CN109796027A - The method of SAPO-34 Molecular sieve aggregate and preparation method thereof and methanol-to-olefins - Google Patents
The method of SAPO-34 Molecular sieve aggregate and preparation method thereof and methanol-to-olefins Download PDFInfo
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Abstract
The present invention relates to SAPO-34 molecular sieve arts, disclose SAPO-34 Molecular sieve aggregate and preparation method thereof and methanol-to-olefins method.Preparation method includes: the solution progress hydrothermal crystallizing that silicon source, phosphorus source, silicon source, triethylamine, triethylamine hydrochloride and water are obtained by mixing by (1)；Wherein, in the solution, silicon source is with Al2O3Meter, phosphorus source are with P2O5Meter, silicon source are with SiO2Meter, source of aluminium, phosphorus source, silicon source, the molar ratio of triethylamine, triethylamine hydrochloride and water are as follows: Al2O3: P2O5: SiO2: triethylamine: triethylamine hydrochloride: H2O=1:(0.9~1.1): (0.1~0.5): (1.5~3): (0.1~0.5): (15~50)；(2) product that step (1) hydrothermal crystallizing obtains is separated by solid-liquid separation, obtained solid is washed, dry, is roasted, obtain the SAPO-34 Molecular sieve aggregate.Selectivity of light olefin can be improved in the reaction for carrying out methanol-to-olefins as catalyst, inhibits the generation of carbon distribution, extends the service life of catalyst.
Description
Technical field
The present invention relates to SAPO-34 molecular sieve arts, and in particular to the preparation method of SAPO-34 Molecular sieve aggregate, it should
SAPO-34 Molecular sieve aggregate made from method and the method for carrying out methanol-to-olefins using the SAPO-34 Molecular sieve aggregate.
Background technique
Silicoaluminophosphate (SAPO) Series Molecules sieve is U.S. combinating carbide company (UCC) in novel point of exploitation in 1984
Son sieve, SAPO-34 are wherein a member.Its crystal structure is Chabazite-type (CHA), and aperture size is 0.43nm, and it is special to have
Water absorbing properties and Bronsted acidity can be used as adsorbent, catalyst and catalyst carrier.Due to the unique small structure of SAPO-34
With the acidity of suitable moderate strength, show it in catalysis methanol/dimethyl ether reaction for preparing light olefins (MTO) very high
Activity and selectivity, selectivity of light olefin is higher than 80% in product, ethylene selectivity up to 50% or more, almost without C6 with
Upper product.MTO process has been successfully applied to by the catalyst of active component of SAPO-34.
But SAPO-34 belongs to the small pore molecular sieve of 8 member rings, and carbon distribution inactivation is very easy in methanol conversion process, so
Industrially generally use the fluidized-bed reactor of circular regeneration.The selectivity and service life for improving catalyst are SAPO-34 points
The research and development emphasis of son sieve.
It is template that the synthesis of SAPO-34 molecular sieve, which generallys use the organic amines such as morpholine, triethylamine, and made crystal is allusion quotation
The micron order cube crystalline substance looks of type are very easy to produce in molecular sieve pore passage since reactants and products molecule diffusion path is long
It gives birth to carbon distribution and inactivates.
《Ultrafast synthesis of nano-sized zeolite SAPO-34with excellent MTO
Catalytic performance " (Qiming Sun, Ning Wang, Guanqi Guo and Jihong Yu, Chemical
Communications 2015,51,16397) it reports using tetraethyl ammonium hydroxide as template preparation SAPO-34, Ke Yihe
At nano-grade SAPO-34 molecular sieve, diffusion path is effectively reduced, improves catalyst life.But tetraethyl ammonium hydroxide valence
Lattice are expensive, and nanocrystal is not easy to separate from synthetic system, cause the SAPO-34 of synthesis at high cost, are unfavorable for industrial application.
《Direct synthesis of hierarchical zeolite from a natural layered
Material " (Zhu J, Cui Y, Wang Y, Wei F, Chemical Communications 2009,3282-3284) report
Road has the SAPO-34 molecular sieve hierarchical organization of flaky nanometer structure using kaolin as Material synthesis.But silicon contains in kaolin
Amount is high, causes made acidic zeolite very high, and carbon distribution inactivation is easy in the reaction of methanol conversion, is not suitable for industrial application.
The method that the prior art does not prepare the required SAPO-34 molecular sieve of industry suitably.
Summary of the invention
The purpose of the invention is to overcome existing for conventional SAPO-34 molecular sieve for methanol-to-olefins product selectivity
It is low, easy to generate carbon-collecting problem, the method for SAPO-34 Molecular sieve aggregate and preparation method thereof He methanol-to-olefins is provided, it should
SAPO-34 Molecular sieve aggregate is the tightly packed micron cube being laminated of multiple nano-sheet SAPO-34 zeolite crystals
Body can both retain the advantage of nanocrystal proliferation in reducing, and can also utilize the micron scale construction to flock together
The larger advantage of scale, is easily isolated zeolite product, and the production cost of molecular sieve is effectively reduced.
To achieve the goals above, first aspect present invention provides a kind of preparation method of SAPO-34 Molecular sieve aggregate,
Include:
(1) it is brilliant to carry out hydro-thermal for the solution for being obtained by mixing silicon source, phosphorus source, silicon source, triethylamine, triethylamine hydrochloride and water
Change；Wherein,
In the solution, silicon source is with Al2O3Meter, phosphorus source are with P2O5Meter, silicon source are with SiO2Meter, source of aluminium, phosphorus source, silicon source,
The molar ratio of triethylamine, triethylamine hydrochloride and water are as follows:
Al2O3: P2O5: SiO2: triethylamine: triethylamine hydrochloride: H2O=1:(0.9~1.1): (0.1~0.5): (1.5~
3): (0.1~0.5): (15~50)；
(2) product that step (1) hydrothermal crystallizing obtains is separated by solid-liquid separation, obtained solid is washed, is dried,
Roasting, obtains the SAPO-34 Molecular sieve aggregate.
Second aspect of the present invention provides the SAPO-34 Molecular sieve aggregate prepared by method of the invention, wherein described
SAPO-34 Molecular sieve aggregate is that shaggy micron made of the aggregation of multiple nano-sheet SAPO-34 zeolite crystals is vertical
Cube.
Preferably, the crystallite size of nano-sheet SAPO-34 zeolite crystal is 20~100nm.
Preferably, a length of 3~20 μm of the rib of the micron cube.
Preferably, the specific surface area of the SAPO-34 Molecular sieve aggregate is 600~800m2/g。
Third aspect present invention provides a kind of method of methanol-to-olefins, comprising:, will under the conditions of methanol to olefins reaction
Methanol is contacted with SAPO-34 Molecular sieve aggregate of the invention.
Through the above technical solutions, in the method provided by the invention for preparing SAPO-34 Molecular sieve aggregate using silicon source,
Phosphorus source and silicon source are raw material, and triethylamine and triethylamine hydrochloride are template, and water is solvent, and it is available to carry out hydrothermal crystallizing
SAPO-34 Molecular sieve aggregate is to be assembled by multiple nano-sheet SAPO-34 zeolite crystals by tightly packed stacking
Micron cube, can both retain the advantage of nanocrystal proliferation in reducing, can also be using flocking together
The larger advantage of micron scale construction scale, is easily isolated zeolite product, and the production cost of molecular sieve is effectively reduced.Use this
Selectivity of light olefin can be improved as the reaction that catalyst carries out methanol-to-olefins in SAPO-34 Molecular sieve aggregate, inhibits
The generation of carbon distribution extends the service life of catalyst.
Detailed description of the invention
Fig. 1 is the XRD spectra of SAPO-34 molecular sieve made from embodiment 1 and comparative example 1；
Fig. 2 a is the stereoscan photograph of the nanocrystal of SAPO-34 Molecular sieve aggregate made from embodiment 1；
Fig. 2 b is the stereoscan photograph of SAPO-34 Molecular sieve aggregate made from embodiment 1；
Fig. 3 is the stereoscan photograph of SAPO-34 molecular sieve made from comparative example 1；
Fig. 4 a is that SAPO-34 Molecular sieve aggregate made from embodiment 1 is used to carry out methanol as catalyst in embodiment 7
In olefins reaction process processed, curve that methanol conversion and olefine selective change with the reaction time；
Fig. 4 b is that SAPO-34 molecular sieve made from comparative example 1 is used to carry out methanol-to-olefins as catalyst in embodiment 7
In reaction process, curve that methanol conversion and olefine selective change with the reaction time.
Specific embodiment
The endpoint of disclosed range and any value are not limited to the accurate range or value herein, these ranges or
Value should be understood as comprising the value close to these ranges or value.For numberical range, between the endpoint value of each range, respectively
It can be combined with each other between the endpoint value of a range and individual point value, and individually between point value and obtain one or more
New numberical range, these numberical ranges should be considered as specific open herein.
First aspect present invention provides a kind of preparation method of SAPO-34 Molecular sieve aggregate, comprising:
(1) it is brilliant to carry out hydro-thermal for the solution for being obtained by mixing silicon source, phosphorus source, silicon source, triethylamine, triethylamine hydrochloride and water
Change；Wherein,
In the solution, silicon source is with Al2O3Meter, phosphorus source are with P2O5Meter, silicon source are with SiO2Meter, source of aluminium, phosphorus source, silicon source,
The molar ratio of triethylamine, triethylamine hydrochloride and water are as follows:
Al2O3: P2O5: SiO2: triethylamine: triethylamine hydrochloride: H2O=1:(0.9~1.1): (0.1~0.5): (1.5~
3): (0.1~0.5): (15~50)；
(2) product that step (1) hydrothermal crystallizing obtains is separated by solid-liquid separation, obtained solid is washed, is dried,
Roasting, obtains the SAPO-34 Molecular sieve aggregate.
In the present invention, triethylamine (TEA) and triethylamine hydrochloride (TEA.HCl) is selected to be combined as template, it can be with
The SAPO-34 zeolite crystal in microstructure with nano-sheet is prepared, then multiple crystal grain are tightly packed is laminated
The SAPO-34 Molecular sieve aggregate of micron cube structure.The SAPO-34 Molecular sieve aggregate that this method obtains, which can retain, to be received
The advantages of rice crystal grain reduces interior diffusion, the advantage that aggregation micron order cube structure scale can also be utilized larger, carries out first
Selectivity of light olefin is improved when the reaction of alcohol alkene and reduces carbon distribution, extends SAPO-34 Molecular sieve aggregate as catalysis
The service life of agent.
In the present invention, source of aluminium, phosphorus source and silicon source are the raw material for preparing SAPO-34 molecular sieve, and conventional conjunction can be used
Raw material is used at SAPO-34 molecular sieve, it is preferable that source of aluminium is in boehmite, sodium aluminate, aluminum nitrate and aluminum sulfate
At least one；Phosphorus source is selected from phosphoric acid and/or ammonium dihydrogen phosphate；The silicon source is selected from silica solution, sodium metasilicate, positive silicic acid second
At least one of ester and white carbon black.
It is further preferred that source of aluminium is boehmite, phosphorus source is phosphoric acid, and the silicon source is silica solution.
In the present invention, step (1) is used to configure the solution for carrying out hydrothermal crystallizing, it is preferable that described to be mixed into room temperature (generally
Be 10~40 DEG C) under closed stirring, mixing rate be 100~500rpm, incorporation time be 1~4h, preferably 3-4h.
In the present invention, the hydrothermal crystallizing is used for raw material silicon source, phosphorus source and silicon source in template triethylamine and triethylamine
SAPO-34 molecular sieve is synthesized in the presence of hydrochloride, it is preferable that the hydrothermal crystallizing is 190~200 DEG C, pressure in temperature
To carry out 12~48h under 2~3MPa.The hydrothermal crystallizing closed progress in a high pressure reaction kettle.
In the present invention, the separation of solid and liquid that step (2) carries out can use conventional separation method therein solid to isolate
Body.According to the method for the present invention, separation of solid and liquid can be realized using filtering.
In the present invention, the solid being separated by solid-liquid separation can be washed first using water, then be carried out under normal conditions
Dry and roasting, obtains the SAPO-34 Molecular sieve aggregate.Specifically, the drying 80~120 DEG C at a temperature of carry out
1~2h, it is described roasting 500~600 DEG C at a temperature of carry out 3~5h.The purpose of the roasting essentially consists in removing molecular sieve
Remain in the substance in molecular sieve pore passage, such as template in synthesis process.The roasting carries out generally in air atmosphere.
Second aspect of the present invention provides the SAPO-34 Molecular sieve aggregate prepared by method of the invention, wherein described
SAPO-34 Molecular sieve aggregate is that shaggy micron made of the aggregation of multiple nano-sheet SAPO-34 zeolite crystals is vertical
Cube.
In the present invention, SAPO-34 Molecular sieve aggregate can be obtained with hydrothermal crystallizing by the above method, wherein synthesize
SAPO-34 molecular sieve crystal is grown to the crystal grain (as shown in Figure 2 a) of nano-sheet, and crystal grain passes through tightly packed formation micron again
The SAPO-34 Molecular sieve aggregate (as shown in Figure 2 b) of cubic.
In the present invention, it is preferable that the crystallite size of nano-sheet SAPO-34 zeolite crystal is 20~100nm.
In the present invention, it is preferable that a length of 3~20 μm of the rib of the micron cube.
In the present invention, the SAPO-34 Molecular sieve aggregate provided can also retain nanocrystal, and aggregate surface is coarse,
Bigger specific surface area is provided.Preferably, the specific surface area of the SAPO-34 Molecular sieve aggregate is 600~800m2/g。
Third aspect present invention provides a kind of method of methanol-to-olefins, comprising:, will under the conditions of methanol to olefins reaction
Methanol is contacted with SAPO-34 Molecular sieve aggregate of the invention.
Specifically, carry out methanol-to-olefins condition may include: temperature be 400~500 DEG C, pressure be 0.1~
0.2MPa, raw material are containing 95 weight % methanol aqueous solutions, and the weight (hourly) space velocity (WHSV) of raw material is 3~5h-1。
The present invention will be described in detail by way of examples below.
In following embodiment, the microscopic appearance of SAPO-34 Molecular sieve aggregate passes through FEI Co. Nova Nano SEM
The scanning electron microscope of 450 models measures；By being carried out on the x-ray diffractometer purchased from the model D/max-2600/pc of Rigaku
X-ray diffraction analyzes (XRD)；The specific surface area of SAPO-34 Molecular sieve aggregate is used by nitrogen absorption under low temperature method
The model tristarII 3020-M nitrogen physisorption instrument of Micromeritics measures.
The crystallite size of SAPO-34 zeolite crystal and SAPO-34 Molecular sieve aggregate in SAPO-34 Molecular sieve aggregate
Cube rib length pass through sweep electron microscopic measure；
Methanol to olefins reaction obtains product composition by measuring on self-made miniature reactor, methanol conversion, ethylene and
Propylene Selectivity is calculate by the following formula:
Methanol conversion %=[(entrance moles of methanol-outlet moles of methanol)/entrance moles of methanol] × 100%
Ethylene and Propylene Selectivity %=[(ethylene carbon atom number+propylene carbon atom number)/all product carbon atom numbers] ×
100%.
Boehmite, phosphoric acid, silica solution, triethylamine, triethylamine hydrochloride are commercial goods in following embodiment, are intended
Boehmite is purchased from Shandong Aluminium Industry Co., Ltd, Al2O370 weight % of contents on dry basis；Silica solution pH is 9-10, SiO2Butt
Content is 30 weight %.
Embodiment 1
Boehmite, phosphoric acid, silica solution, triethylamine, triethylamine hydrochloride and deionized water are added in reaction kettle, room
Warm (25 DEG C) stir 4h in the case where stirring rate is 500rpm, and the molar ratio of above-mentioned each component is Al in acquired solution2O3: P2O5:
SiO2: triethylamine: triethylamine hydrochloride: H2O=1:1.0:0.25:1.5:0.5:20.
Temperature of reaction kettle is subjected to hydrothermal crystallizing, carries out crystallization for 24 hours in the case where temperature is 200 DEG C, pressure is 2MPa.
Product after crystallization is separated by filtration, obtained solid is washed with deionized.120 DEG C of dry 2h, 550 DEG C
3h is roasted, SAPO-34 Molecular sieve aggregate is obtained.
SAPO-34 Molecular sieve aggregate is subjected to XRD spectra analysis, the XRD spectra that Fig. 1 is is shown as SAPO-34
Crystal.
SAPO-34 Molecular sieve aggregate is scanned Electronic Speculum observation, Fig. 2 a is the electromicroscopic photograph of nanocrystal, SAPO-
34 zeolite crystals are nano-sheet, and crystallite size is 50~80nm.Fig. 2 b is that the Electronic Speculum of SAPO-34 Molecular sieve aggregate is shone
Piece, nano-sheet SAPO-34 zeolite crystal in plurality of Fig. 2 a is tightly packed to be laminated for micron cube structure
SAPO-34 Molecular sieve aggregate, aggregate surface is coarse, and a length of 10~15 μm of cube rib.
It is 655m by SAPO-34 Molecular sieve aggregate measurement the specific area2/g。
Embodiment 2
Boehmite, phosphoric acid, silica solution, triethylamine, triethylamine hydrochloride and deionized water are added in reaction kettle, room
Warm (40 DEG C) stir 3h in the case where stirring rate is 100rpm, and the molar ratio of above-mentioned each component is Al in acquired solution2O3: P2O5:
SiO2: triethylamine: triethylamine hydrochloride: H2O=1:0.9:0.12:2.0:0.4:50.
Temperature of reaction kettle is subjected to hydrothermal crystallizing, crystallization 12h is carried out in the case where temperature is 190 DEG C, pressure is 3MPa.
Product after crystallization is separated by filtration, obtained solid is washed with deionized.100 DEG C of dry 1.5h, 500
DEG C roasting 5h, obtain SAPO-34 Molecular sieve aggregate.
SAPO-34 Molecular sieve aggregate is subjected to XRD spectra analysis, is shown as SAPO-34 crystal.
SAPO-34 Molecular sieve aggregate is scanned Electronic Speculum observation, the crystallite size of nanocrystal is 20~50nm.It is more
The tightly packed SAPO-34 Molecular sieve aggregate for being laminated for micron cube structure of a nano-sheet SAPO-34 zeolite crystal,
A length of 15~20 μm of cube rib.
It is 682m by SAPO-34 Molecular sieve aggregate measurement the specific area2/g。
Embodiment 3
Boehmite, phosphoric acid, silica solution, triethylamine, triethylamine hydrochloride and deionized water are added in reaction kettle, room
Warm (10 DEG C) stir 3.5h in the case where stirring rate is 200rpm, and the molar ratio of above-mentioned each component is Al in acquired solution2O3: P2O5:
SiO2: triethylamine: triethylamine hydrochloride: H2O=1:1.1:0.5:3.0:0.25:30.
Temperature of reaction kettle is subjected to hydrothermal crystallizing, crystallization 48h is carried out in the case where temperature is 195 DEG C, pressure is 2.5MPa.
Product after crystallization is separated by filtration, obtained solid is washed with deionized.80 DEG C of dry 3h, 600 DEG C
4h is roasted, SAPO-34 Molecular sieve aggregate is obtained.
SAPO-34 Molecular sieve aggregate is subjected to XRD spectra analysis, is shown as SAPO-34 crystal.
SAPO-34 Molecular sieve aggregate is scanned Electronic Speculum observation, the crystallite size of nanocrystal is 80~100nm.
The tightly packed SAPO-34 molecular sieve aggregation for being laminated for micron cube structure of multiple nano-sheet SAPO-34 zeolite crystals
Body, a length of 3~10 μm of cube rib.
It is 628m by SAPO-34 Molecular sieve aggregate measurement the specific area2/g。
Embodiment 4
Boehmite, phosphoric acid, silica solution, triethylamine, triethylamine hydrochloride and deionized water are added in reaction kettle, room
Warm (25 DEG C) stir 4h in the case where stirring rate is 500rpm, and the molar ratio of above-mentioned each component is Al in acquired solution2O3: P2O5:
SiO2: triethylamine: triethylamine hydrochloride: H2O=1:1.0:0.2:1.5:0.5:40.
Temperature of reaction kettle is subjected to hydrothermal crystallizing, carries out crystallization for 24 hours in the case where temperature is 200 DEG C, pressure is 3MPa.
Product after crystallization is separated by filtration, obtained solid is washed with deionized.120 DEG C of dry 3h, 550 DEG C
3h is roasted, SAPO-34 Molecular sieve aggregate is obtained.
SAPO-34 Molecular sieve aggregate is subjected to XRD spectra analysis, is shown as SAPO-34 crystal.
SAPO-34 Molecular sieve aggregate is scanned Electronic Speculum observation, the crystallite size of nanocrystal is 30~60nm.It is more
The tightly packed SAPO-34 Molecular sieve aggregate for being laminated for micron cube structure of a nano-sheet SAPO-34 zeolite crystal,
A length of 5~10 μm of cube rib.
It is 657m by SAPO-34 Molecular sieve aggregate measurement the specific area2/g。
Embodiment 5
Boehmite, phosphoric acid, silica solution, triethylamine, triethylamine hydrochloride and deionized water are added in reaction kettle, room
Warm (25 DEG C) stir 4h in the case where stirring rate is 500rpm, and the molar ratio of above-mentioned each component is Al in acquired solution2O3: P2O5:
SiO2: triethylamine: triethylamine hydrochloride: H2O=1:1.0:0.3:1.8:0.1:30.
Temperature of reaction kettle is subjected to hydrothermal crystallizing, crystallization 48h is carried out in the case where temperature is 190 DEG C, pressure is 3MPa.
Product after crystallization is separated by filtration, obtained solid is washed with deionized.120 DEG C of dry 3h, 550 DEG C
3h is roasted, SAPO-34 Molecular sieve aggregate is obtained.
SAPO-34 Molecular sieve aggregate is subjected to XRD spectra analysis, is shown as SAPO-34 crystal.
SAPO-34 Molecular sieve aggregate is scanned Electronic Speculum observation, the crystallite size of nanocrystal is 50~80nm.It is more
The tightly packed SAPO-34 Molecular sieve aggregate for being laminated for micron cube structure of a nano-sheet SAPO-34 zeolite crystal,
A length of 3~5 μm of cube rib.
It is 675m by SAPO-34 Molecular sieve aggregate measurement the specific area2/g。
Embodiment 6
Boehmite, phosphoric acid, silica solution, triethylamine, triethylamine hydrochloride and deionized water are added in reaction kettle, room
Warm (25 DEG C) stir 4h in the case where stirring rate is 500rpm, and the molar ratio of above-mentioned each component is Al in acquired solution2O3: P2O5:
SiO2: triethylamine: triethylamine hydrochloride: H2O=1:0.95:0.1:2.0:0.3:20.
Temperature of reaction kettle is subjected to hydrothermal crystallizing, crystallization 12h is carried out in the case where temperature is 200 DEG C, pressure is 3MPa.
Product after crystallization is separated by filtration, obtained solid is washed with deionized.120 DEG C of dry 3h, 550 DEG C
3h is roasted, SAPO-34 Molecular sieve aggregate is obtained.
SAPO-34 Molecular sieve aggregate is subjected to XRD spectra analysis, is shown as SAPO-34 crystal.
SAPO-34 Molecular sieve aggregate is scanned Electronic Speculum observation, the crystallite size of nanocrystal is 60~80nm.It is more
The tightly packed SAPO-34 Molecular sieve aggregate for being laminated for micron cube structure of a nano-sheet SAPO-34 zeolite crystal,
A length of 15~20 μm of cube rib.
It is 668m by SAPO-34 Molecular sieve aggregate measurement the specific area2/g。
Comparative example 1
Boehmite, phosphoric acid, silica solution, triethylamine and deionized water are added in reaction kettle, room temperature (25 DEG C) is being stirred
Mixing rate is to stir 4h under 500rpm, and the molar ratio of above-mentioned each component is Al in acquired solution2O3: P2O5: SiO2: triethylamine: H2O
=1:1.0:0.25:3.0:50.
Temperature of reaction kettle is subjected to hydrothermal crystallizing, carries out crystallization for 24 hours in the case where temperature is 200 DEG C, pressure is 3MPa.
Product after crystallization is separated by filtration, obtained solid is washed with deionized.120 DEG C of dry 3h, 550 DEG C
3h is roasted, SAPO-34 molecular sieve is obtained.
SAPO-34 molecular sieve is subjected to XRD spectra analysis, as shown in Figure 1, being shown as SAPO-34 crystal.
SAPO-34 molecular sieve is scanned Electronic Speculum observation, as shown in figure 3, not having in the microscopic appearance of SAPO-34 molecular sieve
Have nano-sheet crystal grain, be smooth in appearance cube structure, a length of 5~10 μm of cube rib.
It is 565m by SAPO-34 molecular sieve measurement the specific area2/g。
Embodiment 7
The SAPO-34 molecular sieve that embodiment 1 and comparative example 1 are respectively prepared carries out methanol to olefins reaction.
The reaction condition of methanol-to-olefins is 450 DEG C, 0.1MPa, is raw material containing 95 weight % methanol aqueous solutions, raw material
Weight (hourly) space velocity (WHSV) (CH3OH+H2O)=3.5h-1。
Methanol conversion and olefine selective in methanol-to-olefins reaction process will be carried out to be made with the variation in reaction time
Curve, as shown in Fig. 4 a (the SAPO-34 molecular sieve of embodiment 1) and Fig. 4 b (the SAPO-34 molecular sieve of comparative example 1).
It can be seen that method provided by the invention using triethylamine and triethylamine hydrochloride from above-described embodiment and comparative example
The template combined can obtain SAPO-34 Molecular sieve aggregate from silicon source, phosphorus source and silicon source hydrothermal crystallizing, the molecular sieve
It can have nano-sheet SAPO-34 zeolite crystal, crystallite size is 20~100nm；Nano-sheet SAPO-34 molecular sieve is brilliant
Grain is tightly packed to be laminated for a micron cube, and a length of 3~20 μm of the rib of cube.The molecular sieve can have bigger specific surface
Product.All nano-sheet SAPO-34 crystal grain can effectively shorten product molecule in crystal duct in the Molecular sieve aggregate
Diffusion, effectively inhibit carbon distribution generation, extend the service life of catalyst.
Catalyst of the molecular sieve as methanol to olefins reaction, as shown in fig. 4 a, the made SAPO-34 molecule of embodiment 1
After sieve aggregation precursor reactant 185min, detects that dimethyl ether (DME) occurs in product, show that catalyst starts to inactivate.Ethylene and third
The selectivity of alkene is 78%.After the made SAPO-34 molecular sieve of comparative example 1 reacts 90min, dimethyl ether (DME) is detected in product
Occur, shows that catalyst starts to inactivate.The selectivity of ethylene and propylene is 73%.As it can be seen that SAPO-34 molecule provided by the invention
Sieve aggregation selectivity of light olefin is apparently higher than micron order cube SAPO-34 molecular sieve made from comparative example 1, and (template does not have
There is triethylamine hydrochloride).Moreover, SAPO-34 Molecular sieve aggregate provided by the invention carries out the use of methanol to olefins reaction
Time extends one times than comparative example 1.
The preferred embodiment of the present invention has been described above in detail, and still, the present invention is not limited thereto.In skill of the invention
In art conception range, can with various simple variants of the technical solution of the present invention are made, including each technical characteristic with it is any its
Its suitable method is combined, and it should also be regarded as the disclosure of the present invention for these simple variants and combination, is belonged to
Protection scope of the present invention.
Claims (10)
1. a kind of preparation method of SAPO-34 Molecular sieve aggregate, comprising:
(1) solution for being obtained by mixing silicon source, phosphorus source, silicon source, triethylamine, triethylamine hydrochloride and water carries out hydrothermal crystallizing；Its
In,
In the solution, silicon source is with Al2O3Meter, phosphorus source are with P2O5Meter, silicon source are with SiO2Meter, source of aluminium, phosphorus source, silicon source, three second
The molar ratio of amine, triethylamine hydrochloride and water are as follows:
Al2O3: P2O5: SiO2: triethylamine: triethylamine hydrochloride: H2O=1:(0.9~1.1): (0.1~0.5): (1.5~3):
(0.1~0.5): (15~50)；
(2) product that step (1) hydrothermal crystallizing obtains is separated by solid-liquid separation, obtained solid is washed, dry, is roasted
It burns, obtains the SAPO-34 Molecular sieve aggregate.
2. preparation method according to claim 1, wherein source of aluminium be selected from boehmite, sodium aluminate, aluminum nitrate and
At least one of aluminum sulfate；
Phosphorus source is selected from phosphoric acid and/or ammonium dihydrogen phosphate；
The silicon source is selected from least one of silica solution, sodium metasilicate, ethyl orthosilicate and white carbon black.
3. preparation method according to claim 1, wherein it is described to be mixed into closed stirring at room temperature, rate is mixed
For 100~500rpm, incorporation time is 1~4h.
4. according to the method described in claim 1, wherein, the hydrothermal crystallizing temperature be 190~200 DEG C, pressure be 2~
12~48h is carried out under 3MPa.
5. according to the method described in claim 1, wherein, the drying 80~120 DEG C at a temperature of carry out 1~2h, it is described
Roast 500~600 DEG C at a temperature of carry out 3~5h.
6. the SAPO-34 Molecular sieve aggregate of the preparation of the method as described in any one of claim 1-5, which is characterized in that
The SAPO-34 Molecular sieve aggregate is shaggy micro- made of the aggregation of multiple nano-sheet SAPO-34 zeolite crystals
Rice cube.
7. SAPO-34 Molecular sieve aggregate according to claim 6, wherein nano-sheet SAPO-34 zeolite crystal
Crystallite size is 20~100nm.
8. SAPO-34 Molecular sieve aggregate according to claim 6, wherein the rib a length of 3~20 of the micron cube
μm。
9. SAPO-34 Molecular sieve aggregate according to claim 6, wherein the ratio of the SAPO-34 Molecular sieve aggregate
Surface area is 600~800m2/g。
10. a kind of method of methanol-to-olefins, comprising:, will be in methanol and claim 6-9 under the conditions of methanol to olefins reaction
The contact of SAPO-34 Molecular sieve aggregate described in any one.
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