CN102633279A - Aluminum silicophosphate molecular sieve with macro-porous structure and preparation method thereof - Google Patents
Aluminum silicophosphate molecular sieve with macro-porous structure and preparation method thereof Download PDFInfo
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Abstract
The invention provides an aluminum silicophosphate molecular sieve particle. The particle simultaneously has a small-porous molecular sieve crystal structure and a straight-through type macro-porous double-channel structure; and the volume of a macro-porous pore is 5-60% of the volume of a cubic particle. The invention further provides a method for preparing the molecular sieve particle. According to the invention, an SAPO (Silicoaluminophosphate) molecular sieve particle which is provided with abundant straight-through type macro-pores is successfully synthesized, and crystal characteristics and pore structure characteristics are clear. The macro-porous structure of the molecular sieve particle can effectively weaken inner dispersion and is suitable for limiting a serious reaction process by the inner dispersion, such as a process for preparing olefin by alcohol ether.
Description
Technical field
The invention belongs to catalyst field, be specifically related to a kind of have aluminium silicophosphate (SAPO) molecular sieve of macroporous structure and the method for preparation thereof.
Background technology
According to the definition of International Union of Pure and Applied Chemistry (IUPAC), according to the big I of hole dimension the hole is divided three classes: the hole less than 2nm is a micropore, and the hole of 2～50nm is mesoporous, and greater than 50nm is macropore.The zeolite of nature and synthetic has special aperture structure, the molecular size size of manhole appendix is had fabulous selectivity, so zeolite is also referred to as molecular sieve.Zeolite molecular sieve has multiple, all belongs to poromerics, can further be divided into according to its duct size: (duct is by forming more than the twelve-ring, and the aperture is greater than 0.7nm for large pore molecular sieve; Like Y molecular sieve, mercerising molecular sieve, SAPO-5 etc.), mesoporous molecular sieve (ten-ring, the about 0.5～0.6nm in aperture; Like ZSM-5), and small pore molecular sieve (octatomic ring, the about 0.4nm in aperture; Like ZSM-34, SAPO-34, SAPO-18 etc.).SAPO-34 in the small pore molecular sieve and SAPO-18 all belong to aluminium silicophosphate molecular sieve, contain [SiO
2], [AlO
2] and [PO
2] the three-dimensional aperture crystal framework structure of angle tetrahedron element altogether, wherein the SAPO-34 molecular sieve has the structure of similar chabazite (CHA), and its octatomic ring channel diameter is merely 0.38nm.SAPO-18 has similar duct size with SAPO-34, but its crystalline structure is the AEI type.The little duct of SAPO-34, SAPO-18 molecular sieve makes iso-butylene and the C that the molecular dynamics diameter is bigger
5Above hydro carbons receives the serious shape restriction of selecting, thereby in alcohol ether system alkene (MTO/MTP) process, ethene, propylene is had good product selectivity.
At patent documentation USP4440871; CN1037337C; CN1038125C reports among CN1048428C and the CN1088483A, and the SAPO-34 molecular sieve generally adopts Hydrothermal Preparation; Method commonly used is that aluminium source, phosphorus source, silicon source and template are mixed in certain proportion, obtains molecular screen primary powder at 100～250 ℃ of following hydrothermal crystallizings.Owing to use the difference of template, the SAPO-34 molecular sieve size for preparing is different.In Chinese patent CN1048429C, adopt triethylamine and tetraethyl-oxyammonia blended double template to synthesize SAPO-34, through adjusting the ratio of two template, can be in certain scope the size of modulation synthetic molecular sieve.Generally all at 1 micron to tens microns, its macro morphology is near cubes for the particle diameter of above traditional method synthetic SAPO-34 molecular sieve, and molecular sieve length and width height is close.SAPO-18 also has the similar hydrothermal synthesis method with SAPO-34.
Conventional SAPO-34 sieve particle size is at micron order, and the molecular sieve pore passage size is merely 0.38nm, causes the sieve particle inner duct longer relatively, and inside diffusional resistance is big.For oxygenatedchemicals system olefine reaction; Inside diffusional resistance has not only had a strong impact on catalyst efficiency, and reactant generates title product alkene in the cage of molecular sieve after, alkene is in the process of external diffusion; Can on the acidic site in molecular sieve hydrogen transfer reactions generation by product alkane take place further; Also can aggregate into Jiao, both reduce the purpose selectivity of product, cause catalyzer coking inactivation simultaneously again.Therefore, the SAPO molecular sieve of larger particles can cause the selectivity of purpose product alkene to descend, and by product alkane selectivity raises, and the easy inactivation of catalyzer.
From eliminating or weakening the angle of internal diffusion to catalyst activity and selectivity of product influence, preparing more, the nano molecular sieve of small particle size is an important channel of improving catalyst performance.Existing both at home and abroad about nano level SAPO molecular sieve synthetic research report, but there are problems such as percent crystallinity is low, productive rate is low, liquid-solid separation difficulty to some extent, successfully do not eliminate the restriction of small pore molecular sieve particulate internal diffusion as yet.
Second thinking that solves the internal diffusion problem is the sieve particle that has polymorphic structure through design, effectively shortens the internal diffusion path, obtains and the equal effect of nano molecular sieve.The SAPO molecular sieve that has bibliographical information to synthesize to have laminated structure, its lamellar spacing is merely about 100nm.This catalyzer is used for the methanol-to-olefins process and demonstrates good anti-carbon deactivation, proves that polymorphic structure is effective to weakening the internal diffusion restriction.
Multistage porous molecular sieve is the 3rd thinking that solves micro porous molecular sieve internal diffusion restricted problem, promptly through in sieve particle, forming the one-level pore passage structure bigger than molecular sieve pore passage, reinforcing particle internal diffusion.Common mesoporous-micro porous molecular sieve is a type in the multistage porous molecular sieve.The compound method of mesoporous-micro porous molecular sieve is mainly two types, and a kind of is top-down method (Top-down), first synthetic microporous molecular sieve, and then it is mesoporous to produce molecular sieve to be carried out processing such as dealuminzation or desiliconization; Second kind is method (Bottom-up) from bottom to top; Be direct synthesis technique, in the stoste of synthetic microporous molecular sieve, add mesoporous template, commonly used have carbon template, an organic template etc.; Obtain removing these template through roasting again behind the product, can obtain mesoporous.First method changes to acidity of catalyst in producing mesoporous process, and mesoporous homogeneity is wayward; Second method must find the mesoporous template that does not influence the molecular sieve crystal growth, in industrial molecular sieve is synthetic, is not used widely as yet up to now.Patent documentation CN101633508 has reported a kind of SAPO-34 molecular sieve and compound method that contains ghost, hole, concavo-convex, crack, nucleocapsid pattern, and the hole in the document can be used N
2The hysteretic loop identification that adsorption isothermal line and desorption isotherm produce should belong to mesoporous scope; Ghost, convex-concave, crack and nucleocapsid then are the incomplete formed erratic composition of growth.Though the SAPO-34 particle of this erratic composition helps to weaken the internal diffusion restriction, in the batch preparations process, be difficult to control.
Summary of the invention
To the internal diffusion restricted problem of SAPO molecular sieve in the prior art, the purpose of this invention is to provide and a kind ofly have aluminium silicophosphate (SAPO) the small pore molecular sieve particle that enriches through-type macroporous structure, and the application of its preparation method and this sieve particle is provided.
For realizing above-mentioned purpose, technical scheme of the present invention is:
A kind of aluminium silicophosphate molecular sieve particle, particle have the dual pore passage structure of small pore molecular sieve crystalline structure and through-type macropore simultaneously, and the ratio that the pore volume of macropore accounts for the cube particle volume is 5%～60%.
Wherein, Said particle is six cubess; A pair of two relative faces are distributed with macropore in six faces of particulate; Other four faces are four right-angle triangles by the diagonal division on the face separately, in four right-angle triangles wherein two trilaterals of a pair of mutual vertical angles be distributed with macropore, do not have macropore on the gore of two other mutual vertical angles or do not have through-type macropore.
Wherein, the aperture of said macropore is 50～500nm, and the ratio that the macropore pore volume accounts for the cube particle volume is 10%～40%.
Wherein, said small pore molecular sieve crystalline structure is the crystalline structure of CHA type (SAPO-34) and AEI type structure (SAPO-18) intergrowth.
Wherein, the mass ratio of CHA and two kinds of crystalline structure of AEI is the CHA N-type waferN in the crystalline structure of said intergrowth: AEI crystal=1.0～10.0: 1.0.This mass ratio is to obtain through the XRD test.
The present invention also provides the method for the above-mentioned sieve particle of preparation, and it may further comprise the steps:
1) water, aluminium source, phosphorus source, silicon source and organic formwork agent are mixed, wherein, water, aluminium source, phosphorus source, silicon source and organic formwork agent are pressed H
2O: Al
2O
3: P
2O
5: SiO
2: organic formwork agent meter, its mol ratio are 30～200: 1: 0.1～2.5: 0.01～1.0: 0.1～10; With described moisture is two portions, and first part's water mixes with the aluminium source, forms water solution A, and second section water mixes with phosphorus source, silicon source, forms aqueous solution B; Water solution A is mixed the formation gel C with aqueous solution B; Gel C is mixed with organic formwork agent and is obtained the raw material gel, under 15～100 ℃ of conditions, carries out ageing, and digestion time is 0～72 hour;
2) with the mixture after the ageing 150～200 ℃ of following crystallization 4～100 hours, the gained solid matter is a product.
Wherein, said water, aluminium source, phosphorus source, silicon source and organic formwork agent are pressed H
2O: Al
2O
3: P
2O
5: SiO
2: organic formwork agent meter, its mol ratio are 50～180: 1: 0.2～2.0: 0.05～0.9: 0.5～8.
Preferably, said water, aluminium source, phosphorus source, silicon source and organic formwork agent are pressed H
2O: Al
2O
3: P
2O
5: SiO
2: organic formwork agent meter, its mol ratio are 70～160: 1: 0.4～1.5: 0.1～0.3: 1.0～5.
Wherein, the mol ratio of said first part's water and second section water is 0.1～10.
Preferably, the mol ratio of first part's water and second section water is 0.5～6.
Wherein, said aluminium source is one or more the mixture in hydrated aluminum oxide, aluminum isopropylate and the phosphagel phosphaljel; Said silicon source is one or more mixtures of silicon sol, active silica, tetraethoxy or solid silicone; Said phosphorus source is one or more mixtures of phosphoric acid, Hypophosporous Acid, 50, phosphoric acid salt and Organophosphorous compounds; Said organic formwork agent is one or more mixtures of diethylamine, triethylamine, morphine quinoline and tetraethyl-oxyammonia.
Wherein, said aluminium source is pseudo-boehmite (monohydrate alumina), and said phosphorus source is a phosphoric acid, and said silicon source is silicon sol or tetraethoxy, and said organic formwork agent is a triethylamine.
Ageing process is the preparatory crystallization operation of raw material gel before the crystallization.Wherein, said ageing is ageing under normal pressure, and the ageing process of raw material gel can be an immobilized or dynamic.
Preferably, aged temperature is a normal temperature, is about 15～30 ℃, and preferred ageing process is dynamic.So-called ageing process is dynamic, is meant through stirring or rotation or additive method the raw material gel is in dynamically.The ageing operation can increase the homogeneity of the preceding raw material gel of crystallization, produces a certain amount of molecular sieve nucleus, helps to suppress the generation of stray crystal phase in the crystallization process, reduces the size of product particle diameter, improves the homogeneity of product particle diameter.Dynamic ageing can suppress stray crystal better and produce mutually.
Wherein, said crystallization is to carry out under the airtight hydrothermal condition, and the pressure that the pressure during crystallization comes reaction mixture to produce, crystallization process can be dynamic or immobilized.
Preferably, the crystallization process of mixture is dynamic.So-called crystallization process is dynamic, is meant through stirring or rotation or additive method the raw material gel is in dynamically.Crystallization can effectively increase the homogeneity of feed liquid in the crystallization process under the dynamic condition, improves to conduct heat and mass-transfer efficiency, generates thereby suppress stray crystal phase product.
Through said step 1) and 2) afterwards, reclaim and obtain product.The recovery product is meant crystallization product multiple times of filtration, washing, drying is obtained product.
Comprise the catalyzer and the application of this catalyzer in preparation alkene of sieve particle according to the invention.
Beneficial effect of the present invention:
The present invention successfully synthesizes the SAPO sieve particle with abundant through-type macropore, and crystal characteristic and pore structure characteristic are clear.Regular macroporous structure in the sieve particle can effectively weaken internal diffusion, is particularly useful for the serious reaction process of internal diffusion restriction, like alcohol ether system olefin hydrocarbon.
Synthetic sieve particle of the present invention can be used as the catalyzer of fluidized-bed reactor behind mist projection granulating.This catalyzer is used for alcohol ether system olefin hydrocarbon, and catalyst activity is stable, and the once-through propylene selectivity is high, and the alkane selectivity is low.
Description of drawings
Fig. 1 prepares the process synoptic diagram of aluminium silicophosphate of the present invention (SAPO) molecular sieve;
Fig. 2 aluminium silicophosphate (SAPO) molecular sieve X-ray diffracting spectrum;
The mercury penetration method measuring result of the aluminium silicophosphate that Fig. 3 embodiment 1 obtains (SAPO) molecular sieve;
The nitrogen adsorption isothermal curve of the aluminium silicophosphate that Fig. 4 embodiment 1 obtains (SAPO) molecular sieve;
The pattern photo of the aluminium silicophosphate that Fig. 5 Comparative Examples 1 obtains (SAPO) molecular sieve;
The pattern photo of the aluminium silicophosphate that Fig. 6 embodiment 1 obtains (SAPO) molecular sieve.Wherein, Fig. 6 a is a low power (* 12; 000) the pattern photo that amplifies, Fig. 6 b are the pattern photos that high power (* 30,000) is amplified; Fig. 6 c is that the aluminium silicophosphate particle low power after the black line fragmentation among Fig. 6 b is amplified the pattern photo, and Fig. 6 d is aluminium silicophosphate (SAPO) the granule-morphology photo that the high power after the fragmentation is amplified.
Embodiment
Following examples are used to explain the present invention, but are not used for limiting scope of the present invention.
Embodiment 1
Raw material type is identical with Comparative Examples 1, and proportioning raw materials is pressed H according to water, aluminium source, phosphorus source, silicon source and organic formwork agent
2O: Al
2O
3: P
2O
5: SiO
2: organic formwork agent meter, H
2O: Al
2O
3: P
2O
5: SiO
2: TEA=50: 1: 1.5: 0.3: 3 (mol ratios).Earlier a part of water (a1) in the raw material and pseudo-boehmite are mixed fully, obtain uniform solution A, its molar ratio is H
2O: Al
2O
3=40: 1; Water (a2) with remainder in the raw material mixes with phosphoric acid, silicon sol fully simultaneously, obtains uniform solution B, and its molar ratio is H
2O: P
2O
5: SiO
2=10: 1.5: 0.3.The mol ratio a1/a2=4.0 of two portions water under stirring condition, mixes solution A and solution B then fully, obtains the gel C of homogeneous.Under stirring condition, in gel C, add organic formwork agent TEA at last, obtain being used for the raw material gel of hydrothermal crystallizing.
With reaction mixture under room temperature, agitation condition, ageing 20 hours, the polytetrafluoroethyllining lining of packing into then, and be packaged in stainless steel hydro-thermal still, 200 ℃ with autogenous pressure under, rotated crystallization 20 hours.Then with crystallization product multiple times of filtration, washing and 100 ℃ of oven dry, then in retort furnace, be warming up to 600 ℃ and constant temperature 4 hours, in moisture eliminator, naturally cool to room temperature then and promptly get molecular screen primary powder product.
Get the above-mentioned molecular screen primary powder of part and do XRD analysis; Its presentation of results synthetic molecular sieve is SAPO-34 (CHA)/SAPO-18 (AEI) intergrowth phase crystal; Two kinds of crystalline structure are CHA: AEI=1 in the ratio of intergrowth in mutually: 1, and shown in Fig. 2 intermediate curve (mixed crystal phase SAPO-34 molecular sieve).
Get the above-mentioned molecular screen primary powder of part and do nitrogen absorption test.Its nitrogen adsorption isothermal line is as shown in Figure 4, does not have tangible hysteresis loop between adsorption isothermal line and the desorption isotherm, explains that the SAPO-34 molecular sieve of novel batching mode preparation and the SAPO-34 molecular sieve that the traditional proportioning mode prepares all do not contain meso-hole structure.
The molecular sieve pattern is as shown in Figure 6, and sieve particle is cube more, and granule interior contains abundant through-type macropore, and the aperture of macropore is 50～500nm, and the hole wall material between the macropore has crystal structure of molecular sieve.Two facings to the top in six faces of cube sieve particle appear near the hole that is uniformly distributed with; Other four facings are divided into four right-angle triangles by face diagonal separately; Present hole and homogeneous pattern respectively, with two triangular morphology on top are identical relatively in the one side.
Getting molecular screen primary powder after the roasting does and presses mercury to measure; Its result is as shown in Figure 3; The pore passage structure of decidable 1000～1300nm should be particle and gap between particles duct; And tangible duct volume is arranged in the interval of 50～500nm, and should be the duct volume of granule interior, the ratio that the pore volume of macropore accounts for the cubic granules volume is 25%; The SAPO-34 molecular sieve that the preparation of novel batching mode is described contains tangible macroporous structure, and observed appearance structure is consistent on this result and the pattern photo.
Embodiment 2
Tetraethoxy is used in the silicon source instead in the raw material, and organic formwork agent adopts diethylamine, and Hypophosporous Acid, 50 is adopted in the phosphorus source, and phosphagel phosphaljel is adopted in the aluminium source, and the molar ratio of raw material is pressed H
2O: Al
2O
3: P
2O
5: SiO
2: the diethylamine meter is 160: 1: 2.5: 0.7: 5.0.Earlier a part of water (a1) in the raw material and phosphagel phosphaljel are mixed fully, obtain uniform solution A, its molar ratio is H
2O: Al
2O
3=20: 1; Water (a2) with remainder in the raw material mixes with Hypophosporous Acid, 50, tetraethoxy fully simultaneously, obtains uniform solution B, and its molar ratio is H
2O: P
2O
5: SiO
2=140: 2.5: 0.7, the mol ratio a1/a2=0.14 of two portions water.Under stirring condition, solution A and solution B are mixed fully then, obtain the gel C of homogeneous.Under stirring condition, in gel C, add the organic formwork agent diethylamine at last, obtain being used for the raw material gel of hydrothermal crystallizing.
With reaction mixture under 70 ℃, agitation condition, ageing 40 hours, the polytetrafluoroethyllining lining of packing into then, and be packaged in stainless steel hydro-thermal still, 170 ℃ with autogenous pressure rotation crystallization 4 hours down.Then with crystallization product multiple times of filtration, washing and 100 ℃ of oven dry, then in retort furnace, be warming up to 600 ℃ and constant temperature 4 hours, in moisture eliminator, naturally cool to room temperature then and promptly get molecular screen primary powder product.
Get the above-mentioned molecular screen primary powder of part and do XRD analysis, its presentation of results synthetic molecular sieve is SAPO-34 (CHA)/SAPO-18 (AEI) intergrowth phase crystal.Get the above-mentioned molecular screen primary powder of part and do nitrogen absorption test.Its result shows, does not have tangible hysteresis loop between adsorption isothermal line and the desorption isotherm, explains that the SAPO-34 molecular sieve of this compound method preparation does not contain meso-hole structure.Electromicroscopic photograph shows that the sieve particle that synthesizes is cube more, and granule interior is flourishing macroporous network.
Get molecular screen primary powder after the roasting and do and press mercury to measure, its result shows that the SAPO-34 molecular sieve of this compound method preparation contains tangible macroporous structure, and observed appearance structure is consistent on this result and the pattern photo.The ratio that the pore volume of macropore accounts for the cubic granules volume is 10%.
Embodiment 3:
Raw material type is identical with embodiment 1, and proportioning raw materials is pressed H according to water, aluminium source, phosphorus source, silicon source and organic formwork agent
2O: Al
2O
3: P
2O
5: SiO
2: the chemical formula meter of organic formwork agent, H
2O: Al
2O
3: P
2O
5: SiO
2: TEA=70: 1: 0.4: 0.1: 1 (mol ratio).Earlier a part of water (a1) in the raw material and pseudo-boehmite are mixed fully, obtain uniform solution A, its molar ratio is H
2O: Al
2O
3=24: 1; Water (a2) with remainder in the raw material mixes with phosphoric acid, silicon sol fully simultaneously, obtains uniform solution B, and its molar ratio is H
2O: P
2O
5: SiO
2=46: 0.4: 0.1, a1/a2=0.52.Under stirring condition, solution A and solution B are mixed fully then, obtain the gel C of homogeneous.Under stirring condition, in gel C, add organic formwork agent TEA at last, obtain being used for the raw material gel of hydrothermal crystallizing.
With reaction mixture under room temperature, agitation condition, ageing 20 hours, the polytetrafluoroethyllining lining of packing into then, and be packaged in stainless steel hydro-thermal still, 150 ℃ with autogenous pressure under, rotated crystallization 100 hours.Then with crystallization product multiple times of filtration, washing and 100 ℃ of oven dry, then in retort furnace, be warming up to 600 ℃ and constant temperature 4 hours, in moisture eliminator, naturally cool to room temperature then and promptly get molecular screen primary powder product.
Get the above-mentioned molecular screen primary powder of part and do nitrogen absorption test.There is not tangible hysteresis loop between its nitrogen adsorption isothermal line and the desorption isotherm, explains that the SAPO-34 molecular sieve of novel batching mode preparation and the SAPO-34 molecular sieve that the traditional proportioning mode prepares all do not contain meso-hole structure.
Getting molecular screen primary powder after the roasting does and presses mercury to measure; The pore passage structure of decidable 1000～1300nm should be particle and gap between particles duct; And tangible duct volume is arranged in the interval of 50～500nm; Should be the duct volume of granule interior, the ratio that the pore volume of macropore accounts for the cubic granules volume is 40%; The SAPO-34 molecular sieve that the preparation of novel batching mode is described contains tangible macroporous structure, and observed appearance structure is consistent on this result and the pattern photo.
Embodiment 4:
Raw material type is identical with embodiment 1, and proportioning raw materials is pressed H according to water, aluminium source, phosphorus source, silicon source and organic formwork agent
2O: Al
2O
3: P
2O
5: SiO
2: the chemical formula meter of organic formwork agent, H
2O: Al
2O
3: P
2O
5: SiO
2: TEA=200: 1: 2: 0.7: 8 (mol ratios).Earlier a part of water (a1) in the raw material and pseudo-boehmite are mixed fully, obtain uniform solution A, its molar ratio is H
2O: Al
2O
3=170: 1; Water (a2) with remainder in the raw material mixes with phosphoric acid, silicon sol fully simultaneously, obtains uniform solution B, and its molar ratio is H
2O: P
2O
5: SiO
2=30: 2: 0.7, the mol ratio a1/a2=5.7 of two portions water.Under stirring condition, solution A and solution B are mixed fully then, obtain the gel C of homogeneous.Under stirring condition, in gel C, add organic formwork agent TEA at last, obtain being used for the raw material gel of hydrothermal crystallizing.
With reaction mixture under room temperature, agitation condition, ageing 20 hours, the polytetrafluoroethyllining lining of packing into then, and be packaged in stainless steel hydro-thermal still, 200 ℃ with autogenous pressure under, rotated crystallization 20 hours.Then with crystallization product multiple times of filtration, washing and 100 ℃ of oven dry, then in retort furnace, be warming up to 600 ℃ and constant temperature 4 hours, in moisture eliminator, naturally cool to room temperature then and promptly get molecular screen primary powder product.
Get the above-mentioned molecular screen primary powder of part and do nitrogen absorption test.There is not tangible hysteresis loop between its nitrogen adsorption isothermal line and the desorption isotherm, explains that the SAPO-34 molecular sieve of novel batching mode preparation and the SAPO-34 molecular sieve that the traditional proportioning mode prepares all do not contain meso-hole structure.
Getting molecular screen primary powder after the roasting does and presses mercury to measure; The pore passage structure of decidable 1000～1300nm should be particle and gap between particles duct; And tangible duct volume is arranged in the interval of 50～500nm, and should be the duct volume of granule interior, it is 10% that the pore volume of macropore accounts for the cubes ratio.
Raw material type is identical with embodiment 1, and proportioning raw materials is pressed H according to water, aluminium source, phosphorus source, silicon source and organic formwork agent
2O: Al
2O
3: P
2O
5: SiO
2: the chemical formula meter of organic formwork agent, H
2O: Al
2O
3: P
2O
5: SiO
2: TEA=180: 1: 0.1: 0.9: 5 (mol ratios).Earlier a part of water (a1) in the raw material and pseudo-boehmite are mixed fully, obtain uniform solution A, its molar ratio is H
2O: Al
2O
3=30: 1; Water (a2) with remainder in the raw material mixes with phosphoric acid, silicon sol fully simultaneously, obtains uniform solution B, and its molar ratio is H
2O: P
2O
5: SiO
2=150: 0.1: 0.9, the mol ratio a1/a2=0.2 of two portions water.Under stirring condition, solution A and solution B are mixed fully then, obtain the gel C of homogeneous.Under stirring condition, in gel C, add organic formwork agent TEA at last, obtain being used for the raw material gel of hydrothermal crystallizing.
With the reaction mixture polytetrafluoroethyllining lining of packing into, and be packaged in stainless steel hydro-thermal still, 200 ℃ with autogenous pressure under, rotated crystallization 80 hours.Then with crystallization product multiple times of filtration, washing and 100 ℃ of oven dry, then in retort furnace, be warming up to 600 ℃ and constant temperature 4 hours, in moisture eliminator, naturally cool to room temperature then and promptly get molecular screen primary powder product.
Get the above-mentioned molecular screen primary powder of part and do nitrogen absorption test.There is not tangible hysteresis loop between its nitrogen adsorption isothermal line and the desorption isotherm, explains that the SAPO-34 molecular sieve of novel batching mode preparation and the SAPO-34 molecular sieve that the traditional proportioning mode prepares all do not contain meso-hole structure.
Getting molecular screen primary powder after the roasting does and presses mercury to measure; The pore passage structure of decidable 1000～1300nm should be particle and gap between particles duct; And tangible duct volume is arranged in the interval of 50～500nm, and should be the duct volume of granule interior, it is 5% that the pore volume of macropore accounts for the cubes ratio.
Embodiment 6
Raw material type is identical with embodiment 1, and proportioning raw materials is pressed H according to water, aluminium source, phosphorus source, silicon source and organic formwork agent
2O: Al
2O
3: P
2O
5: SiO
2: the chemical formula meter of organic formwork agent, H
2O: Al
2O
3: P
2O
5: SiO
2: TEA=30: 1: 0.2: 0.05: 10 (mol ratios).Earlier a part of water (a1) in the raw material and pseudo-boehmite are mixed fully, obtain uniform solution A, its molar ratio is H
2O: Al
2O
3=27: 1; Water (a2) with remainder in the raw material mixes with phosphoric acid, silicon sol fully simultaneously, obtains uniform solution B, and its molar ratio is H
2O: P
2O
5: SiO
2=3: 0.2: 0.05, the mol ratio a1/a2=9 of two portions water.Under stirring condition, solution A and solution B are mixed fully then, obtain the gel C of homogeneous.Under stirring condition, in gel C, add organic formwork agent TEA at last, obtain being used for the raw material gel of hydrothermal crystallizing.
With reaction mixture under room temperature, agitation condition, ageing 72 hours, the polytetrafluoroethyllining lining of packing into then, and be packaged in stainless steel hydro-thermal still, 200 ℃ with autogenous pressure under, rotated crystallization 4 hours.Then with crystallization product multiple times of filtration, washing and 100 ℃ of oven dry, then in retort furnace, be warming up to 600 ℃ and constant temperature 4 hours, in moisture eliminator, naturally cool to room temperature then and promptly get molecular screen primary powder product.
Get the above-mentioned molecular screen primary powder of part and do nitrogen absorption test.There is not tangible hysteresis loop between its nitrogen adsorption isothermal line and the desorption isotherm, explains that the SAPO-34 molecular sieve of novel batching mode preparation and the SAPO-34 molecular sieve that the traditional proportioning mode prepares all do not contain meso-hole structure.
Getting molecular screen primary powder after the roasting does and presses mercury to measure; The pore passage structure of decidable 1000～1300nm should be particle and gap between particles duct; And tangible duct volume is arranged in the interval of 50～500nm, and should be the duct volume of granule interior, it is 60% that the pore volume of macropore accounts for the cubes ratio.
Comparative Examples
With phosphoric acid (85wt%H
3PO
4, down with) be the phosphorus source, with hydrated aluminum oxide (be pseudo-boehmite, 70wt%Al
2O
3, down together) and be the aluminium source, with silicon sol (30wt%SiO
2, down with) be the silicon source, with triethylamine (TEA, chemically pure reagent, down with) be organic formwork agent.With raw material according to H
2O: Al
2O
3: P
2O
5: SiO
2: TEA=50: 1: 1.5: 2: 3 molar ratio adds one by one, fully mixes, and obtains the raw material gel.
The raw material gel is encapsulated in the polytetrafluoroethyllining lining, is sealed in stainless steel hydro-thermal still then, 200 ℃ with the following rotation crystallization 30 hours of autogenous pressure.Then with crystallization product multiple times of filtration, washing and under 80～100 ℃ of conditions, dry, then in retort furnace, be warming up to 600 ℃ of also constant temperature 4 hours, in moisture eliminator, naturally cool to room temperature then and promptly obtain the molecular screen primary powder product.
Get the above-mentioned molecular screen primary powder of part and do XRD determining, its presentation of results synthetic molecular sieve is SAPO-34 (CHA)/SAPO-18 (AEI) intergrowth phase crystal, shown in Fig. 2 intermediate curve (mixed crystal phase SAPO-34 molecular sieve).
Get the above-mentioned molecular screen primary powder of part and do nitrogen absorption test, do not have hysteresis loop between its adsorption isothermal line and the desorption isotherm, explain that the SAPO-34 molecular sieve that the traditional proportioning mode prepares does not contain significantly mesoporous and macroporous structure.
The pattern of molecular sieve is as shown in Figure 5, is typical cubic granules, and its surface is very smooth regular, does not also have significantly mesoporous or macroporous structure, and this result is consistent with the conclusion that the nitrogen adsorption isothermal line obtains.
Get molecular screen primary powder after the roasting and do and press mercury to measure, its result shows that the SAPO-34 molecular sieve that the traditional proportioning mode prepares does not contain tangible macroporous structure, and observed appearance structure is consistent on this result and the pattern photo.
The catalytic performance test of embodiment 7 sieve particles
With the sample of Comparative Examples after the roasting and embodiment 1～6 respectively compression molding and be broken for 100～120 orders after, on micro fixed-bed reactor, carry out reaction evaluating.The evaluation test parameter is: the molecular sieve loading amount is about 0.03g, and reactant is a methyl alcohol, and the reactant air speed is about 6.0/h, and carrier gas is an argon gas, and carrier gas flux is 14sccm, and temperature of reaction is 400 ℃.Reaction product is analyzed by gas chromatograph, wherein C
2～C
4Alkene is title product.The reaction evaluating result is as shown in table 1.
The diffusion test of embodiment 8 sieve particles
The sample of Comparative Examples after the roasting and embodiment 1～6 is carried out the mensuration of spread coefficient respectively.The evaluation test parameter is: 100 ℃ of adsorption temps, adsorbed gas are propane (dividing potential drop 10%), and carrier gas is an argon gas, total flux 100sccm, and the flowing chromatogram method is adopted in the acquisition of spread coefficient.
It is as shown in table 1 that spread coefficient is measured the result.
Can find out from the data of table 1; Compare with the conventional SAPO molecular sieve of Comparative Examples; The spread coefficient that contains the SAPO molecular sieve (under identical carbon deposition quantity) that enriches macroporous structure provided by the invention is bigger, and the internal diffusion influence that has reduced effectively in the sieve particle is described; Has longer catalytic life, lower alkane selectivity (wherein the propane selectivity significantly descends) and higher propylene selectivity.Owing to propylene/ethylene ratio in the catalytic process of the SAPO molecular sieve that contains macroporous structure is higher, therefore more be applicable to MTP (preparing propylene from methanol) process than conventional SAPO molecular sieve.
The molecular sieve that will have macroporous structure is processed the granules of catalyst that can be used for fluidized-bed reactor through traditional spray granulation, is used for alcohol ether system olefin hydrocarbon and can obtains good catalytic activity and propylene selectivity.
Table 1. embodiment 1 and the reactivity worth of Comparative Examples 1 and the contrast of spread coefficient
* catalytic life: be defined as methanol conversion and be reduced to moment of 80%.
Claims (15)
1. an aluminium silicophosphate molecular sieve particle is characterized in that, particle has the dual pore passage structure of small pore molecular sieve crystalline structure and through-type macropore simultaneously, and the ratio that the pore volume of macropore accounts for the cube particle volume is 5%～60%.
2. sieve particle as claimed in claim 1; It is characterized in that; Said particle is six cubess, and a pair of two relative faces are distributed with macropore in six faces of particulate, and other four faces are four right-angle triangles by the diagonal division on the face separately; In four right-angle triangles wherein two trilaterals of a pair of mutual vertical angles be distributed with macropore, the macropore that does not have macropore on the gore of two other mutual vertical angles or not have to lead directly to.
3. sieve particle as claimed in claim 1 is characterized in that, the aperture of said macropore is 50～500nm, and the ratio that the macropore pore volume accounts for the cube particle volume is 10%～40%.
4. sieve particle as claimed in claim 1 is characterized in that, said small pore molecular sieve crystalline structure is the crystalline structure of CHA type structure SAPO-34 and AEI type structure SAPO-18 intergrowth.
5. sieve particle as claimed in claim 4 is characterized in that, the mass ratio of CHA and two kinds of crystalline structure of AEI is the CHA N-type waferN in the crystalline structure of said intergrowth: AEI N-type waferN=1.0～10.0: 1.0.
6. a method for preparing the described sieve particle of claim 1～5 is characterized in that, may further comprise the steps:
1) water, aluminium source, phosphorus source, silicon source and organic formwork agent are mixed, wherein, water, aluminium source, phosphorus source, silicon source and organic formwork agent are pressed H
2O: Al
2O
3: P
2O
5: SiO
2: organic formwork agent meter, its mol ratio are 30～200: 1: 0.1～2.5: 0.01～1.0: 0.1～10;
With described moisture is two portions, and first part's water mixes with the aluminium source, forms water solution A, and second section water mixes with phosphorus source, silicon source, forms aqueous solution B; Water solution A is mixed the formation gel C with aqueous solution B; Gel C is mixed with organic formwork agent and is obtained the raw material gel, under 15～100 ℃ of conditions, carries out ageing, and digestion time is 0～72 hour;
2) with the mixture after the ageing 150～200 ℃ of following crystallization 4～100 hours, the gained solid matter is a product.
7. preparation method as claimed in claim 6 is characterized in that, said water, aluminium source, phosphorus source, silicon source and organic formwork agent are pressed H
2O: Al
2O
3: P
2O
5: SiO
2: organic formwork agent meter, its mol ratio are 50～180: 1: 0.2～2.0: 0.05～0.9: 0.5～8.
8. preparation method as claimed in claim 7 is characterized in that, said water, aluminium source, phosphorus source, silicon source and organic formwork agent are pressed H
2O: Al
2O
3: P
2O
5: SiO
2: organic formwork agent meter, its mol ratio are 70～160: 1: 0.4～1.5: 0.1～0.3: 1.0～5.
9. like the arbitrary described preparation method of claim 6～8, it is characterized in that the mol ratio of said first part water and second section water is 0.1～10, is preferably 0.5～6.
10. like the arbitrary described preparation method of claim 6～8, it is characterized in that said aluminium source is one or more the mixture in hydrated aluminum oxide, aluminum isopropylate and the phosphagel phosphaljel; Said silicon source is one or more mixtures of silicon sol, active silica, tetraethoxy or solid silicone; Said phosphorus source is one or more mixtures of phosphoric acid, Hypophosporous Acid, 50, phosphoric acid salt and Organophosphorous compounds; Said organic formwork agent is one or more mixtures of diethylamine, triethylamine, morphine quinoline and tetraethyl-oxyammonia.
11. preparation method as claimed in claim 10 is characterized in that, said aluminium source is a pseudo-boehmite, and said phosphorus source is a phosphoric acid, and said silicon source is silicon sol or tetraethoxy, and said organic formwork agent is a triethylamine.
12., it is characterized in that said ageing is under condition of normal pressure like the arbitrary described preparation method of claim 6～8, the ageing temperature is 15～30 ℃, aged process is dynamic.
13. like the arbitrary described preparation method of claim 6～8, it is characterized in that said crystallization is carried out under airtight hydrothermal condition, the pressure that the pressure during crystallization comes reaction mixture to produce, the process of crystallization is dynamic.
14. comprise the catalyzer of the said sieve particle of claim 1～5.
15. the application of the described catalyzer of claim 14 in preparation alkene.
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| CN106564912A (en) * | 2015-10-10 | 2017-04-19 | 神华集团有限责任公司 | Double-micropore SAPO (silicoaluminophosphate)-34/SAPO-18 composite molecular sieve, and preparation method and application thereof |
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| CN110357124A (en) * | 2018-04-09 | 2019-10-22 | 国家能源投资集团有限责任公司 | Multi-stage porous SAPO-34/SAPO-18 hands over interpromoting relation in five elements phase molecule sieve and preparation method and application |
| CN111320186A (en) * | 2018-12-13 | 2020-06-23 | 国家能源投资集团有限责任公司 | SAPO-34 molecular sieve, and preparation method and application thereof |
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