CN103447078A - Nano MFI-type molecular sieve with hierarchical pore structure and preparation method and application thereof - Google Patents
Nano MFI-type molecular sieve with hierarchical pore structure and preparation method and application thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of a catalyst and an application thereof, and particularly relates to a nano MFI-type molecular sieve which is easy to separate and has high hydrothermal stability and a hierarchical pore channel structure, and a preparation method and application thereof. The method comprises the following steps: (1) selecting a prepared nano MFI-type molecular sieve suspension as a mother liquid; (2) adding a cationic flocculant into the mother liquid to assemble the nano molecular sieve; (3) putting the assembled nano molecular sieve into a reaction kettle for hydrothermal synthesis to obtain a nano molecular sieve compound with a block size of 100 nanometers to 100 microns. The nano molecular sieve compound is subjected to conventional filtering, washing, drying and roasting to obtain the nano MFI-type molecular sieve with a hierarchical pore channel structure. The nano MFI-type molecular sieve prepared by the method can be separated through a filtering operation and has the advantages of open intercrystalline pore channel structure, large pore volume, high crystallization rate and high hydrothermal stability; in a methanol-to-propylene reaction, the nano MFI-type molecular sieve shows higher propylene yield and stability than the nano MFI-type molecular sieve prepared by a conventional method.
Description
Technical field
The invention belongs to catalyst and applied technical field thereof, specifically a kind of easily separated, high hydrothermal stability, multi-stage artery structure nanometer MFI type zeolite molecular sieve and preparation method thereof and the application in preparing propylene from methanol thereof.
Background technology
MFI type zeolite molecular sieve is the high silicon micro-pore zeolite of a class of Mobil company 20 century 70s exploitations, but the acid and good shape selectivity of the well-regulated duct of tool modulation, as solid acid catalyst in the petrochemical industry extensive use.
At present, the MFI type molecular sieve catalyst of industrial use is mostly to be of a size of the large crystal grain MFI molecular sieve of several microns.Because the MFI molecular sieve pore passage is long and narrow, crystallite dimension is larger in addition, and large molecule is larger at the crystal inside diffusional resistance, easily generates carbon distribution, causes catalyst life shorter.With respect to conventional microsized zeolite, it is large that nano molecular sieve has surface area, the characteristics that the many and duct of mesoporous volume is short etc., therefore often show catalytic activity high, carbon accumulation resisting ability is strong, the advantages such as stability is lasting, in hydrocracking, fluid catalytic cracking, the alkylation of benzene, the oligomerisation reaction of alkene, preparing gasoline by methanol, the synthetic of methylamine waited in the laboratory research of reacting, nano molecular sieve has all been obtained the effect that significantly is better than conventional microsized zeolite, fully demonstrate nano molecular sieve catalyst to improving chemical industry resource utilization and added value of product, the importance of development high-efficiency cleaning production technology.
Yet, with synthetic the comparing of conventional micron order MFI molecular sieve, preparation nanometer MFI zeolite is very complicated process.Usually, synthetic nanocrystal all is suspended in mother liquor, separate obtain these nano zeolites all will be by ultracentrifugal method, and this is very difficult for industrial extensive preparation, and the resulting nano molecular sieve productive rate of high speed centrifugation is lower.Particularly, the nano molecular sieve crystal, because its outer surface is larger, causes its activity higher, and hydrothermal stability is poor.Above 2 have restricted its widespread adoption.
Summary of the invention
The object of the present invention is to provide a kind of easily separated, high hydrothermal stability, multi-stage artery structure nanometer MFI type zeolite molecular sieve and its preparation method and application, improve the hydrothermal stability of nanometer MFI type molecular sieve, problem is recycled in the separation of mass transfer ability, solution nanometer MFI molecular sieve.
Technical scheme of the present invention is:
The invention provides the preparation method of a kind of high hydrothermal stability, easily separated, multi-stage artery structure nanometer MFI type zeolite molecular sieve, the method step is:
Choose the nanometer MFI molecular sieve suspension that prepared as needed molecular sieve mother liquor, in the molecular sieve mother liquor, add cationic flocculant to be assembled nano molecular sieve in mother liquor; Nano molecular sieve is after cationic flocculant assembling, and the reactor Hydrothermal Synthesis of packing into, obtain being of a size of the assemble nanometer molecular screen composite of 100 nanometers to 100 micron; The nano molecular sieve compound, through routine filtration, washing, dry, roasting, obtains hierarchical porous structure nanometer MFI molecular sieve.
In the present invention, MFI type molecular sieve is Silicalite-1, ZSM-5 or TS-1;
In the present invention, the crystalline size of nanometer MFI type molecular sieve is the 5-500 nanometer;
In the present invention, the preparation process of molecular sieve mother liquor is as follows:
By the 1:0.05-0.5:0.001-0.1:10-100 mixing in molar ratio of silicon source, TPAOH, Huo Tai source, aluminium source, deionized water, after the complete hydrolysis of silicon source, above-mentioned solution is placed on to Hydrothermal Synthesis in reactor, at 120-150 ℃ of Hydrothermal Synthesis 4-8h, obtain nanometer MFI type molecular sieve suspension.
Wherein, the aluminium source is aluminum nitrate, aluminum sulfate, sodium metaaluminate, boehmite, aluminium foil or aluminium isopropoxide etc., and the titanium source is butyl titanate, titanium sulfate, Titanium Nitrate or titanium tetrachloride.
In the present invention, cationic flocculant is one or more in poly-amidine, polyvinylamine, PAMC, PDDA, softex kw, polyaniline, polyacrylamide;
In the present invention, the cationic flocculant addition is the 1%-20% of molecular sieve mother liquor quality, is preferably 2-10%.
In the present invention, the treatment temperature of Hydrothermal Synthesis is 90-200 ℃, is preferably 110-170 ℃; The processing time of Hydrothermal Synthesis is 2-160 hour, is preferably 3-24 hour.
In the present invention, sintering temperature is 450-650 ℃, is preferably 500-600 ℃; Roasting time is 1-24 hour, is preferably 3-10 hour.
In the present invention, high hydrothermal stability, easily separated, hierarchical porous structure nanometer MFI type molecular sieve are assembled by many nano molecular sieve crystal, crystal grain is piled up each other and is formed a large amount of intergranular pore channels, there is open intergranular pore channel structure, hierarchical porous structure nano molecular sieve assembly is of a size of 100 nanometers to 100 micron, and this size refers to the size (particle diameter) of the aggregate that nano molecular sieve crystal grain is assembled into.Wherein, the implication of multistage pore canal is mesoporous between the micropore that had by the MFI zeolite molecular sieve of this material itself, nanometer MFI zeolite molecular sieve crystal, and the macropore between the nano molecular sieve assembly forms.In hierarchical porous structure nanometer MFI type molecular sieve, the specific area scope is 300-600m
2g
-1; The total pore volume scope is 0.2-2.0cm
3g
-1, the micro pore volume scope is 0.01-0.17cm
3g
-1, mesoporous volume range is 0.02-1.0cm
3g
-1, the macropore volume scope is 0.02-1.8cm
3g
-1.Wherein, the micropore size scope is that the 0.5-2nm(micropore size is not containing 2nm), mesoporous pore diameter range is 2-50nm, the macropore diameter scope is that the 50-2000nm(macropore diameter is not containing 50nm).
In the present invention, high hydrothermal stability, segregative nanometer MFI type molecular sieve, wherein, the Si/Al atomic ratio=10-1000 of nano-ZSM-5 type molecular sieve; Si/Ti atomic ratio=the 10-1000 of nano-scale TS-1 type molecular sieve.
In the present invention, hierarchical porous structure nano molecular sieve assembly can be realized separating by filter operation.
The application of described multi-stage artery structure nanometer MFI type molecular sieve, in MTP preparing propylene from methanol process, fill in fixed bed reactors by multi-stage artery structure nanometer MFI type molecular sieve, the industrial methanol that material liquid is 40-95wt%, and mass space velocity is 0.3-10h
-1, reaction temperature is 400-550 ℃.
The present invention has following beneficial effect:
1, the preparation method of high hydrothermal stability of the present invention, easily separated nanometer MFI type molecular sieve catalyst, at first prepare the nano molecular sieve mother liquor; Then, utilize the long-chain cationic polymers such as poly-amidine, polyaniline, polyvinylamine, PAMC, PDDA, softex kw, polyacrylamide, electronegative nano molecular sieve is assembled; The nano molecular sieve solution assembled is added in reactor, under hydrothermal condition, continue crystallization.Make growth mutually between the nano molecular sieve crystal, realize chemical bond, cationic polymer plays the double action of assembling masterplate and pore creating material therein.
2, adopt the prepared nano molecular sieve of the inventive method to realize separating by filter operation, prepared nanometer MFI molecular sieve has open intergranular pore channel structure, pore volume is large, percent crystallization in massecuite is high, hydrothermal stability is high, in the preparing propylene from methanol reaction, show than conventional method and prepare productivity of propylene and the catalyst stability that nanometer MFI molecular sieve is higher.
3, the nanometer MFI molecular sieve pore volume that adopts the inventive method to prepare can reach 2.0cm
3/ g, with traditional MFI type molecular sieve (0.175cm
3/ g) compare and be significantly increased.
The accompanying drawing explanation
The XRD spectra that Fig. 1 is the synthetic product of the embodiment of the present invention 1.
The SEM picture that Fig. 2 is the synthetic product of the embodiment of the present invention 1.
The nitrogen adsorption that Fig. 3 a is the synthetic product of the embodiment of the present invention 1, desorption curve.
Fig. 3 b is the synthetic product B JH method differential pore volume pore size distribution curve of the embodiment of the present invention 1.Wherein, V-volume; The d-aperture.
Fig. 4 is the synthetic product of the embodiment of the present invention 1 and traditional nano-ZSM-5 suspension contrast photo.Wherein, left side is the synthetic ZSM-5 of the embodiment of the present invention 1; Right side is traditional nano-ZSM-5.
Fig. 5 is that nano-ZSM-5 molecular sieve catalytic performance in preparing propylene from methanol reacts prepared with conventional method by the synthetic product of the embodiment of the present invention 1 compares.
The specific embodiment
Below by embodiment in detail the present invention is described in detail.
Embodiment 1
In the present embodiment, the preparation method of high hydrothermal stability, easily separated, nano-ZSM-5 type zeolite molecular sieve:
At first, the mother liquor that preparation comprises the nanoscale ZSM-5 molecular sieve: by the 1:0.32:0.02:29 mixing in molar ratio of ethyl orthosilicate, TPAOH, sodium metaaluminate, deionized water, after the ethyl orthosilicate complete hydrolysis, above-mentioned solution is placed on to Hydrothermal Synthesis in reactor, at 130 ℃ of Hydrothermal Synthesis 6h, obtain the nano-ZSM-5 molecular sieve mother liquor.Add polyphenyl acid amides (polyphenyl acid amides addition be molecular sieve mother liquor quality 5%) in above-mentioned molecular sieve mother liquor, 12000 rev/mins of lower high-speed stirred, after 2 hours, add reactor, at 160 ℃, Hydrothermal Synthesis 6 hours, make the nano-ZSM-5 molecular sieve compound.The gained molecular screen composite, after conventional molecular sieve filter filters, repeatedly cleans for several times in the deionized water of 100 ℃, and under 100 ℃ of conditions, drying is 12 hours.Dry rear sample in Muffle furnace, 550 ℃ of roastings 6 hours (programming rate is 2 ℃/min, cooling with stove).
The XRD collection of illustrative plates that Fig. 1 is products obtained therefrom, therefrom can find out that product has typical MFI type zeolite molecules sieve structure, and sample has higher degree of crystallinity.
The SEM pattern that Fig. 2 is products obtained therefrom, therefrom can find out that the nano molecular sieve aggregate has the type ZSM 5 molecular sieve crystal composition of many Nano grades, has higher intercrystalline pore rate between crystal.In the present embodiment, total pore volume is 0.69cm
3g
-1.The micropore pore volume that the ZSM-5 zeolite molecular sieve itself has is 0.12cm
3g
-1, the mesoporous pore volume between the nano-ZSM-5 zeolite molecular sieve crystal is 0.45cm
3g
-1, the macropore pore volume between the nano molecular sieve assembly is 0.12cm
3g
-1.Wherein, the micropore size scope is 0.5-0.7nm, and mesoporous pore diameter range is 2-10nm, and the macropore diameter scope is 60-150nm.
In the present embodiment, hierarchical porous structure nanometer MFI type molecular sieve is assembled under the effect of cationic flocculant by the nano molecular sieve crystal, nanocrystal is piled up the formation intergranular pore channel each other, has open intergranular pore channel structure, and hierarchical porous structure nano molecular sieve assembly is of a size of 300-500nm.
The nitrogen adsorption that Fig. 3 a is products obtained therefrom, desorption curve, can find out, the specific area of the nano-ZSM-5 molecular sieve obtained (BET) is 380.28m
2g
-1.The pore size distribution curve that Fig. 3 b is products obtained therefrom can find out that the nano-ZSM-5 molecular sieve obtained has multi-stage artery structure.
Fig. 4 is the synthetic product of the embodiment of the present invention 1 and traditional nano-ZSM-5 suspension contrast photo.Therefrom can find out, the synthetic nano-ZSM-5 type molecular sieve of conventional method is suspended in the middle of solution, even still can not separate fully through high speed centrifugation (12000 rev/mins * 2 hours).Products obtained therefrom of the present invention, through the cationic polymer assembling, be deposited on the solution bottom due to the nano molecular sieve crystal, separable by suction filtration.
Embodiment 2
In the present embodiment, the preparation method of high hydrothermal stability, easily separated, nano-ZSM-5 type zeolite molecular sieve:
At first, the mother liquor that preparation comprises nano-ZSM-5 molecular sieve: by the 1:0.32:0.02:29 mixing in molar ratio of ethyl orthosilicate, TPAOH, sodium metaaluminate, deionized water, after the ethyl orthosilicate complete hydrolysis, above-mentioned solution is placed on to Hydrothermal Synthesis in reactor, at 130 ℃ of Hydrothermal Synthesis 6h, obtain the nano-ZSM-5 molecular sieve mother liquor.Add diallyl dimethyl ammoniumchloride (diallyl dimethyl ammoniumchloride addition be molecular sieve mother liquor quality 7.5%) in above-mentioned molecular sieve mother liquor, 12000 rev/mins of lower high-speed stirred after 2 hours, add reactor, at 130 ℃, Hydrothermal Synthesis 12 hours, make the nano-ZSM-5 molecular sieve compound.The gained molecular screen composite, after conventional molecular sieve filter filters, repeatedly cleans for several times in the deionized water of 100 ℃, and under 100 ℃ of conditions, drying is 12 hours.Dry rear sample in Muffle furnace, 600 ℃ of roastings 3 hours (programming rate is 2 ℃/min, cooling with stove).The specific area of the nano-ZSM-5 molecular sieve obtained (BET) is 356.28m
2g
-1, total pore volume is 1.06cm
3g
-1.The micropore pore volume that the ZSM-5 zeolite molecular sieve itself has is 0.08cm
3g
-1, the mesoporous pore volume between the nano-ZSM-5 zeolite molecular sieve crystal is 0.45cm
3g
-1, the macropore pore volume between the nano molecular sieve assembly is 0.53cm
3g
-1.Wherein, the micropore size scope is 0.5-0.65nm, and mesoporous pore diameter range is 2-20nm, and the macropore diameter scope is 500-2000nm.
In the present embodiment, hierarchical porous structure nanometer MFI type molecular sieve is assembled under the effect of cationic flocculant by the nano molecular sieve crystal, nanocrystal is piled up the formation intergranular pore channel each other, has open intergranular pore channel structure, and hierarchical porous structure nano molecular sieve assembly is of a size of the 50-100 micron.
Embodiment 3
In the present embodiment, the preparation method of high hydrothermal stability, easily separated, nano-ZSM-5 type zeolite molecular sieve:
At first, the mother liquor that preparation comprises nano-ZSM-5 molecular sieve: by the 1:0.32:0.02:29 mixing in molar ratio of ethyl orthosilicate, TPAOH, sodium metaaluminate, deionized water, after the ethyl orthosilicate complete hydrolysis, above-mentioned molecular sieve mother liquor is placed on to Hydrothermal Synthesis in reactor, at 130 ℃ of Hydrothermal Synthesis 6h, obtain the nano-ZSM-5 molecular sieve mother liquor.Add softex kw (softex kw addition be molecular sieve mother liquor quality 3%) in above-mentioned solution, after 2 hours, add reactor, at 120 ℃ 12000 rev/mins of lower high-speed stirred, Hydrothermal Synthesis 24 hours, make the nano-ZSM-5 molecular sieve compound.The gained molecular screen composite, after conventional molecular sieve filter filters, repeatedly cleans for several times in the deionized water of 100 ℃, and under 100 ℃ of conditions, drying is 12 hours.Dry rear sample in Muffle furnace, 500 ℃ of roastings 12 hours (programming rate is 2 ℃/min, cooling with stove).The specific area of the nano-ZSM-5 molecular sieve obtained (BET) is 589.28m
2g
-1, total pore volume is 1.72cm
3g
-1.The micropore pore volume that the ZSM-5 zeolite molecular sieve itself has is 0.10cm
3g
-1, the mesoporous pore volume between the nano-ZSM-5 zeolite molecular sieve crystal is 0.52cm
3g
-1, the macropore pore volume between the nano molecular sieve assembly is 1.10cm
3g
-1.Wherein, the micropore size scope is 0.5-0.7nm, and mesoporous pore diameter range is 10-30nm, and the macropore diameter scope is 100-500nm.
In the present embodiment, hierarchical porous structure nanometer MFI type molecular sieve is assembled under the effect of cationic flocculant by the nano molecular sieve crystal, nanocrystal is piled up the formation intergranular pore channel each other, has open intergranular pore channel structure, and hierarchical porous structure nano molecular sieve assembly is of a size of the 10-50 micron.
Embodiment 4
In the present embodiment, the preparation method of high hydrothermal stability, easily separated, nano-scale TS-1 type zeolite molecular sieve:
At first, the mother liquor that preparation comprises the nano-scale TS-1 molecular sieve: by the 1:0.32:0.01:29 mixing in molar ratio of ethyl orthosilicate, TPAOH, butyl titanate, deionized water, after the ethyl orthosilicate complete hydrolysis, above-mentioned solution is placed on to Hydrothermal Synthesis in reactor, at 130 ℃ of Hydrothermal Synthesis 6h, obtain nano-scale TS-1 molecular sieve mother liquor.Add polyaniline (polyaniline addition be molecular sieve mother liquor quality 5.5%) in above-mentioned molecular sieve mother liquor, 12000 rev/mins of lower high-speed stirred, after 2 hours, add reactor, at 150 ℃, Hydrothermal Synthesis 12 hours, make the nano-scale TS-1 molecular screen composite.The gained molecular screen composite, after conventional molecular sieve filter filters, repeatedly cleans for several times in the deionized water of 100 ℃, and under 100 ℃ of conditions, drying is 12 hours.Dry rear sample in Muffle furnace, 550 ℃ of roastings 3 hours (programming rate is 2 ℃/min, cooling with stove).The specific area (BET) of the nano-scale TS-1 molecular sieve obtained is 383.56m
2g
-1, total pore volume is 1.77m
3g
-1.The micropore pore volume that nano-scale TS-1 type zeolite molecular sieve itself has is 0.12cm
3g
-1, the mesoporous pore volume between nano-scale TS-1 type zeolite molecular sieve crystal is 0.45cm
3g
-1, the macropore pore volume between the nano molecular sieve assembly is 1.2cm
3g
-1.Wherein, the micropore size scope is 0.5-0.7nm, and mesoporous pore diameter range is 2-20nm, and the macropore diameter scope is 200-500nm.
In the present embodiment, hierarchical porous structure nanometer MFI type molecular sieve is assembled under the effect of cationic flocculant by the nano molecular sieve crystal, nanocrystal is piled up the formation intergranular pore channel each other, has open intergranular pore channel structure, and hierarchical porous structure nano molecular sieve assembly is of a size of the 20-30 micron.
In the present embodiment, the preparation method of high hydrothermal stability, easily separated, nanometer silicalite-1 type zeolite molecular sieve:
At first, the mother liquor that preparation comprises nanoscale silicalite-1 molecular sieve: by the 1:0.32:29 mixing in molar ratio of Ludox, TPAOH, deionized water, after the ethyl orthosilicate complete hydrolysis, above-mentioned molecular sieve mother liquor is placed on to Hydrothermal Synthesis in reactor, at 120 ℃ of Hydrothermal Synthesis 6h, obtain nanometer silicalite-1 molecular sieve mother liquor.Add softex kw (softex kw addition be molecular sieve mother liquor quality 5%) in above-mentioned solution, 10000 rev/mins of lower high-speed stirred after 2 hours, add reactor, at 120 ℃, Hydrothermal Synthesis 24 hours, make nanometer silicalite-1 molecular screen composite.The gained molecular screen composite, after conventional molecular sieve filter filters, repeatedly cleans for several times in the deionized water of 100 ℃, and under 100 ℃ of conditions, drying is 12 hours.Dry rear sample in Muffle furnace, 500 ℃ of roastings 12 hours (programming rate is 2 ℃/min, cooling with stove).The specific area (BET) of the nanometer silicalite-1 molecular sieve obtained is 467.67m
2g
-1, total pore volume is 1.85m
3g
-1.The micropore pore volume that nanoscale silicalite-1 molecular sieve itself has is 0.13cm
3g
-1, the mesoporous pore volume between nanoscale silicalite-1 molecular sieve crystal is 0.52cm
3g
-1, the macropore pore volume between the nano molecular sieve assembly is 1.20cm
3g
-1.Wherein, the micropore size scope is 0.5-0.7nm, and mesoporous pore diameter range is 5-20nm, and the macropore diameter scope is 70-120nm.
In the present embodiment, hierarchical porous structure nanometer MFI type molecular sieve is assembled under the effect of cationic flocculant by the nano molecular sieve crystal, nanocrystal is piled up the formation intergranular pore channel each other, has open intergranular pore channel structure, and hierarchical porous structure nano molecular sieve assembly is of a size of 200-500nm.
Embodiment 6
In the present embodiment, the nano-ZSM-5 molecular sieve that adopts the present invention the to prepare catalytic effect for the preparing propylene from methanol reaction is described, and is contrasted with the catalytic effect of the synthetic nano molecular sieve of conventional method.
The molecular sieve 20g of embodiment 1 preparation is filled in to fixed bed reactors, and the industrial methanol of mass concentration 90% of take is raw material, methanol quality air speed 3h
-1, under 500 ℃ of reaction temperatures, carry out the catalytic reaction evaluation.
Result as shown in Figure 5, can realize separating by filter operation by the prepared nano-ZSM-5 molecular sieve of the method; Prepared nano-ZSM-5 molecular sieve has open intergranular pore channel structure, and pore volume is large, and percent crystallization in massecuite is high, and hydrothermal stability is high, and in the preparing propylene from methanol reaction, the relatively conventional nano-ZSM-5 molecular sieve of this catalyst, have longer life-span and higher productivity of propylene.The strengthening effect of mass transmitting of this raising owing to the nano molecular sieve hydrothermal stability and intracrystalline pore.
Claims (10)
1. a hierarchical porous structure nanometer MFI type molecular sieve, it is characterized in that, hierarchical porous structure nanometer MFI type molecular sieve is assembled under the effect of cationic flocculant by the nano molecular sieve crystal, nanocrystal is piled up the formation intergranular pore channel each other, have open intergranular pore channel structure, hierarchical porous structure nano molecular sieve assembly is of a size of 100 nanometers to 100 micron.
2. according to hierarchical porous structure nanometer MFI type molecular sieve claimed in claim 1, it is characterized in that, in hierarchical porous structure nanometer MFI type molecular sieve, the specific area scope is 300-600m
2g
-1; The total pore volume scope is 0.2-2.0cm
3g
-1, the micro pore volume scope is 0.01-0.17cm
3g
-1, mesoporous volume range is 0.02-1.0cm
3g
-1, the macropore volume scope is 0.02-1.8cm
3g
-1; Wherein, the micropore size scope is 0.5-2nm, and mesoporous pore diameter range is 2-50nm, and the macropore diameter scope is 50-2000nm.
3. according to the preparation method of hierarchical porous structure nanometer MFI type molecular sieve claimed in claim 1, it is characterized in that, preparation process is as follows:
(1) choose the nanometer MFI type molecular sieve suspension that prepared as mother liquor;
Wherein, MFI type molecular sieve is Silicalite-1, ZSM-5 or TS-1;
Wherein, the crystalline size of nanometer MFI type molecular sieve is the 5-500 nanometer;
(2) in mother liquor, add cationic flocculant to be assembled nano molecular sieve in mother liquor, the cationic flocculant addition is the 1%-20% of molecular sieve mother liquor quality; Wherein:
Described cationic flocculant is one or more in poly-amidine, polyvinylamine, PAMC, PDDA, softex kw, polyaniline, polyacrylamide;
(3) nano molecular sieve is after cationic flocculant assembling, and the reactor Hydrothermal Synthesis of packing into obtains being of a size of the assemble nanometer molecular screen composite of 100 nanometers to 100 micron; Wherein:
The treatment temperature of Hydrothermal Synthesis is 90-200 ℃, and the processing time of Hydrothermal Synthesis is 2-160 hour;
(4) the nano molecular sieve compound, through routine filtration, washing, dry, roasting, obtains hierarchical porous structure nanometer MFI type molecular sieve.
4. according to the preparation method of hierarchical porous structure nanometer MFI type molecular sieve claimed in claim 3, it is characterized in that, in step (1), the preparation process of molecular sieve mother liquor is as follows:
By the 1:0.05-0.5:0.001-0.1:10-100 mixing in molar ratio of silicon source, TPAOH, Huo Tai source, aluminium source, deionized water, after the complete hydrolysis of silicon source, above-mentioned solution is placed on to Hydrothermal Synthesis in reactor, at 120-150 ℃ of Hydrothermal Synthesis 4-8h, obtain nanometer MFI type molecular sieve suspension.
5. according to the preparation method of hierarchical porous structure nanometer MFI type molecular sieve claimed in claim 3, it is characterized in that, in step (2), the cationic flocculant addition is the 2-10% of molecular sieve mother liquor quality preferably.
6. according to the preparation method of hierarchical porous structure nanometer MFI type molecular sieve claimed in claim 3, it is characterized in that, in step (3), the treatment temperature of Hydrothermal Synthesis is preferably 110-170 ℃, and the processing time of Hydrothermal Synthesis is preferably 3-24 hour.
7. according to the preparation method of hierarchical porous structure nanometer MFI type molecular sieve claimed in claim 3, it is characterized in that, in step (4), sintering temperature is 450-650 ℃, and roasting time is 1-24 hour.
8. according to the preparation method of hierarchical porous structure nanometer MFI type molecular sieve claimed in claim 3, it is characterized in that, in step (4), sintering temperature is preferably 500-600 ℃, and roasting time is preferably 3-10 hour.
9. according to the preparation method of hierarchical porous structure nanometer MFI type molecular sieve claimed in claim 3, it is characterized in that the Si/Al atomic ratio=10-1000 of nano-ZSM-5 type molecular sieve; Si/Ti atomic ratio=the 10-1000 of nano-scale TS-1 type molecular sieve.
10. according to the application of hierarchical porous structure nanometer MFI type molecular sieve claimed in claim 1, it is characterized in that, in MTP preparing propylene from methanol process, multi-stage artery structure nanometer MFI type molecular sieve is filled in to fixed bed reactors, the industrial methanol that material liquid is 40-95wt%, mass space velocity is 0.3-10h
-1, reaction temperature is 400-550 ℃.
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| CN104909980A (en) * | 2015-02-18 | 2015-09-16 | 浙江工业大学 | Application of hierarchical pore Ti-ZSM-5 molecular sieve catalyst in synthesis of toluene and xylene |
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