
| Pickling concentration/mole rises after the alkaline purification -1 | 0.1 | 2.0 | 5.0 | 5.0 | 2.0 | 0.1 |
| Pickling time after the alkaline purification/hour | 2 | 2 | 8 | 8 | 5 | 5 |
| Pickling temperature after the alkaline purification/℃ | 40 | 70 | 90 | 90 | 70 | 40 |
| Relative crystallinity/% | 56.6 | 82.4 | 93.7 | 85.9 | 83.7 | 49.9 |
| Total specific surface area/rice 2Gram -1 | 225.4 | 312.0 | 367.8 | 352.1 | 340.4 | 205.1 |
| Micropore specific area/rice 2Gram -1 | 94.8 | 128.2 | 166.5 | 149.2 | 133.4 | 101.5 |
| Cavity volume/rice 3Gram -1 | 1.24 | 1.33 | 1.66 | 1.49 | 1.38 | 1.21 |
| Micro pore volume/rice 3Gram -1 | 0.06 | 0.07 | 0.06 | 0.07 | 0.07 | 0.06 |
| 160～190 lar nanometric cavities volumes account for the above cavity volume per-cent/% of 2 nanometers | 20.2 | 40.7 | 88.6 | 85.0 | 79.7 | 28.6 |
Table 2 nitrogen adsorption-desorption result
| Embodiment | 7 | 8 | 9 | 10 | 11 | Comparative example 1 |
| Silica alumina ratio SiO 2/Al 2O 3 | 40 | 110 | 220 | 110 | 40 | 110 |
| Molecular sieve grain size/micron | 0.4 | 2.0 | 8.0 | 0.4 | 0.4 | 0.4 |
| The alkaline purification kind | Sodium hydroxide | Magnesium hydroxide | Sodium hydroxide | Yellow soda ash | Magnesium hydroxide | — |
| Alkaline purification concentration/mole rises -1 | 0.1 | 1.0 | 0.6 | 0.6 | 2.0 | — |
| Its alkali purification temp/℃ | 60 | 60 | 20 | 80 | 60 | — |
| Alkaline purification time/hour | 12 | 24 | 36 | 36 | 12 | — |
| Relative crystallinity/% | 85.6 | 42.4 | 35.8 | 90.2 | 55.4 | 98.2 |
| Total specific surface area/rice 2Gram -1 | 346.6 | 202.6 | 217.1 | 358.4 | 245.1 | 365.9 |
| Micropore specific area/rice 2Gram -1 | 159.4 | 66.7 | 52.9 | 141.3 | 128.2 | 332.7 |
| Cavity volume/rice 3Gram -1 | 1.45 | 1.89 | 1.98 | 1.52 | 1.36 | 0.56 |
| Micro pore volume/rice 3Gram -1 | 0.07 | 0.06 | 0.06 | 0.06 | 0.06 | 0.07 |
| 160～190 lar nanometric cavities volumes account for the above cavity volume per-cent/% of 2 nanometers | 0 | 95.9 | 97.4 | 91.5 | 88.7 | 0 |
| 100～160 lar nanometric cavities volumes account for the above cavity volume per-cent/% of 2 nanometers | 5.4 | 4.1 | 2.6 | 4.6 | 10.2 | 0 |
| 50～100 lar nanometric cavities volumes account for the above cavity volume per-cent/% of 2 nanometers | 7.5 | 0 | 0 | 2.2 | 1.1 | 0 |
| 10～50 lar nanometric cavities volumes account for the above cavity volume per-cent/% of 2 nanometers | 54.8 | 0 | 0 | 1.4 | 0 | 0 |
| 2～10 lar nanometric cavities volumes account for the above cavity volume per-cent/% of 2 nanometers | 20.1 | 0 | 0 | 0.3 | 0 | 100 |
Claims (6)
1, a kind of preparation method of cavity type ZSM-5 modified zeolite molecular sieve may further comprise the steps:
A) with silica alumina ratio SiO
2/ Al
2O
3Be 20～1000, grain size is that 0.4～10 micron ZSM-5 molecular sieve concentration is that at least a acid solution that 0.01～8.5 mol is selected from hydrochloric acid, nitric acid, sulfuric acid or the acetate was handled 1～8 hour under 20～90 ℃ of conditions of temperature, gets modified zeolite molecular sieve presoma I;
B) be that at least a alkaline solution that 0.1～5.0 mol is selected from sodium hydroxide, magnesium hydroxide, potassium hydroxide, calcium hydroxide, yellow soda ash or the sodium bicarbonate was handled 1～48 hour under 20～90 ℃ of conditions of temperature with modified zeolite molecular sieve precursor I concentration, get modified zeolite molecular sieve precursor II;
C) be that at least a acid solution that 0.01～8.5 mol is selected from hydrochloric acid, nitric acid, sulfuric acid or the acetate was handled 1～8 hour under 20～90 ℃ of conditions of temperature with modified zeolite molecular sieve precursor II concentration, get modified zsm-5 zeolite.
2,, it is characterized in that molecular sieve silica alumina ratio SiO according to the preparation method of the described cavity type ZSM-5 modified zeolite molecular sieve of claim 1
2/ Al
2O
3Be 50～200.
3,, it is characterized in that the molecular sieve grain size is 0.4～2 micron according to the preparation method of the described cavity type ZSM-5 modified zeolite molecular sieve of claim 1.
4,, it is characterized in that the concentration of acid solution in a) step is 0.1～2 mol according to the preparation method of the described cavity type ZSM-5 modified zeolite molecular sieve of claim 1.
5, according to the preparation method of the described cavity type ZSM-5 modified zeolite molecular sieve of claim 1, it is characterized in that b) the alkaline solution treatment temp is 50～90 ℃ in the step, and the treatment time is 10～36 hours, and the concentration of alkaline solution is 0.1～3 mol.
6, according to the preparation method of the described cavity type ZSM-5 modified zeolite molecular sieve of claim 1, it is characterized in that c) concentration of acid solution is 1～5 mol in the step.
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| ZA893132B (en) * | 1989-04-27 | 1990-12-28 | Zeofuels Res Pty Ltd | Modification of natural zeolite and its use as an oligomerisation catalyst |
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