CN113493212B - SAPO-34 molecular sieve, and preparation method and application thereof - Google Patents
SAPO-34 molecular sieve, and preparation method and application thereof Download PDFInfo
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- 239000002808 molecular sieve Substances 0.000 title claims abstract description 135
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 135
- 238000002360 preparation method Methods 0.000 title abstract description 25
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 61
- 238000002425 crystallisation Methods 0.000 claims abstract description 33
- 230000008025 crystallization Effects 0.000 claims abstract description 33
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 31
- 239000002135 nanosheet Substances 0.000 claims abstract description 27
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 25
- 239000010703 silicon Substances 0.000 claims abstract description 25
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 24
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 24
- 239000011574 phosphorus Substances 0.000 claims abstract description 24
- 239000000203 mixture Substances 0.000 claims abstract description 23
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical group CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 108
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 36
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 16
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 10
- 150000001336 alkenes Chemical class 0.000 claims description 10
- 239000002994 raw material Substances 0.000 claims description 10
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 9
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical group [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 9
- 239000011148 porous material Substances 0.000 claims description 9
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 8
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 7
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 2
- 239000006229 carbon black Substances 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 8
- 238000001035 drying Methods 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 17
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 12
- 238000005406 washing Methods 0.000 description 12
- 238000002441 X-ray diffraction Methods 0.000 description 10
- 238000001816 cooling Methods 0.000 description 9
- 239000002149 hierarchical pore Substances 0.000 description 9
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 238000001228 spectrum Methods 0.000 description 7
- 241000269350 Anura Species 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 238000001878 scanning electron micrograph Methods 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- SGRHVVLXEBNBDV-UHFFFAOYSA-N 1,6-dibromohexane Chemical compound BrCCCCCCBr SGRHVVLXEBNBDV-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 150000001993 dienes Chemical class 0.000 description 3
- 125000005843 halogen group Chemical group 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000004417 polycarbonate Substances 0.000 description 2
- 229920000515 polycarbonate Polymers 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 239000011345 viscous material Substances 0.000 description 2
- ULTHEAFYOOPTTB-UHFFFAOYSA-N 1,4-dibromobutane Chemical compound BrCCCCBr ULTHEAFYOOPTTB-UHFFFAOYSA-N 0.000 description 1
- DKEGCUDAFWNSSO-UHFFFAOYSA-N 1,8-dibromooctane Chemical compound BrCCCCCCCCBr DKEGCUDAFWNSSO-UHFFFAOYSA-N 0.000 description 1
- 241000045365 Microporus <basidiomycete fungus> Species 0.000 description 1
- 229910004283 SiO 4 Inorganic materials 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000011852 carbon nanoparticle Substances 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- PFKRTWCFCOUBHS-UHFFFAOYSA-N dimethyl(octadecyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[NH+](C)C PFKRTWCFCOUBHS-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000031068 symbiosis, encompassing mutualism through parasitism Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
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- C01B37/00—Compounds having molecular sieve properties but not having base-exchange properties
- C01B37/06—Aluminophosphates containing other elements, e.g. metals, boron
- C01B37/08—Silicoaluminophosphates [SAPO compounds], e.g. CoSAPO
-
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/82—Phosphates
- B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
- B01J29/85—Silicoaluminophosphates [SAPO compounds]
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- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/54—Phosphates, e.g. APO or SAPO compounds
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Abstract
The invention discloses an SAPO-34 molecular sieve and a preparation method thereof. The preparation method of the SAPO-34 molecular sieve comprises the following steps: and (2) crystallizing a mixture of an aluminum source, a phosphorus source, a structure directing agent, a silicon source, water and an auxiliary structure directing agent, wherein the crystallization adopts dynamic crystallization. The SAPO-34 molecular sieve is a nano sheet with convex outer surfaces, is novel in shape, and can obtain a good catalytic effect when being used for a methanol-to-olefin reaction.
Description
Technical Field
The invention relates to an SAPO-34 molecular sieve, a preparation method thereof and application of the SAPO-34 molecular sieve in preparation of olefin from methanol.
Background
SAPO molecular sieves, which are silicoaluminophosphate molecular sieves with pore sizes around 0.4nm, were invented by United states Union carbide (UCC). The SAPO molecular sieve is made of AlO 4 、SiO 4 And PO 4 The three-dimensional crystal structure of the tetrahedron formed by sharing oxygen atoms, in the pore channel in the crystal, si 4+ Partially substituted P 5+ Or Al 3+ Producing acidity. SAPO series molecular sieves have good thermal stability and hydrothermal stability, moderate acidity, higher specific surface area and highly ordered microporous pores, and are widely applied to the modern petroleum processing industry. The most interesting is SAPO-34 molecular sieves, which show very good catalytic performance in Methanol To Olefins (MTO) reactions: the conversion rate of the methanol reaches 100 percent; the selectivity of ethylene and propylene can exceed 70 percent; c 5 + The content of the components is small and almost no aromatic hydrocarbon is generated. However, the SAPO-34 molecular sieve pore size is 0.38nm, is an eight-membered ring pore, presents a serious shape-selective limitation, on one hand, prevents the contact of raw material molecules with active centers inside the pore, on the other hand, can limit the diffusion and mass transfer of reactants, intermediate transition products and final products, and is very easy to cause the pore to be blocked due to carbon deposition, so that the catalyst is inactivated, and the exertion of the catalytic performance is limited.
Heretofore, methods for hydrothermally synthesizing a hierarchical pore silicoaluminophosphate molecular sieve can be classified into a post-treatment method, a hard template method and a soft template method. SAPO-34 molecular sieves are more stringent for the conditions of the post-treatment process because the silicoaluminophosphate molecular sieves are less stable than silicoaluminophosphate molecular sieves, require precise control of conditions for the removal of aluminum or silicon atoms with acids or bases (Jianwei Zhong, yingxu Wei, chunshan Song and Zhongmin Liu, catal. Sci. Technol.,2017,7,4905-4923), and the post-treatment process results in substantial loss of the molecular sieve crystal structure, destroying the crystal structure and the acidity and basicity of the molecular sieve (X.Chen, A.Vicente, Z.Qin, V.Ruaux, J.P.Gilson and V.Valtchev, chem.Commun.,2016,52, 3512-3515.). Kaskaske et al (f.schmidt, s.paasch, e.brunner and s.kaskaske, microporus mesoporus materoporus mater, 2012,164, 214-221.) during the synthesis of SAPO-34 molecular sieves, add carbon materials (carbon nanotubes and carbon nanoparticles) to eventually form mesopores in the large SAPO-34 molecular sieve particles, either embedded within the molecular sieve crystals or throughout the entire crystal particle. The method for synthesizing the hierarchical pore SAPO-34 molecular sieve by using the carbon material as the hard template in a guiding manner has the disadvantages that the synthesis steps are relatively complicated, the hard template needs to be synthesized firstly, and the hard template needs to be removed by means of burning and the like after the hierarchical pore molecular sieve is synthesized. Danilina, chen Lu and the like (Chen Lu, wang Runwei, ding Shuang and the like, advanced school chemistry report 2010 31 (9): 1693-1696.) respectively hydrothermally synthesize the SAPO-34 molecular sieve with the multi-stage pore structure by taking multifunctional long-chain organosilicon as a silicon source; liu Zhongmin, et al (J. Mater. Chem. A,2015,3,5608-5616) oriented synthesis of spherical SAPO-34 molecular sieve formed by lamellar stacking with [3- (trimethyoxyslyl) propyl ] octadecyldimethylammonium chloride (TPOAC) as surfactant; cui et al (Cui Y, zhang Q, he J, et al, morphology, 2013 (4): 468-474) synthesize SAPO-34 molecular sieve with hierarchical pore structure under hydrothermal condition by using polyethylene glycol (PEG) as mesoporous template, and the size of mesopores can be changed by adjusting the amount of PEG.
In summary, although the preparation of the hierarchical pore material is a hot spot of research by researchers at present, the morphology of the existing preparation of the hierarchical pore SAPO-34 molecular sieve is still similar to a cube. Liu Zhongmin and the like synthesize the lamellar-stacked spherical SAPO-34 molecular sieve by using TPOAC as a surfactant, but the cost of TPOAC is high, so that the development of a preparation route for synthesizing SAPO-34 molecular sieves with other morphologies has important practical significance.
Disclosure of Invention
Aiming at the problem that the shape of the SAPO-34 molecular sieve with the hierarchical pore structure synthesized by the prior art is mostly a tetragonal body with smooth surface, the invention provides the SAPO-34 molecular sieve with novel shape and a preparation method thereof. The invention also provides application of the SAPO-34 molecular sieve in a reaction for preparing olefin from methanol. The SAPO-34 molecular sieve can obtain good catalytic effect when used for preparing olefin from methanol.
The invention provides a SAPO-34 molecular sieve, wherein the SAPO-34 molecular sieve is a nanosheet with bulges distributed on the outer surface, and the size of the nanosheet is 500 nm-3 mu m.
Further, the SAPO-34 molecular sieve nanosheets are hexagonal or hexagon-like.
Further, the thickness of the SAPO-34 nanosheet layer is 80-300 nm. Wherein the thickness of the nanosheet is calculated as being free of raised portions.
Furthermore, the protrusions on the outer surface of the SAPO-34 molecular sieve are preferably pyramid-shaped, and further triangular pyramid-shaped.
Further, the edges of the outer surface of the SAPO-34 molecular sieve are relatively flat.
Furthermore, macropores exist in the SAPO-34 molecular sieve nanosheet, and the diameter of each macropore is 100-400 nm.
Further, the SAPO-34 molecular sieve is present either in a monodisperse state or in an aggregate state.
Further, when the SAPO-34 molecular sieve exists in an aggregate state, all nano sheet layers are in cross symbiosis, the appearance is flower-shaped, and the particle size is 1-5 mu m.
The second aspect of the invention provides a preparation method of a SAPO-34 molecular sieve, which comprises the following steps: crystallizing a mixture of an aluminum source, a phosphorus source, a structure directing agent, a silicon source, water and an auxiliary structure directing agent; the molecular formula of the assistant structure directing agent is as follows:
wherein X is Cl - 、Br - Or I - ；
The crystallization adopts dynamic crystallization.
Further, the structure directing agent is Triethylamine (TEA).
Furthermore, the auxiliary structure directing agent is obtained by the reaction of triethylamine and straight-chain alkane with 6 carbon atoms and two halogen atoms at two ends.
Further, the preparation method of the structure-directing agent can comprise the following steps: triethylamine and linear alkane of which the number of carbon atoms is 6 and both ends of which are respectively provided with a halogen atom are added into an organic solvent (such as acetonitrile), wherein the ratio of triethylamine: a linear alkane having 6 carbon atoms each having one halogen atom at both ends: the molar ratio of the organic solvent is (4-10): 1: (50-100) refluxing for 6-12 hours at 75-90 ℃; cooling the mixture, and removing the organic solvent to obtain a viscous substance; washing and drying the sticky matter to obtain the auxiliary structure guiding agent; wherein, the drying conditions are as follows: drying for 1-5 hours at 20-50 ℃.
Further, the aluminum source is pseudoboehmite. The silicon source is one or a mixture of more of silica sol, white carbon black and tetraethyl orthosilicate. The phosphorus source is phosphoric acid.
Further, in the mixture of the aluminum source, the phosphorus source, the structure directing agent, the silicon source, the water and the structure assisting directing agent, the aluminum source is Al 2 O 3 In terms of phosphorus source H 3 PO 4 The silicon source is SiO 2 Based on the raw material ratio, namely Al 2 O 3 ：H 3 PO 4 : structure-assisting directing agent: structure directing agent: siO 2 2 ：H 2 The molar ratio of O is (0.7-1.3): (1.4-3.0): (0.4-0.8): (2-5): (0.2-0.9): (40-80).
Further, the crystallization conditions were as follows: the first stage is as follows: the crystallization temperature is 150-220 ℃, and the crystallization time is 15-30 hours; and a second stage: the crystallization temperature is 90-140 ℃, and the crystallization time is 5-20 hours.
Further, the dynamic crystallization is carried out under the condition of stirring, wherein the rotating speed is 5-50 r/min.
Further, the crystallization may be followed by conventional post-treatment steps such as separation, washing and drying, wherein the separation, washing and drying may be carried out by conventional methods such as centrifugation, washing may be carried out with deionized water, and drying may be carried out in an oven. For example, the drying conditions are: drying for 2-12 hours at 20-120 ℃.
The SAPO-34 molecular sieve can be used in the fields of catalysis, adsorption, separation and the like.
The third aspect of the invention provides an application of the SAPO-34 molecular sieve in a methanol-to-olefin reaction.
Further, the reaction conditions of the methanol-to-olefin reaction are as follows: the reaction pressure is normal pressure to 1.0MPa, the reaction temperature is 390 to 515 ℃, and the methanol feeding weight space velocity is 1 to 100 hours -1 。
The SAPO-34 molecular sieve is different from the conventional cube-like morphology, and the outer surface is distributed with raised nano-sheets, so that the morphology is favorable for increasing the specific surface area and reducing the reactant transmission path, thereby improving the catalytic activity and the stability. The SAPO-34 molecular sieve is used in the reaction of preparing olefin from methanol, and the yield of ethylene and propylene can reach more than 85 percent under the condition of prolonging the reaction time.
The preparation method of the SAPO-34 molecular sieve adopts the structure-assisting directing agent and combines a specific dynamic crystallization process, so as to obtain the SAPO-34 molecular sieve nanosheet with novel appearance. The SAPO-34 of the invention has the advantages of simple preparation method, easy obtaining of the structure directing agent, simple structure of the structure-assisted directing agent, low cost and low requirement on equipment for molecular sieve synthesis, thus the invention has good industrial application prospect.
Drawings
FIG. 1 is an XRD pattern of a SAPO molecular sieve obtained in example 1 of the invention;
FIG. 2 is an SEM image of a SAPO-34 molecular sieve obtained in example 1 of the invention; wherein the left part is the overall appearance of the molecular sieve, and the right part is a local enlarged view;
FIG. 3 is a TEM image of SAPO-34 molecular sieve obtained in example 1 of the invention; wherein the left part is the overall appearance of the molecular sieve, and the right part is a local enlarged view;
FIG. 4 is an XRD pattern of a SAPO molecular sieve obtained in example 2 of the invention;
FIG. 5 is an SEM image of a SAPO-34 molecular sieve obtained in example 2 of the invention; wherein the left is the overall appearance of the molecular sieve, and the right is a local enlarged view;
FIG. 6 is an XRD pattern of SAPO molecular sieve obtained in example 3 of the invention;
FIG. 7 is an SEM picture of a SAPO-34 molecular sieve obtained in example 3 of the invention; wherein the left is the overall appearance of the molecular sieve, and the right is a local enlarged view;
FIG. 8 is an XRD pattern of a SAPO-34 molecular sieve obtained according to comparative example 1 of the invention;
FIG. 9 is an SEM image of a SAPO-34 molecular sieve obtained according to comparative example 1 of the invention; wherein the left is the overall appearance of the molecular sieve, and the right is a local enlarged view;
FIG. 10 is an XRD pattern of a SAPO-34 molecular sieve obtained according to comparative example 2 of the invention;
FIG. 11 is an SEM image of a SAPO-34 molecular sieve obtained according to comparative example 2 of the invention;
FIG. 12 is an XRD pattern of a SAPO-34 molecular sieve obtained according to comparative example 3 of the invention;
FIG. 13 is an SEM image of a SAPO-34 molecular sieve obtained according to comparative example 3 of the invention; wherein the left part is the overall appearance of the molecular sieve, and the right part is a local enlarged view;
FIG. 14 is an XRD pattern of a SAPO-34 molecular sieve, obtained according to comparative example 4 of the invention;
FIG. 15 is an SEM image of a SAPO-34 molecular sieve obtained according to comparative example 4 of the invention; the left is the overall appearance of the molecular sieve, and the right is a local enlarged view.
Detailed Description
In the present invention, the XRD data was measured with a german bruker AXS D8 Advance type X-ray diffractometer under the test conditions of Cu ka radiation (40kv, 40ma,
) The test step size is 0.02, the step time is 12.6s, and the test 2 theta range is 5-50 degrees.
In the present invention, SEM pictures were obtained from HITACHI S4800 field emission scanning electron microscope (FISEM) under 3kV and at 10. Mu.A.
In the present invention, TEM data is obtained by using a JEM-2100 type transmission electron microscope of JEOL, japan, under the following conditions: a voltage of 200kV and a current of 105 μ A (Cs 1.0mm, point resolution of
)。
The present invention will be further described with reference to the following examples, which are not intended to limit the scope of the present invention.
[ example 1 ]
(1) Preparing a structure-assisting directing agent:
adding triethylamine and 1,6-dibromohexane to acetonitrile, and refluxing at 84 ℃ for 8 hours; triethylamine: 1,6-dibromohexane: acetonitrile (molar ratio) =8:1:80; cooling the mixture, and removing a large amount of acetonitrile to obtain a viscous substance; washing and drying the sticky matter to obtain the auxiliary structure directing agent; wherein the drying conditions are as follows: drying was carried out at 30 ℃ for 2 hours.
The molecular formula of the prepared auxiliary structure directing agent is as follows:
(2) Preparation of SAPO-34 molecular sieve
With silica sol (40% by weight SiO) 2 ) Pseudo-boehmite (70 wt% Al) 2 O 3 ) And phosphoric acid (85 wt% H) 3 PO 4 ) Respectively as a silicon source, an aluminum source and a phosphorus source, triethylamine TEA as a structure directing agent, adding the silicon source, the aluminum source, the phosphorus source, the triethylamine TEA and the structure directing agent into water for mixing, wherein the mixture ratio of the raw materials is Al 2 O 3 ：H 3 PO 4 : structure-assisting directing agent: structure directing agent: siO 2 2 ：H 2 The molar ratio of O is 1.0:2.0: 0.5:3.0:0.38:57. the mixture is crystallized by rotation at 200 ℃ for 24 hours at a rotation speed of 20 rpm, then the temperature is reduced to 120 ℃, and the crystallization is continued for 10 hours. And after crystallization is finished, cooling, centrifuging and washing the crystallized product, and drying for 6 hours at 100 ℃ to obtain the SAPO-34 molecular sieve.
The XRD spectrum of the sample is shown in figure 1, and as can be seen from figure 1, the synthesized molecular sieve has the characteristic diffraction peaks of the SAPO-34 molecular sieve, and the diffraction peaks appear at 9.5 degrees, 15.9 degrees, 20.5 degrees, 26 degrees and 31 degrees of 2 theta, which indicates that the synthesized product is the pure SAPO-34 molecular sieve.
As shown in figure 2, the molecular sieve is a nano-sheet with bulges distributed on the outer surface, mainly exists in a nano-sheet aggregate state, is in a flower-shaped structure, has the thickness of 80-300 nm, and has smooth edges and pyramid-shaped bulges distributed in the middle part.
As shown in FIG. 3, the nano-sheet of the molecular sieve is hexagonal, and macropores exist in the middle of the sheet layer, and the diameter of the macropores is 100-400 nm.
As shown in Table 1, the WHSV was 2.4h -1 And under the reaction condition of 460 ℃, the molecular sieve in the embodiment 1 is adopted to carry out the reaction of preparing olefin from methanol, the yield of the diene can reach 85.05 percent, and a good catalytic effect is shown.
[ example 2 ] A method for producing a polycarbonate
(1) Preparation of structure-assisting directing agent
The same as in example 1.
(2) Preparation of SAPO-34 molecular sieve:
with silica sol (40% by weight SiO) 2 ) Pseudo-boehmite (70 wt% Al) 2 O 3 ) And phosphoric acid (85 wt% H) 3 PO 4 ) Respectively as a silicon source, an aluminum source and a phosphorus source, triethylamine TEA as a structure directing agent, adding the silicon source, the aluminum source, the phosphorus source, the triethylamine TEA and the structure directing agent into water for mixing, wherein the mixture ratio of the raw materials is Al 2 O 3 ：H 3 PO 4 : structure-assisting directing agent: structure directing agent: siO 2 2 ：H 2 The molar ratio of O is 1.0:2.0: 0.5:3.0:0.38:74. the mixture is crystallized by rotation at 200 ℃ for 24 hours at a rotation speed of 20 rpm, then the temperature is reduced to 120 ℃, and the crystallization is continued for 10 hours. And after crystallization is finished, cooling, centrifuging and washing the crystallized product, and drying for 6 hours at 100 ℃ to obtain the SAPO-34 molecular sieve.
The XRD spectrum of the sample is shown in FIG. 4, and it can be seen from FIG. 4 that the synthesized molecular sieve has the characteristic diffraction peaks of the SAPO-34 molecular sieve, and the diffraction peaks appear at 9.5 degrees, 15.9 degrees, 20.5 degrees, 26 degrees and 31 degrees of 2 theta, which indicates that the synthesized product is the pure SAPO-34 molecular sieve.
As shown in FIG. 5, the molecular sieve is a nano-sheet with convex protrusions distributed on the outer surface, the thickness of the nano-sheet layer is 80-300 nm, and the nano-sheet layer mainly exists in a nano-sheet aggregate state and is in a flower-shaped structure. And the edge part of the nano sheet is smoother, and the middle part is distributed with pyramid-shaped bulges.
[ example 3 ] A method for producing a polycarbonate
(1) Preparation of structure-assisting directing agent
The same as in example 1.
(2) Preparation of SAPO-34 molecular sieve:
with silica sol (40% by weight SiO) 2 ) Pseudo-boehmite (70 wt% Al) 2 O 3 ) And phosphoric acid (85 wt% H) 3 PO 4 ) Respectively as silicon source, aluminum source and phosphorus source, triethylamine TEA as structure directing agent, adding the silicon source, aluminum source, phosphorus source, triethylamine TEA and structure directing agent into water, mixing, the mixture ratio of each raw material being Al 2 O 3 ：H 3 PO 4 : structure-assisting directing agent: structure directing agent: siO 2 2 ：H 2 The molar ratio of O is 1.0:2.0: 0.5:3.0:0.25:57. the mixture is rotated and crystallized for 24 hours at 200 ℃ and the rotating speed of 20 r/min, then the temperature is reduced to 120 ℃, and the rotation and crystallization are continued for 10 hours. And after crystallization is finished, cooling, centrifuging and washing the crystallized product, and drying for 6 hours at 100 ℃ to obtain the SAPO-34 molecular sieve.
The XRD spectrum of the sample is shown in FIG. 6, and it can be seen from FIG. 6 that the synthesized molecular sieve has the characteristic diffraction peaks of the SAPO-34 molecular sieve, and the diffraction peaks appear at 9.5 degrees, 15.9 degrees, 20.5 degrees, 26 degrees and 31 degrees of 2 theta, which indicates that the synthesized product is the pure SAPO-34 molecular sieve.
As shown in FIG. 7, the molecular sieve is a nano-sheet with convex protrusions distributed on the outer surface, mainly exists in a nano-sheet aggregate state, is in a flower-shaped structure, and has smooth edge parts and pyramid-shaped protrusions distributed in the middle part. The thickness of the nano-sheet layer is 100-300 nm.
Comparative example 1
With silica sol (40% by weight SiO) 2 ) Pseudo-boehmite (70 wt% Al) 2 O 3 ) And phosphoric acid (a)85. Weight% H 3 PO 4 ) Respectively as a silicon source, an aluminum source and a phosphorus source, triethylamine TEA is used as a structure directing agent, the silicon source, the aluminum source, the phosphorus source and the triethylamine TEA are added into water to be mixed, and the mixture ratio of the raw materials is Al 2 O 3 ：H 3 PO 4 : structure directing agent: siO 2 2 ：H 2 The molar ratio of O is 1.0:2.0:3.0:0.38:57. the mixture is crystallized by rotation at 200 ℃ for 24 hours at a rotation speed of 20 rpm, then the temperature is reduced to 120 ℃, and the crystallization is continued for 10 hours. And after crystallization is finished, cooling, centrifuging and washing the crystallized product, and drying for 6 hours at 100 ℃ to obtain the SAPO-34 molecular sieve.
The XRD spectrum of the sample is shown in FIG. 8, and it can be seen from FIG. 8 that the synthesized molecular sieve has the characteristic diffraction peaks of SAPO-34 molecular sieve, and the diffraction peaks appear at 9.5 degrees, 15.9 degrees, 20.5 degrees, 26 degrees and 31 degrees of 2 theta, which indicates that the synthesized product is pure SAPO-34 molecular sieve.
As shown in fig. 9, when no structure-directing agent is added, the directed synthesis is a similar cubic morphology, which is the characteristic morphology of the SAPO-34 molecular sieve, i.e., the morphology of the conventional SAPO-34 molecular sieve, and the existence of hierarchical pores is not observed through the magnified scanning picture, and the surface is very smooth.
The molecular sieve of comparative example 1 was used in a methanol to olefins reaction under the same evaluation conditions as in example 1; comparative example 1 the diene yield was 81.62% under the same reaction conditions and the reaction life of the comparative example was shorter than that of example 1; therefore, the catalytic effect of the catalyst in example 1 is obviously better than that of the catalyst in comparative example 1, and the SAPO-34 synthesized by the method disclosed by the invention is proved to be novel in morphology and structure, and capable of improving the diene yield in the reaction of preparing olefin from methanol and prolonging the service life of the catalyst. See table 1 for specific catalytic performance results.
Comparative example 2
(1) Preparation of structure-assisting directing agent
The procedure is as in example 1 except that 1,6-dibromohexane is replaced by 1,4-dibromobutane.
(2) Preparation of the molecular sieve:
with silica sol (40% by weight SiO) 2 ) Pseudo-boehmite (70 wt% Al) 2 O 3 ) And phosphoric acid (85 wt% H) 3 PO 4 ) Respectively as a silicon source, an aluminum source and a phosphorus source, triethylamine TEA as a structure directing agent, adding the silicon source, the aluminum source, the phosphorus source, the triethylamine TEA and the structure directing agent into water for mixing, wherein the mixture ratio of the raw materials is Al 2 O 3 ：H 3 PO 4 : structure-assisting directing agent: structure directing agent: siO 2 2 ：H 2 The molar ratio of O is 1.0:2.0: 0.5:3.0:0.38:57. the mixture is crystallized by rotation at 200 ℃ for 24 hours at a rotation speed of 20 rpm, then the temperature is reduced to 120 ℃, and the crystallization is continued for 10 hours. And after crystallization is finished, cooling, centrifuging and washing the crystallized product, and drying for 6 hours at 100 ℃ to obtain the molecular sieve.
The XRD spectrum of the sample is shown in FIG. 10, and it can be seen from FIG. 10 that the synthesized molecular sieve has the characteristic diffraction peaks of both SAPO-34 and SAPO-5 molecular sieves, the diffraction peaks of 2 theta at 9.5 degrees, 15.9 degrees, 20.5 degrees, 26 degrees and 31 degrees are attributed to SAPO-34, and the diffraction peaks of 2 theta at 7.4 degrees, 14.9 degrees, 19.7 degrees and 22.4 degrees are attributed to SAPO-5.
As shown in FIG. 11, the molecular sieve has both hexagonal prism type (typical morphology of SAPO-5 molecular sieve) and tetragonal-like type (typical morphology of SAPO-34 molecular sieve). And from both the scanning and XRD data, it can be seen that SAPO-5 is the predominant component in the product, and that the SAPO-5 particles are between 0.5 and 2 μm.
Comparative example 3
(1) Preparation of structure-assisting directing agent
The procedure is as in example 1 except that 1,6-dibromohexane is replaced by 1,8-dibromooctane.
(2) Preparation of the molecular sieve:
with silica sol (40% by weight SiO) 2 ) Pseudo-boehmite (70 wt% Al) 2 O 3 ) And phosphoric acid (85 wt% H) 3 PO 4 ) Respectively as a silicon source, an aluminum source and a phosphorus source, triethylamine TEA as a structure directing agent, adding the silicon source, the aluminum source, the phosphorus source, the triethylamine TEA and the structure directing agent into water for mixing, wherein the mixture ratio of the raw materials is Al 2 O 3 ：H 3 PO 4 : structure-assisting directing agent: structure directing agent: siO 2 2 ：H 2 The molar ratio of O is 1.0:2.0: 0.5:3.0:0.38:57. the mixture is crystallized by rotation at 200 ℃ for 24 hours at a rotation speed of 20 rpm, then the temperature is reduced to 120 ℃, and the crystallization is continued for 10 hours. And after crystallization is finished, cooling, centrifuging and washing the crystallized product, and drying for 6 hours at 100 ℃ to obtain the molecular sieve.
The XRD spectrum of the sample is shown in FIG. 12, and it can be seen from FIG. 12 that the synthesized molecular sieve has the characteristic diffraction peaks of both SAPO-34 and SAPO-5 molecular sieves, the diffraction peaks of 2 theta at 9.5 degrees, 15.9 degrees, 20.5 degrees, 26 degrees and 31 degrees are attributed to SAPO-34, and the diffraction peaks of 2 theta at 7.4 degrees, 14.9 degrees, 19.7 degrees and 22.4 degrees are attributed to SAPO-5.
As shown in FIG. 13, the molecular sieve has both hexagonal prism type (typical morphology of SAPO-5 molecular sieve) and tetragonal-like type (typical morphology of SAPO-34 molecular sieve). And from both the scanning image and XRD data, it can be seen that SAPO-34 is the major component in the product, and that the SAPO-34 particles are in the range of 2-8 μm.
Comparative example 4
(1) Preparation of structure-assisting directing agent
The same as in example 1.
(2) Preparation of SAPO-34 molecular sieve:
with silica sol (40% by weight SiO) 2 ) Pseudo-boehmite (70 wt% Al) 2 O 3 ) And phosphoric acid (85 wt% H) 3 PO 4 ) Respectively as a silicon source, an aluminum source and a phosphorus source, triethylamine TEA as a structure directing agent, adding the silicon source, the aluminum source, the phosphorus source, the triethylamine TEA and the structure directing agent into water for mixing, wherein the mixture ratio of the raw materials is Al 2 O 3 ：H 3 PO 4 : structure-assisting directing agent: structure directing agent: siO 2 2 ：H 2 The molar ratio of O is 1.0:2.0: 0.5:3.0:0.38:57. the mixture is statically crystallized at 200 ℃. And after crystallization is finished, cooling, centrifuging and washing the crystallized product, and drying for 6 hours at 100 ℃ to obtain the SAPO-34 molecular sieve.
The XRD spectrum of the sample is shown in figure 14, and the synthesized molecular sieve has the characteristic diffraction peaks of the SAPO-34 molecular sieve, and the diffraction peaks appearing at 9.5 degrees, 15.9 degrees, 20.5 degrees, 26 degrees and 31 degrees of 2 theta are attributed to the SAPO-34.
As shown in FIG. 15, the molecular sieve appearance is tetragonal-like (typical of SAPO-34 molecular sieve morphology), with SAPO-34 particles in the range of 2-8 μm. Hierarchical pores exist on the SAPO-34 type cube particles.
TABLE 1 catalysis results in methanol to olefins with example 1 and comparative example 1 samples
Note: in the present invention, the yield of each product is by mass.
Claims (13)
1. An SAPO-34 molecular sieve, wherein the SAPO-34 molecular sieve is a nano sheet with protrusions distributed on the outer surface, and the size of the nano sheet is 500nm to 3 mu m;
the bulges on the outer surface of the SAPO-34 molecular sieve are in a pyramid shape.
2. The molecular sieve of claim 1, wherein the SAPO-34 molecular sieve nanosheets are hexagonal or hexagonally-like.
3. The molecular sieve of claim 1, wherein the thickness of the SAPO-34 nanosheet is 80 to 300nm.
4. The molecular sieve of claim 1, wherein the edges of the exterior surface of the SAPO-34 molecular sieve are relatively flat with respect to the middle.
5. The molecular sieve of claim 1, wherein the SAPO-34 molecular sieve nanosheets have large pores with a diameter of 100 to 400nm.
6. The molecular sieve of any one of claims 1 to 5, wherein the SAPO-34 molecular sieve is present in either a monodisperse state or an aggregate state.
7. The molecular sieve of claim 6, wherein the SAPO-34 molecular sieve has an aggregate state in which nanosheets are cross-intergrown, has a flower-like appearance, and has a particle size of 1~5 μm.
8. The method for preparing a SAPO-34 molecular sieve of any one of claims 1 to 7, comprising: crystallizing a mixture of an aluminum source, a phosphorus source, a structure directing agent, a silicon source, water and an auxiliary structure directing agent; the molecular formula of the auxiliary structure directing agent is as follows:
wherein X is Cl - 、Br - Or I - ；
Wherein, the crystallization adopts dynamic crystallization.
9. The method of claim 8 wherein the aluminum source is pseudoboehmite; the silicon source is one or a mixture of more of silica sol, white carbon black and tetraethyl orthosilicate; the phosphorus source is phosphoric acid; the structure directing agent is triethylamine.
10. The method of claim 8, wherein the aluminum source is Al, the phosphorus source, the structure directing agent, the silicon source, the water, and the structure directing agent in a mixture comprising the aluminum source, the phosphorus source, the structure directing agent, the silicon source, the water, and the structure directing agent 2 O 3 In terms of phosphorus source H 3 PO 4 The silicon source is SiO 2 Based on the raw material ratio, namely Al 2 O 3 ：H 3 PO 4 : structure-assisting directing agent: structure directing agent: siO 2 2 ：H 2 The molar ratio of O is (0.7 to 1.3): (1.4 to 3.0): (0.4 to 0.8): (2~5): (0.2 to 0.9): (40 to 80).
11. The method of claim 8, wherein the crystallization conditions are as follows: the first stage is as follows: the crystallization temperature is 150 to 220 ℃, and the crystallization time is 15 to 30 hours; and a second stage: the crystallization temperature is 90 to 140 ℃, and the crystallization time is 5 to 20 hours.
12. The method according to claim 8 or 11, wherein the dynamic crystallization is carried out under stirring, wherein the rotation speed is 5 to 50 rpm.
13. Use of the SAPO-34 molecular sieve of any one of claims 1 to 7 in a methanol to olefin reaction.
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