CN102874829A - Preparation method of mesopore-micropore zeolite molecular sieve - Google Patents
Preparation method of mesopore-micropore zeolite molecular sieve Download PDFInfo
- Publication number
- CN102874829A CN102874829A CN2011101927660A CN201110192766A CN102874829A CN 102874829 A CN102874829 A CN 102874829A CN 2011101927660 A CN2011101927660 A CN 2011101927660A CN 201110192766 A CN201110192766 A CN 201110192766A CN 102874829 A CN102874829 A CN 102874829A
- Authority
- CN
- China
- Prior art keywords
- zeolite
- preparation
- micropore
- mesoporous
- solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Landscapes
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
The invention discloses a preparation method of a mesopore-micropore zeolite molecular sieve, comprising the following steps of: firstly mixing micropore zeolite and aqueous alkali and carrying out ultrasonic treatment; then carrying out heat treatment on the micropore zeolite in an enclosed system in the presence of an organic solvent; and finally processing the micropore zeolite by the use of an acid solution. According to the method, supersonic wave can generate a cavitation effect so as to activate the micropore zeolite's framework silicon atom; during the alkali treatment, the addition of the organic solvent can promote the generation of a meso-structure so as to more efficiently convert the micropore structure to mesopores and simultaneously stabilize and protect the micropore structure; and acid treatment can reach the purpose of dredging pore canal and increasing total specific surface area. By the adoption of the method, more complete mircopores of the mesopore-micropore zeolite molecular sieve can be retained, more mresopores can be provided, and simultaneously the total BET specific surface area can be increased.
Description
Technical field
The present invention relates to a kind of preparation method of mesoporous-microporous zeolite molecular sieve, belong to Zeolite synthesis modification field, specifically a class micro-pore zeolite is carried out modification to prepare a kind of zeolite molecular sieve with mesoporous-compound pore canal system of micropore.
Background technology
Micro-pore zeolite is because of its regular microvoid structure, suitable acidity, and good thermostability and hydrothermal stability are widely used in petroleum industry.But micro-pore zeolite inevitably has some natural defects, its narrow duct (less than 2nm) is in relating to macromolecular reaction, the mass transfer diffusional resistance of material of very easily inducing reaction is excessive, react inside, macromolecular reaction thing crystal extremely difficult to get access duct, so just can not give full play to the catalysis efficiency of zeolite; And the macromole product is out also comparatively difficult from the duct internal divergence, and very easily coking causes catalyst deactivation.The invention of M41S series mesopore molecular sieve is for the micro-pore zeolite synthesis modification provides good reference.M41S series mesopore molecular sieve has the mesoporous aperture structure of regulating of 2～10nm, can solve the mass transfer problem in micro-pore zeolite such as reaction mass, but thermally-stabilised and hydrothermal stability is poor because of it, low and very difficult industrial application was measured in acid.Exploitation has the micro-pore zeolite molecular sieve of meso-hole structure, makes micropore and mesoporous organic combination, is a focus in the synthetic field of present catalytic material.
" Appl Catal " (2001,219:33-43) the NaOH solution-treated ZSM-5 zeolite 300min of employing 0.2mol/L obtains a kind of Microporous zeolite ZSM-5 with meso-hole structure, and mesoporous specific surface area is from 6.6 m behind the alkali modification
2/ g is increased to 115.4m
2/ g, micropore specific area are then from 296.4 m
2/ g is reduced to 205m
2/ g.Although it is more that micropore specific area keeps, mesoporous content is also lower.
Patent CN101428817A processes ZSM-5 zeolite 10～48 hours in 20～90 ℃ with the alkaline solution of 0.1～5mol/L, obtains the ZSM-5 zeolite that a kind of diameter is the large cavity structure of 160～190nm, and mesoporous specific surface area is the highest can reach 217 m for it
2About/g, but its micropore specific area is seriously damaged, and 141.3m is only arranged
2/ g can reduce the reactive behavior of zeolite so greatly.
Patent CN1530322A processes ZSM-5 zeolite 1～7 hour in 50～100 ℃ with the alkaline solution of 0.1～0.5mol/L, the highlyest can obtain 250 m
2The mesoporous specific surface area of/g, but its microvoid structure also is to destroy seriously.
" Journal of Catalysis " (2007,251:21-27) adopt the NaOH solution of 0.2mol/L to process mordenite 30min at 65 ℃, also obtain a kind of microporous filament geolyte with meso-hole structure, mesoporous specific surface area is from 8 m behind the alkali modification
2/ g is increased to 115m
2/ g.
" Microporous and Mesoporous Materials " (2004,69:29-34) with micro-pore zeolites such as NaOH solution-treated β, mordenite, ZSM-5, all obtain containing the zeolitic material of meso-hole structure.Wherein behind the alkali modification the mesoporous specific surface area of β zeolite from 45m
2/ g is increased to 325m
2/ g; The mesoporous specific surface area of mordenite is from 50m
2/ g is increased to 140m
2/ g; The mesoporous specific surface area of ZSM-5 zeolite is from 40 m
2/ g is increased to 225m
2/ g.But this mesoporous-microporous zeolite material preparation efficiency ratio is lower, and the mesoporous area that produces awaits to improve.
At present, that has reported prepares document and the patent of mesoporous-microporous zeolite about alkali treatment modifying, main purpose is to make mesoporous with the part microvoid structure of alkali destruction micro-pore zeolite, improve mesoporous specific surface area, the internal diffusion of material in zeolite crystal improved in the aperture that enlarges zeolite crystal, thereby reaches the purpose that improves catalytic performance.Yet prior art also has two obvious shortcomings: the one, and the mesoporous specific surface area that produces is also lower; The 2nd, when obtaining higher mesoporous specific surface area, the microporous crystal structure deteriorate of micro-pore zeolite is more serious, and micropore surface amassed low, and this can the serious catalytic activity that reduces zeolite.So higher mesoporous specific surface area is provided, and keeps the zeolitic material of complete microvoid structure to await to develop.
Summary of the invention
The present invention is directed to the deficiencies in the prior art part, proposed a kind ofly to aim to provide higher mesoporous specific surface area, and kept complete microvoid structure, have the preparation method of the zeolite molecular sieve of mesoporous-compound pore canal system of micropore.
The preparation method of mesoporous-microporous zeolite molecular sieve provided by the invention may further comprise the steps:
(1) gets micro-pore zeolite, add according to a certain percentage alkaline solution, place ultrasonic environment to process 10 ~ 60 min;
(2) mixture that step (1) is obtained places encloses container, adds the lower molecular weight organic solvent, in 30～180 ℃ of alkaline purification 0.5～7h;
(3) step (2) gained mixture is separated and wash;
(4) add acid solution, stir process for some time in the zeolite after step (3) the gained alkaline purification;
(5) products therefrom that obtains of step (4) is through separating, wash, be drying to obtain the compound pore canal system zeolite molecular sieve of mesoporous-micropore.
According to the preparation method of mesoporous-microporous zeolite molecular sieve of the present invention, the silica alumina ratio scope of described micro-pore zeolite is 10～200, preferred 10～50.Wherein the micro-pore zeolite described in the step (1) is selected from a kind of in β zeolite, mordenite, ZSM-22 zeolite, ZSM-5 zeolite and the MCM-22 zeolite.
Alkaline solution described in the step (1) can be a kind of or several mixing solutions in NaOH, KOH, the LiOH aqueous solution.The concentration of alkaline solution is generally 0.1～7 mol/L, preferred 0.2～2 mol/L; The liquid-solid ratio that adds alkaline solution and micro-pore zeolite is 8～100 mL/g, preferred 10～80 mL/g.
Hyperacoustic frequency is 15KHz-10MHz described in the step (1), and the power of supersound process is 3 ~ 30W/100mL alkaline solution, and the supersound process time is 10 ~ 60 min, preferred 20 ~ 40 min.Preferably when supersound process, carry out simultaneously mechanical stirring.
Alkaline purification process in the step (2) is carried out in encloses container.Described its alkali purification temp is 30～180 ℃, preferred 40～120 ℃; Treatment time is generally 0.5～7 h, preferred 2～4 h.
The liquid-solid ratio of the lower molecular weight organic solvent described in the step (2) and micro-pore zeolite is 0.5～10 mL/g, preferred 1～5 mL/g.Described lower molecular weight organic solvent refers to that generally carbonatoms is 1～4 pure and mild ketone, is selected from one or more in methyl alcohol, ethanol, propyl alcohol, Virahol and the acetone usually.
Separation described in the step (3) and washing are routine operation well known to those skilled in the art.As separating the method for filtering can taked, washing generally refers to use deionized water wash.Step generally includes separating for several times and washing operation in (3), is generally 1～6 time.
Acid solution described in the step (4) can be a kind of or several mixing solutions in sulfuric acid, hydrochloric acid and the salpeter solution.The concentration of acid solution is generally 0.1～3mol/L, preferred 0.2～2mol/L.The liquid-solid ratio of described acid solution and micro-pore zeolite is 20～100 mL/g, is preferably 30～80 mL/g.
Churning time is 5～60min described in the step (4), preferred 20～40min.Described acid-treated temperature is 40～150 ℃, preferred 50～120 ℃; Treatment time is 0.5～7 h, preferred 2～5 h.
Mesoporous-microporous zeolite molecular sieve according to method preparation of the present invention has following feature: this material has the XRD feature spectrogram of original micro-pore zeolite; At N
2The measured aperture of adsorption-desorption exists mesoporous aperture to concentrate.
Compared with prior art, the preparation method of mesoporous-microporous zeolite molecular sieve of the present invention has following characteristics:
Mesoporous-microporous zeolite molecular sieve preparation method provided by the invention can form meso-hole structure, far above prior art in the micro-pore zeolite crystal.And mesoporous-microporous zeolite molecular sieve provided by the invention not only has higher and mesoporous specific surface area, can also keep complete microvoid structure, greatly is better than prior art; And the BET surface-area of zeolite also has significantly lifting.
In the prior art, making meso-hole structure in micro-pore zeolite mainly is to rely on the microvoid structure of alkaline solution destruction zeolite and produce a large amount of losses that mesoporous, such consequence must be brought micropore, reduces the chain carrier of zeolite.And alkali modification treatment process provided by the invention is to carry out first ultrasonication, then airtight, carries out alkaline purification in the environment that the lower molecular weight organic solvent exists.Ultrasonic wave can produce extremely strong cavitation effect, so that the activation of the framework silicon atom of ZSM-5 zeolite is conducive to next step alkaline purification.In the alkaline purification process of zeolite, the lower molecular weight organic solvent of adding can promote the generation of meso-hole structure, changes into mesoporously so that microvoid structure is more efficient, also microvoid structure is played stable provide protection simultaneously.Alkaline solution can optionally remove the part element silicon in the micro-pore zeolite crystal, so that part microvoid structure recurring structure is reset and formed mesoporous; Acid treatment process after the alkaline purification, the amorphous aluminium in can the wash-out zeolite crystal, thus reach the dredging duct and increase the purpose of total specific surface area.Therefore of the present invention mesoporous-zeolite molecular sieve of the compound pore canal system of micropore can keep more complete micropore, provide more mesoporous, but also can increase total BET specific surface area.
Description of drawings
Fig. 1 is the XRD spectrogram of the mordenite that obtains of embodiment 1.
Fig. 2 is the hole XRD spectrogram of the β zeolite that obtains of embodiment 3.
Fig. 3 is the graph of pore diameter distribution of the mordenite that obtains of embodiment 1.
Fig. 4 is the graph of pore diameter distribution of the β zeolite that obtains of embodiment 3.
Embodiment
In the inventive method, obtained mesoporous-D/max-2500 type full-automatic rotating target x-ray diffractometer that the crystalline structure of the zeolite sample in the compound duct of micropore adopts Rigaku Co., Ltd. to produce characterizes.Experiment condition: the Cu target, K α source of radiation, graphite monochromator, operating voltage 40kV, tube current 80mA, sweep limit is 5～40 °, and sweep velocity is 8 °/min, and step-length is 0.1 °.
The porous of sample is tested at the ASAP2420 physical adsorption appearance that U.S. Mai Ke company produces.Experiment condition is: sample is at 300 ℃, and under the 0.1MPa condition degassed 4 hours, take off sample be filled with the nitrogen of 101.325kPa until sample bottle after, accurately analyze after the weighing.Total specific surface area gets according to BET thermoisopleth Equation for Calculating, and micro pore volume and outer surface area are tried to achieve according to the t-Plot graphing method, and pore size distribution adopts the BJH method to calculate.
Below by specific embodiment mesoporous-microporous zeolite molecular sieve preparation method of the present invention is given detailed description, but be not limited to embodiment.
The raw material sources that use in the embodiment of the invention and the comparative example: ZSM-5 zeolite, β zeolite, mordenite are all available from the Fushun Petrochemical Company catalyst plant, and silica alumina ratio is respectively 18.7,20.1 and 30.8; ZSM-12 zeolite, MCM-22 zeolite are self-control, and its silica alumina ratio is 28.6 and 26.5.The main porous of micro-pore zeolite is listed in the table 1.Employed acid, alkali and solvent are the analytical pure chemical reagent.
Embodiment 1
Get the NaOH solution 2400mL of 30g microporous filament geolyte, 0.30 mol/L in beaker, (the 4.12W/100mL alkaline solution 40KHz), adds mechanical stirring, ultrasonication 30min to place ultrasonic cleaner; Then change in the closed reactor, add again the methyl alcohol of 75mL, process 4h, filtration, washing in 60 ℃.Mordenite after the washing is placed beaker, add the hydrochloric acid soln 1500mL of 0.2mol/L, stir 20min under room temperature condition, change 70 ℃ of processing 3h in the water-bath over to, filter, wash, place 110 ℃ of dry 12h of baking oven again, the gained sample number into spectrum is CL1.
As seen from Figure 1, the CL1 sample has the feature spectrogram of mordenite, still keeps good zeolite structured.As seen from Figure 3, through after the modification, exist significantly mesoporous aperture to concentrate in the microporous filament geolyte, the most probable aperture is 3.5nm, illustrates after treatment, has formed a large amount of meso-hole structures in the mordenite.
Get the KOH solution 1200mL of 30 g Microporous zeolite ZSM-5s, 0.60 mol/L in beaker, (the 12.5W/100mL alkaline solution 25KHz), adds mechanical stirring, ultrasonication 20min to place ultrasonic cleaner; Under room temperature condition, stir 30min, change in the closed reactor, add again the ethanol of 90mL, process 3h, filtration, washing in 80 ℃.ZSM-5 zeolite after the washing is placed beaker, add the salpeter solution 900mL of 0.2mol/L, stir 20min under room temperature condition, change 90 ℃ of processing 2h in the water-bath over to, filter, wash, place 110 ℃ of dry 12h of baking oven again, the gained sample number into spectrum is CL2.
Embodiment 3
Get the NaOH solution 2100mL of 30 g micropore β, 0.50 mol/L in beaker, (the 4.76W/100mL alkaline solution 45KHz), adds mechanical stirring, ultrasonication 40min to place ultrasonic cleaner; Then change in the closed reactor, add again the propyl alcohol of 50mL, process 4h in 100 ℃; Filter, wash; β zeolite after the washing is placed beaker, add the sulphuric acid soln 1500mL of 0.8mol/L, stir 30min under room temperature condition, change 90 ℃ of processing 3h in the water-bath over to, filter, wash, place 110 ℃ of dry 12h of baking oven again, the gained sample number into spectrum is CL3.
As seen from Figure 2, the CL3 sample has the feature spectrogram of β zeolite, still keeps good Beta zeolite structures.As seen from Figure 4, through after the modification, exist significantly mesoporous aperture to concentrate in micropore β zeolite, the most probable aperture is 3.5nm.
Embodiment 4
Get the LiOH solution 2400mL of 30 g micropore ZSM-12,0.20 mol/L in beaker, (the 4.17W/100mL alkaline solution 48KHz), adds mechanical stirring, ultrasonication 30min to place ultrasonic cleaner; Change in the closed reactor, add again the propyl alcohol of 60mL, process 2h, filtration, washing in 120 ℃.ZSM-12 zeolite after the washing is placed beaker, add the sulphuric acid soln 900mL of 0.5mol/L, stir 20min under room temperature condition, change 100 ℃ of processing 3h in the water-bath over to, filter, wash, place 110 ℃ of dry 12h of baking oven again, the gained sample number into spectrum is CL4.
Get the NaOH solution 2100mL of 30 g micropore MCM-22 zeolites, 0.35 mol/L in beaker, (the 4.76W/100mL alkaline solution 48KHz), adds mechanical stirring, ultrasonication 30min to place ultrasonic cleaner; Change in the closed reactor, add again the propyl alcohol of 60mL, process 3.5h, filtration, washing in 50 ℃.MCM-22 zeolite after the washing is placed beaker, add the sulphuric acid soln 1200mL of 0.5mol/L, stir 40min under room temperature condition, change 80 ℃ of processing 3h in the water-bath over to, filter, wash, place 110 ℃ of dry 12h of baking oven again, the gained sample number into spectrum is CL5.
Comparative example 1
According to method described in " Microporous and Mesoporous Materials " (2004,69:29 – 34) the microporous filament geolyte is carried out modification.The NaOH solution 3000mL that gets 30g mordenite, 0.10 mol/L places beaker, stirs 30min under room temperature condition.Change in the flask again, in 60 ℃ of stirring 30min, filter, wash under refluxing, place 110 ℃ of dry 12h again, the gained sample number into spectrum is CL6.
Comparative example 2
According to method described in " Microporous and Mesoporous Materials " (2004,69:29 – 34) micropore β zeolite is carried out modification.The NaOH solution 3000mL that gets 30g β zeolite, 0.20 mol/L places beaker, stirs 30min under room temperature condition.Change in the flask again, in 85 ℃ of stirring 30min, filter, wash under refluxing, place 110 ℃ of dry 1h again, the gained sample number into spectrum is CL7.
Comparative example 3
The NaOH solution 2100mL that gets 30 g micropore β zeolites, 0.35 mol/L places beaker, stirs 30min under room temperature condition, changes in the closed reactor, processes 3.5h, filtration, washing in 50 ℃.β zeolite after the washing is placed beaker, add the sulphuric acid soln 1200mL of 0.5mol/L, stir 40min under room temperature condition, change 80 ℃ of processing 3h in the water-bath over to, filter, wash, place 110 ℃ of dry 12h of baking oven again, the gained sample number into spectrum is CL8.
Comparative example 4
The NaOH solution 2100mL that gets 30 g microporous filament geolytes, 0.35 mol/L places beaker, stirs 30min under room temperature condition, changes in the closed reactor, processes 3.5h, filtration, washing in 50 ℃.Mordenite after the washing is placed beaker, add the sulphuric acid soln 1200mL of 0.5mol/L, stir 40min under room temperature condition, change 80 ℃ of processing 3h in the water-bath over to, filter, wash, place 110 ℃ of dry 12h of baking oven again, the gained sample number into spectrum is CL9.
The pore structure character of the zeolite sample that embodiment 1～5 and comparative example 1～4 are prepared is listed in table 1.
Embodiment 6
Prepare mordenite according to comparative example 1 method.Get the mordenite 20g of preparation, the NH of 0.8 mol/L
4NO
3After mixing, solution 200mL in 80 ℃ of water bath processing 2h, refilters washing.Repeat above step 2 time.Again the gained solid matter is placed 110 ℃ of dry 12h of baking oven.Then process 4h in 550 ℃.Then carry out the high pressure compressing tablet, sieve is got 30～40 order samples and carry out xylene isomerization in micro-reaction equipment.Raw materials used composition (massfraction) is: less than C
7Straight-chain paraffin and naphthenic hydrocarbon 0.12%, C
8Straight-chain paraffin and naphthenic hydrocarbon 5.83%, benzene 0.35%, toluene 0.87%, ethylbenzene 10.85%, p-Xylol 0.87%, m-xylene 54. 77%, o-Xylol 26.34%.Reaction conditions is: air speed 3.0h
-1, hydrogen-oil ratio 1000,390 ℃ of temperature of reaction, reaction pressure 0.9 MPa.C
8Hydrocarbon yield 94.23%, p-Xylol account for 13.87% in product, p-Xylol proportion in dimethylbenzene is 21.22%.
Embodiment 7
Prepare mordenite according to embodiment 1 method.Get the mordenite 20g of preparation, 0.8mol/L NH
4NO
3After mixing, 200mL in 80 ℃ of water bath processing 2h, refilters washing.Repeat above step 2 time.Again the gained solid matter is placed 110 ℃ of dry 12h of baking oven.Then process 4h in 550 ℃.Then carry out the high pressure compressing tablet, sieve is got 30～40 order samples and carry out xylene isomerization in micro-reaction equipment.Raw materials used composition (massfraction) is: less than C
7Straight-chain paraffin and naphthenic hydrocarbon 0.12%, C
8Straight-chain paraffin and naphthenic hydrocarbon 5.83%, benzene 0.35%, toluene 0.87%, ethylbenzene 10.85%, p-Xylol 0.87%, m-xylene 54. 77%, o-Xylol 26.34%.Reaction conditions is: air speed 3.0h
-1, hydrogen-oil ratio 1000,390 ℃ of temperature of reaction, reaction pressure 0.9MPa.C
8Hydrocarbon yield 98.26%, p-Xylol account for 19.85% in product, p-Xylol proportion in dimethylbenzene is 25.05%.
Embodiment 8
Prepare the β zeolite according to comparative example 2 methods.Get the β zeolite 20g of preparation, the NH of 0.8mol/L
4NO
3After mixing, solution 200mL in 80 ℃ of water bath processing 2h, refilters washing.Repeat above step 2 time.Again the gained solid matter is placed 110 ℃ of dry 12h of baking oven.Then process 4h in 550 ℃.Then carry out the high pressure compressing tablet, sieve is got 30～40 order samples, and as stock oil carries out catalytic cracking, reaction conditions is: air speed 0.3 h take standard diesel oil (235～337 ℃ of diesel oil distillates) in micro-reaction equipment
-1, 70 seconds oil-feed time, 460 ℃ of temperature of reaction.Cracking activity index MA 61.5%, yield of gasoline 28.2%.
Embodiment 9
Prepare the β zeolite according to embodiment 3 methods.Get the β zeolite 20g of preparation, the NH of 0.8mol/L
4NO
3After mixing, solution 200mL in 80 ℃ of water bath processing 2h, refilters washing.Repeat above step 2 time.Again the gained solid matter is placed 110 ℃ of dry 12h of baking oven.Then process 4h in 550 ℃.Then carry out the high pressure compressing tablet, sieve is got 30～40 order samples, and as stock oil carries out catalytic cracking, reaction conditions is: air speed 0.3 h take standard diesel oil (235 ~ 337 ℃ of diesel oil distillates) in micro-reaction equipment
-1, 70 seconds oil-feed time, 460 ℃ of temperature of reaction.Cracking activity index MA 66.6%, yield of gasoline 31.3%.
The pore structure character of the related sample of table 1 embodiment
| Sample number into spectrum | The BET specific surface area, m 2/g | Mesoporous specific surface area, m 2/g | Micropore specific area, m 2/g | The most probable aperture, nm |
| CL1 | 586 | 215 | 371 | 3.5 |
| CL2 | 580 | 286 | 294 | 3.5 |
| CL3 | 849 | 432 | 417 | 3.5 |
| CL4 | 426 | 237 | 189 | 4 |
| CL5 | 486 | 232 | 254 | 4.5 |
| CL6 | 473 | 140 | 333 | 8 |
| CL7 | 575 | 227 | 348 | 4 |
| CL8 | 587 | 273 | 314 | 4 |
| CL9 | 485 | 133 | 352 | 4 |
| Micropore β | 617 | 99 | 518 | Nothing |
| Micropore ZSM-5 | 364 | 66 | 298 | Nothing |
| The microporous filament geolyte | 505 | 70 | 435 | Nothing |
| Micropore ZSM-12 | 340 | 87 | 253 | Nothing |
| Micropore MCM-22 | 403 | 23 | 380 | Nothing |
Claims (10)
1. the preparation method of a mesoporous-microporous zeolite molecular sieve may further comprise the steps:
(1) gets micro-pore zeolite, add according to a certain percentage alkaline solution, place ultrasonic environment to process 10～60 min;
(2) mixture that step (1) is obtained places encloses container, adds the lower molecular weight organic solvent, in 30～180 ℃ of lower alkaline purification 0.5～7h; Wherein the liquid-solid ratio of lower molecular weight organic solvent and micro-pore zeolite is 0.5～10 mL/g, and described lower molecular weight organic solvent is that carbonatoms is 1～4 alcohol or ketone;
(3) step (2) gained mixture is separated and wash;
(4) add acid solution, stir process for some time in the zeolite after step (3) the gained alkaline purification;
(5) products therefrom that obtains of step (4) is through separating, wash, be drying to obtain the compound pore canal system zeolite molecular sieve of mesoporous-micropore.
2. according to preparation method claimed in claim 1, it is characterized in that hyperacoustic frequency is 15KHz～10MHz described in the step (1), supersound process power is 3 ~ 30W/100mL alkaline solution, and the supersound process time is 20～40 min.
3. according to claim 1 or 2 described preparation methods, it is characterized in that, carry out mechanical stirring in when supersound process in the step (1).
4. according to preparation method claimed in claim 1, it is characterized in that the alkaline solution described in the step (1) is selected from one group of material of NaOH, KOH and LiOH aqueous solution composition, the concentration of alkaline solution is 0.1～7 mol/L.
5. according to preparation method claimed in claim 1, it is characterized in that the temperature of alkaline purification is 40～120 ℃ described in the step (2), the treatment time is 2～4h.
6. according to preparation method claimed in claim 1, it is characterized in that described lower molecular weight organic solvent is selected from one group of material that methyl alcohol, ethanol, propyl alcohol, Virahol and acetone form.
7. according to preparation method claimed in claim 1, it is characterized in that, the liquid-solid ratio of acid solution and micro-pore zeolite is 20～100 mL/g described in the step (4), and the concentration of acid solution is 0.1～3mol/L, and acid treatment refers at 40～150 ℃ of lower stir process 0.5～7 h.
8. according to preparation method claimed in claim 1, it is characterized in that described acid solution is one or more in sulfuric acid, hydrochloric acid and the salpeter solution.
9. according to preparation method claimed in claim 7, it is characterized in that acid-treated temperature is 50～120 ℃ described in the step (4), the treatment time is 2～5h.
10. according to preparation method claimed in claim 1, it is characterized in that the micro-pore zeolite described in the step (1) is selected from β zeolite, mordenite, ZSM-22 zeolite, ZSM-5 zeolite or MCM-22 zeolite.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110192766.0A CN102874829B (en) | 2011-07-11 | 2011-07-11 | Preparation method of mesopore-micropore zeolite molecular sieve |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110192766.0A CN102874829B (en) | 2011-07-11 | 2011-07-11 | Preparation method of mesopore-micropore zeolite molecular sieve |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102874829A true CN102874829A (en) | 2013-01-16 |
| CN102874829B CN102874829B (en) | 2014-07-23 |
Family
ID=47476394
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110192766.0A Active CN102874829B (en) | 2011-07-11 | 2011-07-11 | Preparation method of mesopore-micropore zeolite molecular sieve |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102874829B (en) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103359758A (en) * | 2013-07-25 | 2013-10-23 | 广东中烟工业有限责任公司 | Water-containing material, and preparation method thereof and application in cigarettes |
| CN104909384A (en) * | 2015-05-27 | 2015-09-16 | 中国科学院广州地球化学研究所 | Mordenite having diatomite morphology and multi-level pore channel structure, and preparation method thereof |
| CN105293514A (en) * | 2014-07-03 | 2016-02-03 | 中国石油化工股份有限公司 | Hierarchical porous silica-alumina zeolite molecular sieve, synthetic method and application of hierarchical porous silica-alumina zeolite molecular sieve |
| WO2016145617A1 (en) * | 2015-03-17 | 2016-09-22 | 中国科学院大连化学物理研究所 | Method for preparation of, and application of, mordenite having mesopores and micropores |
| CN109317191A (en) * | 2018-11-19 | 2019-02-12 | 包头稀土研究院 | Molecular sieve catalyst and preparation method and use thereof |
| CN109319803A (en) * | 2018-11-19 | 2019-02-12 | 包头稀土研究院 | Composite pore molecular sieve and preparation method thereof |
| CN111054303A (en) * | 2020-01-08 | 2020-04-24 | 中国计量大学 | Natural zeolite multifunctional modification method for improving ammonia nitrogen removal rate of water body |
| CN111378300A (en) * | 2020-03-20 | 2020-07-07 | 上海安费诺永亿通讯电子有限公司 | Laser-enhanced chemical plating filler and preparation method thereof, laser-enhanced chemical plating material and method for carrying out selective metallization on surface of laser-enhanced chemical plating material |
| CN112601800A (en) * | 2018-09-25 | 2021-04-02 | 禾大国际股份公开有限公司 | Catalyst and its use in fatty acid isomerization |
| CN113398981A (en) * | 2021-05-24 | 2021-09-17 | 南京师范大学 | Preparation method of micro-mesoporous mordenite, mordenite obtained by preparation method and application of mordenite |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1530322A (en) * | 2003-03-11 | 2004-09-22 | 中国石油化工股份有限公司 | ZSM-5 structure zeolite, preparation and use thereof |
| CN101428817A (en) * | 2007-11-07 | 2009-05-13 | 中国石油化工股份有限公司 | Process for producing cavity type ZSM-5 modified zeolite molecular sieve |
-
2011
- 2011-07-11 CN CN201110192766.0A patent/CN102874829B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1530322A (en) * | 2003-03-11 | 2004-09-22 | 中国石油化工股份有限公司 | ZSM-5 structure zeolite, preparation and use thereof |
| CN101428817A (en) * | 2007-11-07 | 2009-05-13 | 中国石油化工股份有限公司 | Process for producing cavity type ZSM-5 modified zeolite molecular sieve |
Non-Patent Citations (3)
| Title |
|---|
| J.C. GROEN ET AL.: "On the introduction of intracrystalline mesoporosity in zeolites upon desilication in alkaline medium", 《MICROPOROUS AND MESOPOROUS MATERIALS》 * |
| 宋春敏: "新型微孔-介孔复合结构硅酸铝分子筛的合成、表征及应用研究", 《中国博士学位论文全文数据库 工程科技Ⅰ辑》 * |
| 王劲松: "正丁醇在无机硅源合成介孔分子筛过程的作用", 《石油与天然气化工》 * |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103359758A (en) * | 2013-07-25 | 2013-10-23 | 广东中烟工业有限责任公司 | Water-containing material, and preparation method thereof and application in cigarettes |
| CN103359758B (en) * | 2013-07-25 | 2015-09-02 | 广东中烟工业有限责任公司 | A kind of hydrous material and preparation method thereof and the application in cigarette |
| CN105293514A (en) * | 2014-07-03 | 2016-02-03 | 中国石油化工股份有限公司 | Hierarchical porous silica-alumina zeolite molecular sieve, synthetic method and application of hierarchical porous silica-alumina zeolite molecular sieve |
| WO2016145617A1 (en) * | 2015-03-17 | 2016-09-22 | 中国科学院大连化学物理研究所 | Method for preparation of, and application of, mordenite having mesopores and micropores |
| CN104909384A (en) * | 2015-05-27 | 2015-09-16 | 中国科学院广州地球化学研究所 | Mordenite having diatomite morphology and multi-level pore channel structure, and preparation method thereof |
| CN112601800A (en) * | 2018-09-25 | 2021-04-02 | 禾大国际股份公开有限公司 | Catalyst and its use in fatty acid isomerization |
| CN112601800B (en) * | 2018-09-25 | 2023-06-02 | 禾大国际股份公开有限公司 | Catalyst and its use in isomerisation of fatty acids |
| CN109319803A (en) * | 2018-11-19 | 2019-02-12 | 包头稀土研究院 | Composite pore molecular sieve and preparation method thereof |
| CN109317191A (en) * | 2018-11-19 | 2019-02-12 | 包头稀土研究院 | Molecular sieve catalyst and preparation method and use thereof |
| CN109317191B (en) * | 2018-11-19 | 2021-06-08 | 包头稀土研究院 | Molecular sieve catalyst and preparation method and use thereof |
| CN111054303A (en) * | 2020-01-08 | 2020-04-24 | 中国计量大学 | Natural zeolite multifunctional modification method for improving ammonia nitrogen removal rate of water body |
| CN111378300A (en) * | 2020-03-20 | 2020-07-07 | 上海安费诺永亿通讯电子有限公司 | Laser-enhanced chemical plating filler and preparation method thereof, laser-enhanced chemical plating material and method for carrying out selective metallization on surface of laser-enhanced chemical plating material |
| CN113398981A (en) * | 2021-05-24 | 2021-09-17 | 南京师范大学 | Preparation method of micro-mesoporous mordenite, mordenite obtained by preparation method and application of mordenite |
| CN113398981B (en) * | 2021-05-24 | 2023-09-22 | 南京师范大学 | Preparation method of micro-mesoporous mordenite and its obtained mordenite and applications |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102874829B (en) | 2014-07-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102874829B (en) | Preparation method of mesopore-micropore zeolite molecular sieve | |
| CN102464325B (en) | Preparation method of mesoporous-microporous zeolite molecular sieve | |
| CN102874830B (en) | Method for preparing mesopore-micropore zeolite molecular sieve material | |
| CN102464336B (en) | Modification method of ZSM-5 zeolite | |
| CN102190316B (en) | Method for synthesizing mesoporous mordenite | |
| Weissenberger et al. | Hierarchical ZSM‐5 catalysts: The effect of different intracrystalline pore dimensions on catalyst deactivation behaviour in the MTO reaction | |
| EP3423405A1 (en) | Controlled alkaline treatments on molecular sieves | |
| WO2015100171A1 (en) | Introducing mesoporosity into zeolite materials with a modified acid pre-treatment step | |
| CN103007983A (en) | HZSM-5 molecular sieve based catalyst for producing gasoline from methanol, and preparation method and application thereof | |
| CN101269340A (en) | A kind of ZSM-5 zeolite catalyst with high silicon-aluminum ratio and its preparation method and application | |
| Kowalska‐Kuś et al. | Solketal formation in a continuous flow process over hierarchical zeolites | |
| Yu et al. | Synthesis and applications of SAPO‐34 molecular sieves | |
| CN103950951A (en) | Method for synthesizing heteroatomic ZSM-5 molecular sieve and application thereof | |
| CN1789127A (en) | Preparation method of Y type molecular sieve enriched with mesopore | |
| Coppens et al. | Nature‐Inspired, Computer‐Assisted Optimization of Hierarchically Structured Zeolites | |
| JP2020158389A (en) | Zeolitic material having distinctive macroporosity in single crystal, and method for producing the zeolitic material | |
| Mirshafiee et al. | A green approach for template free synthesis of Beta zeolite incorporated in ZSM-5 zeolite to enhance catalytic activity in MTG reaction: Effect of seed nature and temperature | |
| Geng et al. | Structure evolution of Zn species on fresh, deactivated, and regenerated Zn/ZSM-5 catalysts in ethylene aromatization | |
| CN102874840B (en) | Modification treatment method of ZSM-5 zeolite | |
| Zhou et al. | One-step synthesis of hierarchical lamellar H-ZSM-5 zeolite and catalytic performance of methanol to olefin | |
| CN102874841B (en) | Method for modifying ZSM-5 zeolite material | |
| CN107032367A (en) | A kind of order mesoporous ZSM 5 of utilization in-situ carburization templated synthesis method | |
| US8609910B1 (en) | Catalytic pyrolysis using UZM-39 aluminosilicate zeolite | |
| CN102839010A (en) | Preparation method for modified magnesium aluminum spinel having acidity and alkality | |
| CN109179450A (en) | The preparation method that a kind of cotton thread is templated synthesis small particle multilevel structure SAPO-34 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |